/
Автор: Roeges N.P.G.
Теги: organic chemistry analytical chemistry spectroscopy structural analysis
ISBN: 0-471-93998-6
Год: 1994
Текст
А Guide to the Complete
Interpretation of Infrared
Spectra of Organic Structures
NОЁL Р. О. ROEGES
Katholickc Industriele Hogcschool О-У!
Campus Rabot, Gent, Bclgium
JOHN WILEY & SONS
Chiche5ter . New York . Brisbane . Toronto . Singapore
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Library 0/ COlIgress Cala/oging-in-РIlЬ/iсаtiоn Data
Rocges, Noel Р. О.
А guidc 10 (Ьс complctc intcrprclation of infrarcd spcclra of
organic structurcs I Nocl Р.О. Roegcs.
p
ст.
lncludcs bibIiographical rcfcrences and index.
ISBN 0
471
93998
6
1. Organic compounds.......spcctra
Handbooks, manua]s, etc.
2. Infrared spectroscopy
Handbooks, manuals, etc. 3. Chcmistry,
Organic
Handbooks, manuals, etc. 1. Тitlc.
QC462.85.R64 1994
547.04&------<1с20 94-2445
CIP
I
r
()
British Library Cala/ogиillg in P/lb/icatioll Dala
А calalogue rccord for this book is availabIe from (Ье British Library
ISBN 0471939986
Typeset in 10112pl Тimes from author's disks Ьу Production Tcchnology
Depanmenl, John Wiley & Sons Ltd, Chichester
Prinled and bound in Greal Brilain Ьу Biddles Ltd, Guildford, Surrcy
BELLEVUE UNIVERSIТY LIВRARY
Dedicated to the memory of W.A. Seth Paul
Contents
Preface
xi
AcknowIedgements
xiii
Abbreviations
xv
Introduction
1.1 Fundamental vibrations оС а mo\ecular fragment . . . . . . . . . . . 1
1.2 Fundamental vibrations оС а mоlесиlе . . . . . . . . . . . . . . . . . . . 2
1.3 Intcrpretation оС spectra Ьу means of tabIes with absorption
regions of molecu\ar fragments . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 NonnaI Vibrations and Absorption Regions of СХ 3
10
2.1 Methy\ снз . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.1.1 a Saturated ....................................... 11
2.1.2 a Unsaturated and aromatic . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.1.3 Nitrogen bonded methyl .. . . .. . . . . . . . . . . . . . . . . . . .. . . 15
2.1.4 Sulfur bonded methy\ . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1.5 Mercury and si\icon bonded methy\ . . . .. . . . . . . . . . . . . . 19
2.1.6 Acetyl ........................................... 20
2.1.7 Methy\ esters . .. . . . . . . . . . . .. . . . . . . . .. . . .. . . . . . . . . . 23
2.1.8 Methy\ ethers .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.2 Triha\ogenomethy\ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.2.1 Trifluoromethy\ СFз . . . . . . . . . . . . . . ., . . .. . . .. . . . . . 29
2.2.2 Trich1oromethyl ССlз . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.2.3 Tribromomethy\ СВrз . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3 Tertiary buty\ С(СНз)з . .. . . . . . . . . . . . . . . . . . . . . . . . .. . 40
viii
cOlllelllS
з
NоrшаI Vibl'ations and Absorplion Regiolls of СН 2 Х
48
3.1 Наlоgепошеtllуl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.1.1 Fluоroшеthуl CH2F ........,..................... 48
3.1.2 Сll10rошеthуl CHzCI ............................. 51
3.1.3 Bromomethyl CH2Br ............................. 57
3.1.4 Iоdошеtllуl СН2I ................................ 62
3.2 Охушсtl1уl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.2.1 Нуdrохушсthуl CHzOH . . . . . . . . . . . . . . . . . . . . . . . . . . 64
3.2.2 Methoxymetllyl CHzOMe .. . . . . . . . . . . . . . . . . . . . . . . . 68
3.3 Sulfur bonded methylene .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.3.1 Mercaptomet11yl CH2SH ... . . . . . . . . . . . . . . . . . . . . . . . 72
3.3.2 Methylthiomethyl CH2SMc . . . . . . . . . . . . . . . . . . . . . . . 75
3.3.3 Thiocyanatometl1yl CHzSCN . . . . . . . . . . . . . . . . . . . . . . 78
3.4 Nitrogen bonded methylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.4.1 Aminometl1yl CHzNHz ... . . . . . . . . . . . . . . . . . . . . . . . . 80
3.4.2 AmmoniomethyI СНzNНз+ ....................... 83
3.4.3 Isocyanatomethyl CHzNCO . . . . . . . . . . . . . . . . . . . . . . . 87
3.4.4 IsothiocyanatomethyI CHzNCS . . . . . . . . . . . . . . . . . . . . 88
3.5 Carbon bonded methylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.5.1 Ethyl СНzСНз .................................. 89
3.5.2 Trichloroethyl СНzССlз . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.5.3 Chloroethyl CHzCHzCI ............. . . . . . . . . . . . . . . 95
3.5.4 HydroxyethyI CHzCHzOH . . . . . . . . . . . . . . . . . . . . . . . . 98
3.5.5 n Propyl СНzСНzСНз . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
3.5.6 Propynyl CHzC=CH ............................. 104
3.5.7 Cyanomethyl CHzC=N ........................... 108
4 NonnaI Vibrations and Absorption Regions of CHX z . . . . . . . . . . 113
4.1 Dihal0genomethyl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.1.1 Difluoromethyl CHFz . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.1.2 Dichloromethyl CHClz . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.1.3 Dibromomethyl CHBrz . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.2 IsopropyI СН(СНз)z . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
5 NonnaI Vibrations and Absorption Regions of СИХ . . . . . . . . . . . 125
5.1 Halogenomethylene . . . . . . . . . . .. . . . . . . . .. . . . . . . . . . . .. . 125
5.1.1 Fluoromethylene CHF . . . . . . . . . . . . . . . . . . . . . . . . . 125
5.1.2 Chloromethylene CHC1 ........................ 126
5.1.3 Bromomethylene CHBr ........................ 126
5.2 Cyanomethylene СН(СN) . . . . . . . . . . . . . . . . . . . . . . . . . 127
5.3 Hydroxymethylene CH(OH) . . . . . . . . . . . . . . . . . . . . . . . 128
cOllleпlS
ix
6.1
6.2
6.3
Dinuoromctllylcne CFz
Dichloromcthylcnc CClz
Dibromomcthylcnc CBrz
132
132
133
134
6 NоrшаI Vibrations and Ab5orption Regions of CX z
7 NоrшаI ViI)rations and Absorption Region of с(==х)у
137
7.1 Carbonyl compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
7.1.1 Formyl C( ==О)Н .......................... .. . .. . 137
7.1.2 Fluoroformyl C(==O)F . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
7.1.3 Chloroformyl C(==O)CI . . .. . . . . . . . .. . . . . . . . . . . .. . 148
7.1.4 Bromoformyl C(==O)Br .. .. . . . . . . . .. . . . . . . .. . . .. . 152
7.1.5 Acetyl C(==O)Me ............................... 155
7.1.6 Propionyl C(==O)E! . . . . . .. . . . . . . . .. . . .. . . .. . . .. . 160
7.1.7 Carboxyl C(==O)OH ...... . . . . . . . . . . . . . . . . . . . . . . . 163
7.1.8 Methoxycarbonyl C(==O)OMe ..................... 169
7.1.9 Ethoxycarbonyl C(==O)OE! .. . . . . . . .. . . .. . . .. . . .. . 174
7.2 Amino(thio)carbonyl compounds ........................ 178
7.2.1 Carbamoyl C(==O)NHz .......................... 179
7.2.2 Thiocarbamoyl C(==S)NHz . . . .. . . . .. . . .. . . .. . . .. . 184
7.3 Methylamino(thio)carbonyl compounds . . . . . . . . . . . . . . . . . . 189
7.3.1 Methylcarbamoyl C(==O)NHMe ................... 190
7.3.2 Methylthiocarbamoyl C(==S)NHMe ................ 195
7.4 Carboxylate C02 ................................. 198
8 Nоrшаl Vibrations and Absorption Regions of Alkenes and
Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.1 Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
8.1.1 Vinyl CH==CHz ................................ 204
8.1.2 Vinylidene >C==CHz . . .. . . .. . . . . . . . . . . . .. . . .. . . .. . 212
8.1.3 Vinylene CH==CH ............................ 218
8.2 Alkynes ......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
8.2.1 EthynyI C=CH ................................. 225
8.2.2 Chloroethynyl C=CCl .. . . . . . . . . . . . . . . . . . . . . . . . . . 227
8.2.3 Bromoethynyl C=CBr ........ . . . . . . . . . . . . . . . . . . . 228
8.2.4 Iodoethynyl C=CI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
9 Nоrшаl Vibrations and Absorption Regions of Nitrogen
Сошроuпds ............................................. 2ЗЗ
9.1 Amino NHz ...................................... 233
9.2 Methylamino NHMe ............................... 239
9.3 Acetylamino NНC(==O)Me . .. . . .. . . . .. . . . . . . . . . . . . . 242
х
cOlllelllS
9.4 Dimctl1ylamil10 NMcz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
9.5 Nitro NOz ........................................ 250
10 NonnaI Vibrations and Absorption Regions of Оху COI11(>ounds . 258
10.1 R' oxy compOUl1ds ................................... 258
10.1.1 Hydroxy OH . .. .. .. .. .. .. . .. .. .. .. .. .. .. .. .. .. 258
10.1.2 MctllOXY OMc ................................. 263
10.1.3 EtllOXY OE! . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
10.2 R' yloxy compounds . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . 272
10.2.1 Formyloxy OC(==O)H . . . . . . . . . . . . . . . . . . . . . . . .. . 272
10.2.2 Chloroformyloxy OC(==O)Cl . . . . . . . . . . . . . . . . . . . . 273
10.2.3 Acetyloxy OC(==O)Me . . . . . . . . . . . . . . . . . . . . . . . . . 274
11 NonnaI Vibrations and Absorption Regions of SuIfur Compounds 277
11.1 Thio compounds ...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
11.1.1 Methylthio SMe ............................... 277
11.1.2 Ethylthio SEt .................................. 281
11.2 Metl1ylsulfinyl S(==O)Me ........................... 284
11.3 Sulfonyl compounds ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
11.3.1 Methylsulfonyl S(==O)zMe . . . . . . . . . . . . . . . . . . . . . . 286
11.3.2 Fluorosulfol1yl S(==O)zF . . . . . . . . . . . . . . . . . . . . . . . . 289
11.3.3 Chlorosulfonyl S(==O)zCI . . . . . . . . . . . . . . . . . . . . . . . 291
11.3.4 R' oxysulfonyl S(==O)zO . . . . . . . . . . . . . . . . . . . . . 292
11.3.5 Aminosulfonyl S(==0)2NHz . . . . . . . . . . . . . . . . . . . . . 294
11.3.6 R' aminosulfonyl S(==O)zNH .................. 295
11.3.7 Sulfonyl S(==O)z .. . . .. . . . . . . . . . . . .. . . . . . . . . . 296
12 NormaI Vibrations and Absorption Regions of Ring Structures 301
12.1 Cyclopropyl cPr .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . 301
12.2 Oxiranyl Ox . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
12.3 Aziridinyl Лz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
12.4 Phenyl . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
12.4.1 Monosubstituted benzene derivatives Ph . . . . . . . . . . . . 313
12.4.2 Disubstituted benzene derivatives Ph ............. 314
12.4.3 Trisubstituted benzene derivatives Ph< . . . . . . . . . . . . . 318
12.5 Pyridyl Py ........................................ 329
12.6 Pyrimidinyl Pyт ...................... ............ 331
12.7 Thienyl Th ....................................... 332
12.8 Furyl Fu . .. . . . . . . . . . . .. . . . . . . .. . . . . . . . . . . . . . . . .. . 334
Index ...................................................... 337
Preface
When interpreting infrared spectra of organic compounds, the chemist will restrict
himself (о the treatment of the typical group vibrations that produce vibrationaI
bands in а characteristic spectral region : the 'group Crequencies' or 'characteristic
frequencies'. This procedure is widely known and сап Ье considered as а
'qualitative interpretation' оС ап infrared spcctrum. This work has а tentative
assignment of аll normal vibrations оС а molecule in view: а 'quantitative
interprctation'. То attain this objective, the 3N 6 absorption frequencies of the
most important functional groups in distinct surroundings have Ьееп compared
and classified in tabIes. In this way complete interpretations of the absorption
frequcncics of а number of molecular fragments сап Ье made, based оп data of
vibrational analysis. When these molecular fragments join to form а molecule, it
is pos5ibIe (о interpret the infrared spectrum of this molecule for the most рап.
Iп the first place this work tries to Ье а guide for the organic chemist to
interpret infrared spectra as extensively as possibIe. А preliminary knowledge of
the interpretation of spectra is de5irabIe ри! по! necessary. Much information is
provided (о the spectroscopist оп starting а vibrational analysis. In this case а
description of the types of vibration is useful information.
Abbreviations and Symbols
Az aziridinyl m moderate
br broad Ме methyl
iВи isobutyl Naph naphthyl
пВи normal butyl Ох oxiranyl
sBu secondary butyl Реп! pentyl
'Ви tertiary butyl Ph phenyl
def deformation Pr propyl
Е! ethyl Ру pyridyl
ех! external Рут pyrimidinyl
Fu furyl Pyr рупоlуl
g gallC/le s strong
сНех cyclohexyl sh shoulder
HW high wavenumber sk skeletal
1т imidazolyl Th thienyl
LW low wavenumber /т /raпs
У а antisymmetric stretch w weak
У . symmetric stretch w wagging vibration
Б in plane deformation Р rocking vibration
I out of plane deformation т twisting vibration
(i/alic,upright): in case of extreme values, опlу the value in upright type is extreme.
1
Introduction
1.1 FUNDAMENTAL VIВRAТIONS OF А
MOLECUIAR FRAGMENT
In the infrared а chemical compound displays 3N 6 fundamental vibrations, in
which N represents the number of atoms from which the compound is Ьиil! up.
For each molecular fragment also 3N 6 vibrations are assigned if опе external
bond is caIculated as ап atom. lПе fundamental viЬrаtiопs are easily derived from
the following models:
CX: three vibralions
уСХ, БСХ, , or wCX (or tor5ion in а terminaI multi
atomic fragment).
VaCXZ, vsCXz, БСХz, wCXz, pCXz, TCXz (or torsion).
vаСХз, v СХз, vsСХз, Б а СХ з , Б СХз, Б s СХ3, Р СХ3,
р'СХ3, torsion.
or five vibrations in the case of С 3о symmetry: У а СХ 3 ,
v s CX 3 , dаСХз, Б s СХ з , Р СХ 3'
CXZ: six vibrations
CX3: nine vibrations
For the X substituted 11 ring 311 6 ring vibrations are expected.
X Oxirane (сСzНзОХ): 15 vibrations
vaCH z , vsCHz, БСНz, TCHz, wCHz,
pCHz, уСН, БСН, ,(w)CH, БСХ,
,СХ, torsion (or уСХ), vring,
Баriпg, Бsriпg.
two vaCHz, two vsCHz, two БСН z ,
two TCHz, two wCHz, two pCHz,
БСХ, ,СХ, torsion (or уСХ), vring,
Баriпg, Бsriпg.
X Aziridine (cCzH4NX): 18 vibrations
2
Illll"O(llICliOIl
X Cyclopropanc (cC-,Н 5 Х): 21 vibratiol1s t\VO v"CI-I z , two 1/,CHz, two bCI- I 2,
two TC112, two wCHz, two pCHz,
,/СН, ЬСН, ")'СН, ЬСХ, ")'СХ, torsion
(or I/СХ), l/ril1g, b"ring, b.,ring.
X Pllel1yl ( PI1 X): 30 vibrations fivc I/СН, fivc БСН, five ")'СН, уСХ
(or torsion), БСХ, ")'СХ, six vring,
three Бriпg, tlпее ")'ring.
TI1C following схашрlсs iI1ustrate how the fuпdашспtаl vibrations of а molccular
frаgшепt are found.
The nine vibrations of снз (У а СН 3 , v;снз, vsснз, Б а СН з , Б СНз, БsСНз,
рСНз, Р'СНз, torsion) togcther with the three vibrations of ОС (yO C, Б О С,
torsion) шаkе ир the 12 vibrations of ОСНз.
For the С(==О)ОСНз fragment another six vibrations (уС==О, БС==О,
")'с==о, and l/C O, Б С О, IOrsion) are added.
СНзСНz possesses 18 vibrations: nine of СНз, six of CHz and yC C,
Б С С, torsion.
The 12 vibrations of the HzC==CH fragment are: six of CHz, three of СН,
уС==С, Б С==С and torsion.
1.2 FUNDAМENTAL VIВRAТIONS OF А MOLECULE
Since the external C X stretching vibration in а molecular fragment, ехсер! for
aromatic structures, depends largely ироп Х, the wavenumbers of the torsions rather
than the stretching vibrations, are colIected in tabIes. If, for the construction of а
molecule, the coupling of two fragments leads to two torsions, опе torsion has
to Ье replaced Ьу а C stretching vibration. In the case of fragments with two
free bonds, опе of them is coupled (о ап atom or another group Ьу which three
vibrations are added: а stretching vibration, ап in plane deformation and ап out
of plane deformation (or torsion).
The following examples iIIustrate the determination of the fundamental vibrations
of а molecule.
When СIСНzСНз splits into CI and СНzСНз опе finds 17 of the 18
vibrations in the tabIe for ethyl (Section 3.5.1). Evident1y there is по ethyl torsion
and the missing Cl CHz stretching vibration is located in thc (аЫе for CHzCl
(Section 3.1.2). Ву splitting into CICHz and СНз, eight vibrations in the (аЫе
for CHzCI and nine vibrations in the tabIe for methyl (Section 2.1) need to Ье
considered for the interpretation. The missing yC C takes the place of а torsion
and is found in the tabIe for ethyl.
HzC==CH C(==O)H possesses 18 normal vibrations: the 12 vibrations of
HzC==CH together with the six vibrations of C(==O)H Ьи! опе of the two
torsions has to Ье substituted Ьу опе C C stretching vibration.
1.3 AlJsorp/ioп regioпs о/ то/еСII/а, fragmellls
3
Thc 21 normal vibrations of Me CH==CH CI are deduced in а similar way
from thc ninc vibrations of Ме and thc 12 vibrations of CH==CH CI. Tho5e
of CH==CH CI arc found Ьу adding (о the nine vibrations of CH==CH а
C CI strctching vibration, ап C==C CI in planc deformation and а C==C CI
torsion.
Thc 30 vibrations of the monosubstitutcd benzcne ring (Scction 12.4) with
the 12 vibrations of C( ==O)NH z (Scction 7.2.1) give the 42 vibrations of
Ph C(==O)NHz.
1.3 INTERPRETATION OF SPECТRA ВУ MEANS
OF TAВLES WIТH AВSORPТION REGIONS OF
MOLECULAR FRAGMENTS
Example 1: Me C(==O) CHzOH
The 27 normal vibrations of Me C(==O) CHzOH are divided into 15 vibrations
of Me C(==O) and 12 vibrations of CHzOH. lПе C C stretching vibration
between the two groups takcs the рlасе of опе of the two torsions. lПе remaining
torsion is this опе between the two groups.
No. WаvепuшЬеr Me C(==O) C(==O) CHz CHzOH
(Section 7.1.5) (Scction 3.2.1)
1 3390 br уОН...О
2 2990 w УаМе, Y Me vaCНz
3 2897 m vsMe V s CH 2
4 1721 s ус==о
5 1416 m БаМе, Б Ме Бснz, БОн. . .0
6 1359 s БsМе
7 1286 m wCHz
8 1228 m TCHz
9 1187 m yC C
10 1083 s рМе yC O
11 971 m р'Ме
12 871 m pCHz
13 813 m yC C
14 613 s Бс==о
15 575 m,br ')'ОН...О
15' 503 m ')'с==о
16 409 m Б-с-о
17 277 m БС-С-
torsion Ме
torsion
4
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о
о
Il')
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о
о
Е
Е:
:J:
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с.?
z
ш
з:
8
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ш
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CI:
LL
о
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о
C\I
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Il') о
..... Il') C\I
(о;.,) 3:)NV.LLI SNVI::I.l
8
o
1.3 AlJsorp/ioп regioпs о/ то/еСII/а, /ragments 5
Examplc 2: HOCHzCHzOMe
Тhc molcculc HOCHzCHzOMc (33 vibrations) сап split into HOCH2 (12
vibrations) and CHzOMe (21 vibrations), or into HOCHzCHz (21 vibrations)
and OMc (] 2 vibrations).Thc formcr splittinggives thc C O C stretchings but
thc lattcr dcscribcs thc CHz vibrations and somc skeletal vibration5 more precisely.
No. Wavenumber HOCHz CHz CHz CHzOMe
(Section 3.2.1) (Scction 3.2.2)
1 3400 br уОН...О
2 2980 sh vaCHz УаМе, Y Me
3 2928 s vaCHz
4. 2879 s vsCHz v,CHz
5 2827 m у,Ме
6 1470 sh Бснz БаМе
7 1457 m БСНz, Б Ме, БsМе
8 1408 br Бон...О
9 1368 m wCHz
10 1326 w wCHz
11 1286 w TCHz
12 1233 m TCHz
13 1193 m рМс
14 1155 sh р'Ме
15 1123 s YaC O C
16 1066 s y O C
17 1017 m yC C
18 963 vsC O C
19 891 m pCHz
20 834 m pCHz
21 6J5 br ,он...о
22 539 m БО С
23 463 w БС О С
24 376w Бс с о
25 225 w torsion
torsion
torsion
No. Wavenumbcr HOCHzCHz CHz O OMe
(Scction 3.5.4) (Section 10.1 .2)
1 3400 br уОН...О
2 2980 sh vaCHz УаМе, Y Me
3 2928 s vaCHzOH
4 2879 s vsCHz, vsCHzOH
5 2827 m l/,Me
6 1470 sh БСн,он БаМе
7 1457 m БСН; Б Ме, БsМе
8 1408 br Бон...О
6
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о 00
ц) N О
N
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1.3 Absorplioп regioпs о/ то/еси/а, /ragmeпts 7
No. Wavenumber HOCHzCHz CHz o OMe
(Section 3.5.4) (Scction 10.1.2)
9 1368 m wCHzOH
10 1326 w wOlz
11 1286 w TCHzOH
12 1233 m TCHz
13 1193 m рМс
]4 1155 sh р'Ме
]5 1123 s y o
]6 1066 s yO C
17 1017 m yC C
18 963 m vO C
19 891 m pCHzOH
20 834m pCHz
21 615 br ')'ОН. . .0
22 539 m БО С С
23 463 w Б О С
24 376 w БС С
25 225 w torsion
torsion
torsion
Ехаmрlе 3: Ph C(==O)Et
Тhe 54 normal yibrations of Ph C(==O)Et are divided into 30 vibrations for the
benzene ring and 24 vibrations for the C(==O)E! group.
No. Wavenumber Ph Wilson С(==О)СНzСНз
(Section 12.4.1) (Section 7.1.6)
1 3085 w уСН 20а
2 3062 m уСН 20Ь,2
3 3038 sh уСН 13
4 3028 w уСН 7Ь
5 2980 m УаМе, v Me
5' 2950 m vaCHz
6 2910 w vsMe
6' 2880 w vsCHz
7 1686 s vC==O
8 1600 m vPh 8а
9 1582 m vPh 8Ь
10 1490 w vPh 19а
11 1460 m БаМе, Б Ме
12 1448 s vPh 19Ь
13 1413 m Бснz
14 1377 m БsМе
15 1352 m vPh 14
8
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z.з Absorp/ioп regioпs о/ то/еси/а, /ragmeп/s 9
No. Wavcnumbcr Ph Wilson с(==о)снzснз
(Scction 12.4.1) (Scction 7.1.6)
16 1320 w wCHz
17 1301 w Бсн
18 1278 m TCHz
19 1219 s vPh C 7а (Х)
20 II!Ю m ьсн 9а рМс
21 J 159 w БСН 9Ь
22 1077 m оСН 15 р'Мс
23 1025 sh оСН 18а
24 1013 m !lC(==O) C
25 1002 m vPh 1
26 974 sh ,СН 5
27 951 s ,СН 17а !lC Mc
28 935 w (CH 17Ь
29 847w ,сн 10а
30 817 w рС Н 2
31 782w БРh 12 (Х)
32 745 s ,СН 11
33 690 s ,Ph 4
34 640 m БРh 6Ь
35 565 m ,Ph 16Ь (Х) оС==О
36 475 m БРh 6а (Х) А(С==О
37 414w ,Ph 16а
38 339 w БС(==О)С С
39 302 m Б С(==О) С
40 238 w БРh С 18Ь (Х) torsion
,Ph C 10Ь (Х)
torsion
torsion
2
Normal Vibrations and
Absorption Regions of СХ 3
2.1 METHYL
The 5imp\est molecules containing а melhyl group are the СНзХ molecules (Х = F,
CI, Br, CN, ССН, ...) which belong 10 point group Сз". The methyl group possesses
буе norrnal vibrations, i.e. two stretchings, two deformations and а rocking:
vaMe, vsMe, ОаМе, БsМе and рМе
The methy\ group accounts for nine normal vibrations when the symmetry of
the molecule is 10wered from С3.. (о С . or CI. Stated differently, а methyl group
possesses ап anti5ymmetric stretching, а deformalion and а rocking vibration with
С З .. symmetry and two of each \vhen the symmetry is Iowered from СЗV 10 C s ,
whcre Ihe degeneracy is removed. Moreover, the methyl torsion now becomes а
norrna1 vibration. With Сз.., {с . or С 1 } molecules Ihe torsion is а rotation {exlernal
deforrnalion} which is по! aClive {active} in Ihe IR. The normaI vibralions of
methyl mау Ье de5cribed as follows:
v a v'a
Сз\. е
С . а" а'
V s
Ба
Б'а
Б s
р
р'
т
а)
а'
е
а"
а'
а.
а'
е
а"
а'
а"
With thc а' {a"}-vibrations the dipole change proceeds in {is perpendicular to} the
plane of 5ymmelry.
ln5tead of describing three stretchings (deformations) in terms of two
anlisymmetric and опе 5ymmetric mode of vibration, these modes сап aIso Ье
2.1 Me//1Y/
11
dcscribcd in terms of three independent СН strctchings (dcformations). These
approximations arc derived from the fact that in а methyl group the СН bonds are
по! always equal (about 0.11 пт) Ьи! dcpend оп the surroundings. For instance, а
halogcn atom in (Ьс gallc/le position of the mcthyl group often causes dissimilar
СН bonds. Dcspitc thc [ас! (Ьа! а methyl group providcs two antisymmetric modes
of vibrations thcse fundamcntal vibrations will по! always Ье observed separately.
Iп practicc, and in particular with largcr molccules, thesc vibrations often coincide
with or arc supcrposcd оп thc тисЬ stronger absorptions of the CH z vibrations.
The two rockings arc oftcn scparately obscrved Ьи! are generaIly strongly coupled
to skelctal vibrations and vicc vcrsa, which is reflected in the wide absorption
regions and the dcscription СС stretch/Me rocking or Ме rocking!CC stretch. Опе
also refers (о the parallcl {perpendicular} methyl rocking when the dipole changes
paraIlel {perpendicular} (о the direction of thc 10cal С3 axis. Generally, the parallel
rocking is strongly coupled (о the СС stretching vibrations.
2.1.1 a:-Saturated
The group consists of Mc R molecules in which R is а substituent and the a:
carbon atom is fuIly or partly substituted or по! substituted (see Sections 3.5.1 and
3.5.5). Differentiation has Ьееп made between the molecules МеСНХУ, MeCXz У
and МеСХ з in which Х equals F, Сl, Br, ОН, 00 and CN.
Stretching vibrations
For molccules of the (уре МеСНХУ, the methyl antisymmetric stretchings are
found in thc neighbourhood of 2970 and 2960 cm l. lПе absorptions are generaIly
situated а! higher wavenumbers, i.e. in the vicinity of 3005 and 2980 cm 1 for
molecules of the (уре МеСХ2 У, and this tendency continues for МеСХз (Х = F,
СI and Br), whereas the methyl antisymmetric stretching absorbs somewhere near
3010 cm l.
Behaviour similar (о that of the antisymmetric stretchings has Ьееп observed
for the symmetric mode. For МеСНХУ molecules this vibration is active in the
neighbourhood of 2910 сm 1, whereas molecules of the (уре MeCX z У absorb in
the vicinity of 2940 cm l. This region becomes 2955::1:20 cm 1 for МеСХ з (Х =
F, СI and Br). ТаЫе 2.1 iIIustrates the influence of the fluorine оп the wavenumber
ТаЫе 2.1
Molecule УаМе у'а Ме vsMe
Me CHP Me 2989 2935 2893
Me CFz Me 3018 3018 2959
Ме СFз 3035 2975
12 Norllla/ Vi/JI"a/iOl/s IlIlll AlJsOI7J/io/l Regio/ls о/ СХ3
of tllc П1сthу\ strctcltings. lПс intcnsity varics frоП1 strollg for МсСНХУ, mcdium
for MeCX У (о \veak t'or МсСХз nlOlcculcs.
Dcformations
lПс wavenumbcr regions in \\Ihicll tllesc vibrations are active clearly indicatc that in
mапу cases the \vаvеПUП1Ьсrs of botll апtiSУП1mсtric dcformations often or always
coincide.
For molecules of the (уре МеСНХУ thc antisymmctric deformations are
observcd around 1455 and 1450 cm 1 and for MeCXz У mo\ccules both
deformations absorb in the neighbourhood of 1450 cт 1 with а medium (о strong
intensity. For МеСХз (Х = F, С\ and Br) the antisymmctric deformations absorb
weakly around the value 1445 cm 1.
With the symmetric deformation, again the wavenumbcr tends to increase with
degree of substitution and thc nature of the substituents. If the region is 1370::1: 25
cт 1 for МеСНХУ molecules, for MeCXz У it is 1380::1: 20 cт 1 and it increases
ир to 1390:1: 20 cm 1 for МеСХ з . lПе intensity varies from medium (о strong.
Ethane disp\ays the symmetric deformation а! 1379 cm 1. In the spectra of СН з Х
molecules (Х = F, Cl, Br and 1) this vibration is observed а! 1475, 1355, 1305 and
1252 cm 1 respectively.
Rockings
lПе \\Iavenumbers of these modes occur over such broad regions that опе сап hardly
speak of group wavenumbers. lПе Ме rockings are, like the symmetric deformation,
mass sensitive. Because of coupling with ske\etal modes, these rockings occur in
\arger regiolls of wavenumber compared with the stretchings and dеfоrП1аtiопs. The
intensity, however, is опlу weak (о mcdium. Ethane disp\ays both rockings а! 1155
(Raman) and 821 cm 1. Hydrocarbons display опе of the rockings very weakly in
t\Je vicinity of 1 138 cm t.
For many МеСНХУ molecu\es опе of the rockings, пате\у рМе, is observed
in the region 1150:1: 35 cm t, which is more or \ess acceptable as а group wave-
number. However, mo\ecu\es of the (уре MeCXz У display this methy\ rocking in the
region 1080:1: 115 cт 1. l..ow values have Ьееп observed in the spectra of 1-ch\oro-
2,2-diftuoropropane which absorbs а! 968 ст 1, and 2,2-difluoropropane, which
disp\ays rockings а! 991 and 988 cт 1. When these values are по! considered, the
region becomes more user friendly: 1135::1: 60 cm l.
МеСНХУ molecu\es disp\ay the р'Ме in the region 1010::1: 120 cm l.
2-Fluoropropane absorbs а! 1129 cm l. If this va\ue is neglected the absorption
region is reduced to 975:1:85 cm 1. MeCXz У molecules absorb а! 1000::1:95 cm 1
and МеСХ з mo\ecu\es in the region 1020::1: 60 cm l. Undoubted\y, the coupling
with СС and СХ stretchings serious\y affects and broadens the regions in which
these rockings have been observed.
2.1 Me//1Y/
13
Torsion
Torsion has Ьссп observcd а! relativcly high values, that is 250:1:65 cm l, although
valucs lowcr than 185 cт 1 тау по! Ье excluded. Мапу МеСНХУ {MeCXzY}
moleculcs display thc torsion in thc region 245 :1:30 {280:l:35} cm l. lПе highest
{Iowest} val ис: 314 {187} ст 1 has Ьсеп observed for 2,2-difluoropropane {2,2-
dibromopropanc} .
ТаЫе 2.2 Absorption regions (cm I) of Methyl in alkane fragmcnts
CHzMe CHzCHzMe CHXMc CXzMe СХзМс
УаМе 2985 ::1: 25 2975::1: 15 2970 :1: 30 3005 :1: 25 3010 :1: 25
у'а Ме 2970 ::1: 30 2965 ::1: 15 2960 :1: 35 2980 :1: 40
vsMe 2905 ::1: 65 2890 ::1: 50 2910:1: 50 2940 :1: 50 2955 :1: 20
БаМе 1465 ::1: 20 1465::1: 10 1455 :1: 20 1450 :1: 20 1445:i: 15
Б'а Ме 1445 ::1: 25 1450 ::1: 15 1450:1: 15 1450:1: 20
БsМе 1380 ::1: 20 1375 ::1: 15 1370 :1: 25 1380 :1: 20 1390 :1: 20
рМе 1100::1: 95 1105 ::1: 45 1150::1: 35 1080 :1: 115
р'Ме 1080 ::1: 80 1055 ::1: 45 1010 :1: 120 1000 :1: 95 1020 :i: 60
тМе 230 ::1: 105 210::1: 70 245 ::1: 30 250 :1: 65
R Ме molecules
R = R'CH2 (see Section 3.5.1), R'CHzCHz (see Section 3.5.5)
R = Me CHF [1----4], Me CHCI [5 7], CICHz CHCI [8---10],
CI2CH CHCI [10], Et CHCI [ll 13], Me CHBr [5, 6, 18],
CICHz CHBr [9], BrCHz CHBr [9], FзС СН(ОН) ,
FзС СН(ОD) , FзС СD(ОН) and FзС СD(ОD) [19],
FзС СН(СN) , FCHCI [14], ClzCH [15 17], Me CFz [20],
CICHz CFz [21], Me CHz CClz [22], Me CClz [2 25],
ClzCH CClz [10], F CClz [14], Me (CClВr)z [26],
Me CBrz [27], Me (CBrz)z [28], FзС [29 32], СlзС [15, 31,
33 36], ВrзС [31,37].
2.1.2 a-Unsaturated and aromatic
Stretching vibrations
lПе band intensity of the stretchings varies from medium (о strong. А smaIl part
of the region covers that of the ==СН stretching modes. Опе should therefore Ье
cautious in assigning bands within this region. In contrast (о saturated hydrocarbons,
both antisymmetric stretching vibrations are regularly displayed in separate regions.
In the region of the symmetric stretch а second smalIer band is due to an overtone
of the methyI bending vibration, intensified Ьу Fermi resonance.
14 Norllla/ VilJralio/ls аlll/ AlJsOIplio/l Ucgio/ls о/ СХ.I
lПе у.Мс vibration is observed in thc rcgion 2980 ::1: 30 cт " gcncrally
in the neighbourhood of 3000 cт 1 or 10wcr. Exccptiol1s occur in tllc spcctra
of НС=СМе, DС=СМе and HzC==CFMc \vhicll absorbs :::;3010 cm l. Tllc
10\vest value (2950 cm l) Iшs Ьссп assigl1cd in tlle spcctra of McDC==NOD and
3-NаО,С Рh Ме.
111е / аМе vibration displays а band in thc region 2950 ::1: 45 ст 1. Tlle higllcst
{10\vest} value, i.e. 2995 {2905} ст 1, has Ьсеп assigned in thc spcctrum of
4 Na02c Ph Me {MeO CH=CH Me}.
The symmctric stretching vibration appears in the rcgion 2895 ::1: 50 cm l.
А molecule such as 3 methylpllenol absorbs а! the HW sidc а! 2944 cm t,
foJ\o\ved Ьу H 2 C==CFMe (2942 cm 1) and Me CH==CH C(==O)H with 2938
cm l. Me CH==NOH \vith 2847 cт l absorbs а! the LW side foJ\o\ved Ьу
MeO CH ==СН Ме, for \vl1ich the methyl stretching vibration has Ьееп assigned
а! 2855 cm l.
Dcforrnations
The antisymmetric deformations are observed with band intensitics that are weak,
mostly medium or sometimcs strong. lПе overlap between the two regions is quite
con5iderabIe so that for тапу molecules the deformations often coincide. In the
HW region (БаМе: 1457 ::1: 27 cт 1) the highest {Iowest} value is assigned (о
the БаМе in the spectrum of 1,3-dimethylbenzene {Me C=C C(==O)CI}. In
the LW region (Б'аМе: 1435 :f: 35 cm J) these values are 1470 and 1400 cm t,
respectively occurring in the spectra of Hz==C(OMe)Me and сСзНзМе.
In manу molecules the symmetric deformation (БsМе: 1380 ::1: 25 ст 1) appears
with ап intensity varying from medium (о strong. lПе wavenumber 1401 cт 1 is
the highest value as5igned in the spectrum of 2-fluoropropene. The lowest value for
this vibration is 1357 cm J, observed in the spectrum of cis Me CH==CH Me.
Rockings
Aromatic molecules clearly display а methyl rock in the neighbourhood of 1045
cт 1. lПе second rock in the region 970 ::1: 70 cт 1 is more difficult to find
among the ==СН out of plane deformations.
The рМе vibration provides а band with а weak (о medium, rarely strong
intensity, in the region 1О65:!: 65 cm J. DON==CH Me occupies the (ор place
with 1130 cm l, foJ\owed Ьу DON==CD Me (1122 cт 1) and HON==CH Me
(1110 cm I). lПе va1ues 1000, 1005 and 1007 are the 10west which have
Ьееп found in the spectra of 2,6 Me2 Ph OH, 2,6 Mez Ph F and 2,3
Mez Ph F respectively. In the series Me C=C R in which R equals
C(==O)Cl, C(==O)F, 1, Br and CI, this rocking absorbs respectively а! 1016, 1023,
1021, 1027 and 1033 crn l.
2.1 Me/hy/
15
Thc р'Мс is cxpcctcd (о give а band with а wcak (о medium intensity in the
rcgion 980::1: 80 cm l. Thc highcst wavenumber, namely 1060cm 1, is assigned in
thc spcctrum of HzC==C(CH 2 CN)Me followed Ьу 1050 in that of HzC==CMez. In
thc scrics Mc CH==CH R whcre R equals С(==О)Н, С(==О)ОМе, С(==О)ОЕ!
and С(==О)Мс this rocking has respectivcly Ьееп observed а! 1042, 1030, 1030
and 1020 ст 1. Thc lowcst values havc Ьееп assigned in the spectra of 2,3-
Mcz Ph OH (990, 901 cm I), 2,6 Mcz Ph OH (987, 912 cm 1 ) and
Рh СI-I==СН Мс (910 cm I).
Torsion
Very little information is availabIe as (о the torsion although it is expected that
тапу of these torsions absorb а! 185 ::1: 65 cm l.
ТаЫе 2.3 Absorption regions (cm I) of mcthyl in alkcncs,
alkynes and phenyl
==c Ме =c Ме Ph Me
УаМе 2980 ::1: 30 2985 :1: 25 2975 :1: 25
у'а Ме 2940 ::1: 35 2960 :1: 35
У..Ме 2895 ::1: 50 2910 ::1: 30 2925 :1: 20
БаМе 1455 ::1: 25 1445::1: 15 1460 :1: 25
Б'а Ме 1435 ::1: 35 1435 :1: 35
БsМе 1380 ::1: 25 1375 ::1: 15 1375 :1: 15
рМе 1070::1: 60 1035 ::1: 20 1045:1: 45
р'Ме 985 ::1: 75 970 :1: 70
тМе 185::1: 65
R Me molecules
R = HzC==CR' (see Section 8.1.2), R' CH==CH (see Section 8.1.3),
Х C=C (Х = Н, CI, Br, 1) (see Section 8.2);
R = HzC==CH , HzC==CD and DzC==CH [38, 39], Me CH==CO
and Me CO==CO [40], HDC==CBr and DzC==CBr [41],
сСзНз [42], HON==CH , DON==CH and DON==CD [43,
44], O C=C [45, 46], Me C=C [92], Et C=C
[47], F C(==O) C=C [48], CI C(==O) C=C [49],
N=C [50.-.-55];
R = (substituted) phenyl (see Section 12.4).
2.1.3 Nitrogen bonded methyI
Molecules of (уре NHMe and of (уре X Me in which Х = H2N ,
DzN , (SiНз)zN , O==C==N , S==C==N , OzN , NЗ and CN will
Ье considered in this section.
16 NOl"llla/ Vibra/iolls alld Absorp/ioll Regiolls о/ СХз
Stretching vibrations
Me NOz (3060 cm l) and Мс Nз (3023 cm l) providc tllc higllcSt valucs for
the methyl antisymmctric strctching. Mctllyl stretcl1ings of N mcthyl su!Jstitutcd
amines or amides absorb belo\v 3000 cm l. TllC higl1cst va\uc (2995 cm l) has
Ьсеп obscrved in thc spcctrum of MeSC(==S)NHMe, followcd Ьу 2990 cт l in
thc spectra of McOC(==S)NHMc and KOC(==O)C(==O)NHMc.
With the exception of (l1е X Me n1Olecules, the symmetric strctching absorbs
sharp\y in the neighbourhood of 2850 cm l, with а band intensity varying from
medium (о strong. lПе highest values are shown Ьу MeNHNOz (2923 ст 1 ),
MeC(==O)NHMe (2915 cm l) \vhere the methy\ group is /ralls with respect (о the
с==о group, and MeSC(==S)NHMe (2910 cm I). Dimethylamine, which absorbs
at 2791 cm l, provides the 10west wavenumber, followed Ьу 2810 cт 1 in the
spectrum of, for instance, MeNHC(==O) C(==S)NHMe and 2824 cт l in that
of NC C(==O)NHMe. If these extreme va\ues are neg\ected, the region of this
vsMe is reduced (о 2855 :!: 40 cm l. This band is often quite usefu\ in identifying
NMe or ОМе groups in unknown molecu\es.
Deformations
With Me N molecules, а separate observation of both Ме antisymmetric
deformation5 (1455 :!: 35 and 1445 ::1: 35 cm l) is ап exception rather than а
rule.
DimethY\an1ine disp\ays the antisymmetric deformations а! 1483, 1467, 1463 and
1445 cm l. DЗСS(==0)2NНМе absorbs а! 1472 and 1466 cm l. HC(==O)NHMe
disp\ays the antisymmetric deformations а! 1467 and 1458 cm l. А wavenumber
of 1480 cm l is found for both antisymmetric deformations of HzNC(==O)NHMe
and 1420 cт l for those of R'C(==O)NHMe (R'== С' and Br).
lПе symmetric deformations of dimethy\amine have Ьееп assigned а! 1441 and
]412 cm t, Ьи! БsМе of nitromethane absorbs а! а lower value: 1376 cm l. The
region of this symmetric deformation (1410 :!: 35 cm l) narrows (о 1410 :!: 20
cm l for most nitrogen-substituted methy\ compounds.
Rockings
With Me N mo\ecules both rockings (1150:!: 50 and 1090::1: 75 cm l) are more
or \ess strongly coupled (о the C N stretching vibration, often assigned in the
region 1010 :!: 90 cm l. Therefore, one of the methy\ rockings also absorbing in
this region often receives the notation pMe/vCN or vCN/ рМе, which is reftected
in the large over\ap of both ranges. lПе assignment of vCN/ рМе is more difficu\t
when the Q atom of the R substituent comprises а saturated С atom because the
CNC ske\eton now providcs two C N stretchings. For some R' NНMe
mo\ecules ТаЫе 2.4 summarizes the C N stretching and methyl rockings and
2.1 Me/IIY/ 17
ТаЫе 2.4
R рМе р'Ме vC N
HzNC(==O) 1169 1106 1106
CIC(==O) 1163 1163 1003
McC(==O) 1 ]61 1114 IU45
MeNHC(==O) 117О 1132 1038
1148 1035 1020
HC(==O) IJ48 1040 951
Me 1158 1079 930
1145 1022 925
ТаЫе 2.5 Absorption regions (cm I) of nitrogcn bondcd mcthyl
NHMe SOzNHMe C(==O)NHMe C(==S)NHMe X Me
УаМС 2965 ::1: 25 2965 ::1: 25 2970 ::1: 30 2970 :!: 30 3005 :!: 55
у'а Ме 2950 ::1: 25 2950 ::1: 25 2945 ::1: 45 2945 :!: 25 (2990 :!: 55)
vsMe 2855 ::1: 70 2855 ::1: 70 2870 ::1: 45 2875 :!: 45 2895 :!: 75
БаМе 1470::1: 15 1470::1: 15 1450:!: 30 1450:!: 25 1445 :!: 20
Б'а Ме 1460::1: 15 1460 ::1: 15 1445 ::1: 35 1435 :!: 25 (1435 :!: 15)
БsМе 1410 ::1: 35 1410::1: 35 1400::1: 25 1400:!: 25 1405 :!: 25
рМе 1150::1: 30 1135::1: 15 1155 :!: 30 1145:!: 45 1160:!: 40
р'Ме 1085 ::1: 65 1070 ::1: 15 1100::1: 65 1075 :!: 40 (1075 :!: 50)
тМе 230 ::1: 30 230 ::1: 30 230 :!: 30 195:!: 50
also includes high and low wavenumbers of each series. lПе highest methyl rocks,
in the neighbourhood of 1200 cm l, are assigned in the spectra of МеN(SiН з )z,
MeNH z and МезN.
R Me molecules
R = R'NH (see Section 9.2), R'SOzNH (see Section 9.2), R'C(==O)NН
(see Section 7.3.1), R'C(==S)NH (see Section 7.3.2).
х Ме molecules
Х = H2N [56, 57], DzN [56, 57], (SiНз)zN [58, 59], O==C==N [6 2],
S==C==N [63 68], OzN [69 73], NЗ (74, 75], CN [52,76].
2.1.4 Sulfur-bonded methyI
Stretching vibrations
The region 3015 ::1: 35 cm 1 is assigned (о УаМе and the region 2995 :!: 55 cт 1
to у' аМе of the sulfur substituted methyl group. lПе intensity of the band i5 weak
or medium. Some sulfonyl compounds of (уре MeS(==O)zR' (R' = Ме, Ph, PhNH,
18 NomlU/ \libт/iolls ши/ A/)SOI'f)/ioll Regiolls о/ СХ з
NH , NDz, F, Cl, Br) sl\O\v botll П1сtllуl апti5УI11П1сtriс strctcl1il1gs in thc rcgion
3О30:!: 20 al1d 3025 :i: 25 СI11 1 \vitll tllC I1igllcst val\lcs in tllc vicil1ity of 3045
cm 1 for R' = F, Сl and Br. Botll vibrations arc I10! al\vays ol)scrvcd scparntcly.
Most R SMc nlO1cclllcs display llllMc а! 3005 :i: 25 СП1 l witll tllc I1igllCSt vnl\lc
(3030 СП1 l) Cor NCSMc al1d EtSSMc and tllC lo\vest Cor McSMc (2982 cm I).
Тhey display thc l/аМС а! 2980 :i: 45 cт l \vitll 3022 СП1 1 for NCSMc and 2940
cm 1 for HzNc(==S)SMe.
Тhe SУП1mсtriс stretching n\Ode absorbs around 2930 ::1: 30 cm 1 witl1 пп
intensity varying from \veak (о П1еdium. 111е I1ighcst value obscrved for У-,Ме
is 2958 cт 1 in the spectrUln of FS(==0)2Me. R SMe molcculcs absorb around
2925 :i: 20 сm 1, tlшt is, аЬои! 100 ст I higher than the corresponding mode
in ОМе. For instance, П1еthохуmсthапе {metllylthiomcthane} displays the vsMe
а! 2820 {2917} cm 1 and Ph OMe {Ph SMe} disp]ays the same vibration а!
2834 {2922} cm 1.
Deforrnations
lПе absorption regions of both antisymmetric deformations (1435 ::1: 35 and ]430
:i: 30 cm l) overlap each other appreciabIy. The highcst values of БаМе, патеlу
1468 and 1457 cm l, are a5signed in the spectra of methylthio-2-pyrimidine and
CICH z CH z OS(==O)zMe al1d the 10we5t, namcly 1404 and 1409 cm l, in those of
iPrzNS(==O)zMe and 4 HOC(==0)PhS(==0)zMe. Мапу БаМе are centered around
]435 cm l.
Тhe highest {]owest} \vavenumber for Б'аМе, пате]у 1460 {1400} cm 1
has a]5o Ьееп assigned to methylthio 2 pyrimidine {4 HOC(==0)PhS(==0)zMe}.
ClSMe absorbs around 1408 cm l, although most of the Б' аМС absorptions occur
in the vicinity of 1425 cm l.
Тhe methyl symmetric deformation is observed in the low \vavenumber region
1320:!: 30 cm 1 with а band intensity betwecn medium and strong. The highcst
value, 1350 cm l, has Ьееп observed in the spectrum of EtOS( ==O)zMe, the 10west,
1295 cm l, in that of MeS(==O)Me. Whereas vsMe of SMe absorbs near]y 100
cm 1 higher compared with ОМе, the reverse is true for Б.,Ме, whcre the difference
amounts 'о аЬои! ]25 cm l. Methoxymethane {methy]thiomethane} shows БsМе а!
]449 and 1432 {1328 and 1303} cm 1 and methoxybenzene {methylthiobenzene}
absorbs а! 1442 {1317} cт 1. lПе methyl symmetric deformation for sulfonyl
compounds ab50rbs also а! lower \vavenumbers (1325 ::1: 25 cт 1) than those
u5ually observed for paraffins. This is attributed to the influence (including mass)
of the S atom.
Rockings
lПе methyl rockings of S-attached methyl occur in the regions 990 ::1: 45 and 940
:i: 45 cm 1. lПе overlap is considerabIe, both rockings therefore often coincide.
2.1 Mc/hy/
19
Again, thc rcgions arc 10wer (Ьу аЬои! 200 cm l) than those of the corresponding
O attachcd methyl groups.
Lcaving asidc thc high valuc for рМе (1065 cm l) in the spectrum of MeSH,
most of thc рМс havc Ьссп observcd in thc range 990 ::!: 45 cm l. High values are
furnisllcd Ьу MeSMc (1032 cm l) and McS(==O)Me (1022 cm l) and 10w values
Ьу CIS(==O)Mc (948 cm l) and thc disulfides McSSMe, EtSSMe and tBuSSMe
(' 955 ст I ).
lп thc rcgion 940 ::1: 45 cm 1 thc highcst {Iowcst} wavcnumber for р'Ме, 981
{896} cт 1, is obscrvcd in the spcctrum of FS(==O)zMc {McS(==O)Me} fol1owed
Ьу 976 {900} cт 1 in that of CIC(==O)SMe {4-СIРhNНS(==0)zМс}.
R Ме molecules
R = R'S (sce Section 11.1.1), R'S(==O) (sec Section 11.2), R'S(==O)z (see
Section 11.3.1).
2.1.5 Меrcш-у- and silicon-bonded methyl
Stretching vibrations
The three stretchings are found in the region 2945 ::!: 55 cm l in which the band
intensitics vary from weak (о mcdium. lПе two molecules MeHgMe and MeSHgMe
do по! show separate antisymmetric Ме stretchings. lПе number of investigated
molecules, however, is (оо smal1 'о attach much value (о the observed regions.
Deformations
The antisymmetric deformations are weak1y active in the region 1420 ::!: 30 cm 1.
The symmetric deformation absorbs in the lowest of al1 regions in which this
vibrational mode has Ьееп observed: 1265 ::1: 25 {1180 ::1: IO} cm 1 for Si{Hg}-
bound methyl. TI1e band intensity is mostly medium. In the spectrum of F з SiМе
{lзSiМе} БsМе has Ьееп assigned а! 1286 {1247} cт 1. If methyl is attached (о
ап еlетеп! other than carbon, the wavenumber region of the methyl symmetric
deformation is largely dctermined Ьу the electronegativity of the element and its
position in the Periodic ТаЫе. It has already Ьееп menlioned that for Х Me
molecules (Х = F, Сl, Br and 1) this mode absorbs а! 1475, 1355, 1305 and 1252
cт 1. O{N} attached methyl displays this mode around 1450 {1410} cm l, S{P}
attached methyl in the neighbourhood of 1320 {1280} cт 1 and Si{Hg} attached
methyl around 1265 {1180} cт 1.
Rockings
Both methyl rockings absorb in the 10west of al1 regions in which these vibrations
are found: 840 ::1: 50 and 805 ::1: 65 cm l for Si-attached methyl. For R HgMe
20 Norllla/ ViЬпl/iО/lS тиl Absol1J1io/l Rcgio/ls о/ СХ з
1'dbIe 2.6 Absorplion regions (СП1 I) of sulfur-, silicon- and mcrcllry bondcd mcthyl
SMc S(==O)Me S(==0)2Mc SiMe HgMc
v"Me 3005 :1: 25 3005 :1: 20 3030 :1: 20 2965 :1: 35 2975 ::1: 10
II'"Mc 2980 :1: 45 2995 :1: 15 3025 :1: 25 2950 :1: 25 2975 :1: 10
IlsMe 2925 :1: 20 2925 :1: 25 2940 :1: 20 2910:1: 20 2915::1: 10
б"Ме 1445 :1: 25 1425:1: 15 1430:1: 30 1425:1: 15 1425::1: 25
Б'а Ме 1430:1: 30 1415:1: 15 1415:1: 15 1415:1: 25 1420 ::1: 25
БsМе 1320 :1: 20 1305:1: 15 1325 :1: 25 1265 :1: 25 1180::1: 10
рМс 995 :1: 40 985 :1: 40 985 :1: 35 840 ::1: 50 745 ::1: 45
р'Ме 940 :1: 40 930 :1: 35 940 :1: 40 805 :1: 65 745 ::1: 45
тМе 175:1: 55
molecules the t\VO rocking5 are по! separated in the region 745:1: 45 cm l. Usual]y
the inten5ity varies from medium to strong.
R Me molecu]es
R = НзSi , HDzSi and DзSi [77], HzC==CH SiHz [78],
MeOSiНz and MeOSiDz [79], MeSSiH2 [80], MeSiНX
and MeSiDX (Х = F, CI, Br, 1) [81], MeSi(OH)z [82], MeSiClz [83,
88], MeSiВr2 [89], iPr SiClz [84], FзSi [85, 87], СlзSi [88],
ВrзSi [89], IзSi [86], MeHg [90], MeSHg [91].
2.1.6 Acetyl
Тhe ab5orption regions of the normal vibrations of the methyl group in acctyl
molecules of (уре R'C(==O)Me have Ьееп grouped with R' representing saturated,
un5aturated and aromatic fractions. Acetamides, acetates and thioacetates are a]so
considered in this section.
Stretching vibration5
Typical for acetyl molecules is the weak intensity of the Ме stretching vibrations.
De5pite the strong overlap of the wavenumber regions of the antisymmetric
stretchings, both modes are observed separately.
Acetyl substituents often display УаМе in the region 3005 ::1: 40 ст 1. The
HW side of this region is limited Ьу 3043 cm 1 from the spectrum of acetyl
fluoride followed Ьу 3029 cm l as5igned in the spectra of acetyl chloride and
1,1,l trifluoro-2-propanone. А! the LW side опе finds 2966 and 2974 cm 1 in
the spectra of cPrC(==O)Me and МеzС(ОН)СНzС(==О)Ме respectively. Aromatic
acetyl 5ubstituents absorb in а narrow region (3010 ::1: 10 cm I), ап absorption
which sometime5 coincides with а СН stretching mode of the ring.
2.1 Me/IIY/
21
Acctyl substitucnts display thc у'аМе in the region 2975 :i: 45 cm l. Acctyl
cl1lori{lc, bromidc and iodidc absorb ncar 3015 cт 1, cPrC(==O)Me а! 2954 cm 1
and 4 X PhNHC(==0)Mc (Х = Н, Et, Br, НО) in the neighbourhood of2930 cm l.
Thc mcthyl symmctric strctching has Ьссп traced in thc region 2905 :i: 65 cm l.
This largc rcgion is causcd Ьу thc absorption of у"Ме in Fermi rcsonance with the
ovcrtone of thc Мс bcnding. Thc highcst valuc (2970 cm l) has Ьееп obscrved in
thc spcctrum of acctyl fluoridc and thc lowest (2846 cm l) in that of ОС(==О)Ме,
foIlowcd Ьу 2895 cт 1 for MezC(OH)CHzC(==O)Mc. Q Unsaturated acetyl
moleculcs absorb in thc range 2900 :i: 50 cт 1 with 2947, 2937 or 2850 cт 1 for
HzC==CH C(==O)Mc and 2858 cm 1 for Me HC==CH Me. For acetamides
this rangc is 2900 :i: 45 cm 1 ехсер! for dimethylacetamidc in which 50metimes
thc value 2816 or 2810 cт 1 is assigncd to this modc.
Deformations
Опе of thc two deformations absorbs а! 1445 :i: 35 cm l, the other 5pans the region
1430 ::1: 40 cm 1 with band intensities bcing wcak or mcdium. Consequently the
two bands often coincidc.
Maximum values for БаМе are observed а! 1480 cт 1 for
4 EtOPhNHC(==0)Me and а! 1470 cm 1 for PhNHC(==O)Me and 3
РуС(==О)Ме. Witl1 1411, 1416 and 1420 cm 1 re5pectively, the molecules
BrC(==O)C(==O)Me, HOCHzC(==O)Me and cPrC(==O)Me оссиру the lower
edges of the region.
For Б' аМе thc highest values (1470,1460 and 1447 cm l) have Ьееп observed in
the spcctra of 3 PyC(==0)Me, MezNC(==O)Me and ЕtOС(==О)Ме respectively,
whereas molecules such as NaOC(==O)Me (1390 cm I), BrC(==O)C(==O)Me
(1406 cm I), MeC(==O)SC(==O)Me (1412 cm l) and НС(==О)Ме with 1414
cт 1 absorb in the lowest part of the region.
The Б..Ме of acetyl absorbs а! 1365 :i: 25 cт 1 with ап intensity varying from
medium (о strong, although the weakest bands have Ьееп observed in the spectra of
acetyl halides. The highest value (1388 cm l) has Ьееп assigned iп the spectrum
of cPrC(==O)Me, which coincides with а СН bend of the ring. F з СС(==О)Ме
foIlo\vs with 1381 cm l. The lowest value (1342 cm l) comes from the spectrum
of ОС(==О)Ме foIlowed Ьу НОС(==О)С(==О)Ме and 2 OzNPhC(==0)Me, both
absorbing а! 1349 cm 1. If these extreme value5 are neglected, the region is reduced
(о 1365 ::1: 15 cm l, which makes this mode in acetyl ап appropriate group wave
number. 2 Propanone absorbs а! 1359 and 1355 cm l.
Rockings
The melhyl rockings of the acetyl group generally appear in the regions 1085
::1: 70 and 985 ::1: 85 cm l as а weak, moderate or sometimes 5trong band, the
22 Norllla/ VilJra/iolls ащ/ AlJsOIp/io/l Regio/ls о/ СХ з
wаVСПUП1Ьсr of \vl1icll is coup\cd 10 tlle СС strctcl1il1g vilJration, wl1icll occurs
in thc псigl1lюurhооd of 900 сm 1. TIIC modcs arc 1101 considercd (о providc
reliabIe group \vavel1umIJcr5. With acetatcs IIIC rockil1gs arc clcarly separatcd
and sho\v \veak 10 П1сdiuП1 activity in thc rcgions 1050 :i: 30 and 980 :i: 45
СП1 I. Ho\vever, тапу esters also sho\v thc C O al1d C C stretching bands
in the 1050 cm l region so that thc first П1Сl1tiопеd rocking саппоl always Ьс
as5igned uпаП1Ыguоuslу; tlle band might Ье I1iddcn bchil1d thesc (somclimcs strong)
vibrational bands.
High values for рМе, паП1сlу 1155, 1151, 1140 and 1135 cm l, have Ьесп
assigned in the spectra of CICH2C(==0)Me, ClzCHC(==O)Me, MeSC(==O)Me
and MeC(===O)SC(===O)Me. 1l1с lo\ver region is occupied Ьу СDзОС(==О)Ме and
Ме2С(ОН)СН2С(===0)Мс (1020 cm l) and Ьу MeC(==O)CHzC(==O)Me with
1020 and 1040 cm J.
For р'Ме, molecules such as IC(==O)Me (1070 cm l), HSC(==O)Me
(1065 cm l) and DSC(===O)Me with 1060 cт 1 absorb а! the HW side,
\vhereas МеС(===О)Ме (902 cm l), MezC(OH)CHzC(==O)Me (913 cm J) and
НС(===О)Ме wilh 918 cт ! are found 'о absorb а! thc LW side of the range. Both
regions of the melhy\ rockings are 'оо broad (о lаЬе\ these modes as suilabIe group
\vavenumbers.
Torsion
Тhe torsion is often found in the region 190 :!: 80 ст J .
ТаЫе 2.7 Absorption regions (cm J) of П1Сlhуl in acetyl
C(==O)Mc C(===O)Mc C(===O)Mc >NC(==O)Mc OC(==O)Mc SC(==O)Mc
satur31cd unsaturated aromatic acelamidcs acclates thioacctalcs
УаМе 3005 :i: 40 3000 :i: 30 3010 ::1: 10 2990 :i: 20 3010:!: 30 3000::1: 10
У'оМе 2990 :i: 30 2960 :i: 30 2975 :!: 25 2965 :i: 35 2965 ::1: 35 2990::1: 10
vsMc 2905 :i: 65 2900 :i: 50 2925 ::1: 15 2900 :i: 45 2910:!: 50 2920 ::1: 10
бамс 1440 :!: 25 1425:!: 15 1445 :!: 25 1450 :i: 30 1440::1: 25 1435::1: 15
б'а МС 1425:!: 15 1415:!: 25 1445 :!: 25 1440 :i: 20 1430:!: 20 1420 ::1: 10
бsмс 1365 :i: 25 1355 :!: 10 1360:!: 15 1365:!: 10 1370 :i: 20 1355 ::1: 10
рМс 1085 :i: 70 1060:!: 40 1070 :i: 25 1080 :i: 50 1050::1: 30 1t20 :i: 20
р'Ме 985 :!: 85 1000 :i: 25 1020:!: 20 995 :i: 55 980 :!: 45 1000 ::1: 65
тМе zoo :i: 70 205 :i: 20 160:!: 50
R Ме molecules
R = R'C(===O) (see Section 7.1.5), R'HNc(==O) (see Section 9.3),
R'R"NC(==O) (see Section 7.1.5), R'OC(==O) (see Section 10.2.3),
R'SC(==O) (see Section 7.1.5).
2.1 Me/hy/
23
2.1.7 Methyl esters
Discusscd will Ьс mainly mcthyl cstcrs ofthe (урс R'C(==O)OMc, Ьи! mcthyl esters
of tllc (урс R'C(==S)OMc, R'S(==O)OMc, R'R"P(==O)OMe and R'R"P(==S)OMc
arc also mcntioncd.
Strctching vibrations
In thc spcctra of mcthyl cstcrs thc ovcrlap of the regions in which both
antisymmctric strctchings absorb with а weak (о medium intcn5ity (3020 :i: 30 and
2990::1: 40 cт 1) is по! large. Both normal modes are u5ually observed 5eparateJy.
Methyl formate displays the stretching vibrations in the neighbourhood of 3037
and 3010 cm l and methyl acetate а! 3030 and 3001 cm l. With methyl esters of
unsaturated carboxylic acids thc l.IaMe саппо! always Ье attributed unambiguously
because the ==СН stretching modes also occur in the vicinity of 3000 cm l. А
molecule such as ClzP(==S)OMe displays both antisymmetric stretches а! 3030
and 3004 cт 1.
AJthough methyl esters absorb weakly or with medium intensity in the region
2920::1: 80 cm l, the literature is по! always unanimous concerning the assignment.
The discrepancics result because, for ОМе substituents, overtones and combination
bands of thc symmetric and antisymmetric bends сап adopt considerabIe intensities
Ьу Fermi resonance so that these absorptions mау wrongly Ье interpreted as normal
vibrations. This сопсер! is gradually being abandoned. lПе extra bands are рroЬаЫу
the result of individual СН strctching modes of the methyl group сараЫе of taking
different positions relative to the free pair of electrons of the О atom. lПе highest
wavenumbers for this vsMe are found in the spectra of КОС(==О)ОМе (2996
cm l), FzP(==O)OMe (2978 cm l) and FC(==O)OMe (2974 cm l). If these high
valucs are neglectcd the region is reduced (о 2905 :i: 65 cт 1.
Dcformations
With methyl esters the overlap of the regions in which the methyl antisymmetric
deformations are active (1460 ::1: 25 and 1455 :i: 20 cm l) is quite strong,
which lcads to тапу coinciding wavenumbers. This is obvious, по! опlу for
the antisymmetric deformations, Ьи! also for the symmetric deformation mostly
displayed а! the LW side (1435 :i: 35 cm l). lПе symmetric deformation of
oxygen attached methyl absorbs а! higher wavenumbers than are norma1ly shown
Ьу saturated hydrocarbons. lПе intensity of these absorptions is опlу weak to
moderate.
Rockings
Both rockings are active in the region 1170 ::1: 50 cт l with а band intensity
which is sometimes weak although the band сап also Ье of medium intensity
24 Norтa/ \Ii/тr/iol/S ат/ AbsOllJ/ioll UegiOlls 0/ СХ.!
or SОl11еtiП1СS CVCI1 ЬС strong. ТllC vibratiol1al nlOdcs arc gCl1crally ollscrvcd
scparatcly, for instancc 1202 al1d 1159 for CIC(==O)OMe. IIlJ4 al1d 1163 for
МсС(==О)ОМс and 1I72 al1d 1145 СП1 1 for CICH 2 C(==0)OMc. Tllis is по!
111C case for МС2Р(==0)ОМс, Cl2P(==S)OMe al1d McS(==O)OMc, \VllCrC both
rockings havc Ьееп placcd rcspcctivcly аl 1187, 1 175 al1d 1173 ст 1 .
ТаЫе 2.8 Absorption regions (cm l) of nlctllyl in mctllyl csters
C(==O)OMc C(==S)OMc S(==O)OMc >Р(==О)ОМс
and
>P(==S)OMc
vaMe 3020 :J: зо 3015 :J: 25 3015 :J: 25 3020 ::1: 30
v'a Me 2990 :J: 40 2995 :J: 15 3000 :J: 25 2985 ::1: 35
vsMe 2920 :J: 80 2940 :J: 20 2940 :J: 25 2930 ::1: 30
БаМе 1460 :J: 25 1460 :J: 15 1465 ::1: 20 1460::1: 15
Б'а Ме 1450:!: 15 1450:!: 15 1455 ::1: IO 1455 ::1: 15
БsМе 1435:!: 15 1415:!: 15 1445:!: 15 1445 ::1: 25
рМе 1185 :J: 35 1175::1: 25 1195::1: 25 1185::1: 15
р'Ме 1155 :J: 35 1145 :J: 25 1165::1: 25 1165::1: 25
тМе 225 :J: 65 250 :J: 40 220 :J: 50
R Me molecules
R = R'C(==O)O (see Section 7.1.8), R'C(==S)O (see Seclion 10.1.2),
R'S(==O)O (see Seclion 10.1.2), R'R"P(==O)O and
R'R"P(==S)O (see Section 10.1.2).
2.1.8 MethyI ethers
Molecules of the [уре R' OMe, in \vhich R' is а salurated or ап unsaturatcd
sub5tituent or а (substituted) aromatic ring, have served (о estabIish the absorption
regions of the ОМе group.
Stretching vibrations
lПе antisymmetric stretchings are observed in the regions 2990 ::1: 40 and 2955
:J: 35 cm J. Тhe band intensity is generally weak or medium. lПе highest values
for the methyI antisymmetric stretchings have Ьееп attributed in the spectra of
ClzHCCFzOMe (3027 and 2974 cm I). FCHzOMe (3024 and 2976 cm l) and
BrcHzOMe (3021 and 2965 cm 1). Lo\v values for these modes are found in (Ье
spectra оС МеОСН==СНОМе (both stretchings а! 2955 cm I), HzC==CHOMe
(2959 and 2927 cm l) and МеОМе (2988 and 2922 cm I). Most of (Ье aromatic
ethers give these stretching5 in the neighbourhood of 2985 and 2950 ст 1 .
2.1 Me//1Y/
25
Thc mcthyl symmctric stretching in ethers absorbs in thc neighbourhood of 2850
сm 1 as а sharp discrctc pcak with а medium intcnsity, that is аЬои! 50 cт 1
lowcr than in mcthyl cstcrs and typical for mcthyl ethcrs. I! seems that the methyl
strctching vibrations absorb а! thc HW sidc оС the abovc-mentioned wavcnumbcr
rcgions if ОМе is adjaccnt (о а partly or complctcly halogen substituted carbon
atom. IС morc bands arc prcscnt than cxpcctcd, this is almost ccrtainly due (о the
various positions оС thc СН bonds with rcspcct to thc free pair of elcctrons of the
О atom.
Deformations
Both methyl antisymmctric (1465::1: 20 and 1455:!:: 20 cm l) and 5ymmetric (1450
::1: 20 cт 1) deformations absorb in narrow wavcnumber regions with varying band
intensities. In addition, the overlap is considerabIc, so that coinciding wavenumbers
frequently occur. It is obvious that the antisymmctric dcformations of methyl esters
and ethers absorb in almost similar rcgions although the symmctric deformation in
esters generaJJy absorbs аЬои! 15 cт l lower than in ethers.
Rockings
The mcthyl rockings of saturated, unsaturated and aromatic methyl ethers absorb
in the regions 1190 ::1: 45 and 1155 ::1: 35 cт 1. With saturated ethers, the anti
symmetric СОС stretcl1ing vibration (1110::1: 70 cm l) is aIso active in the above-
mentioned region. This band is strong and mostly occurs а! the LW side of both
rockings. With aromatic methyl ethers some planar СН bends absorb in the above
mentioncd regions and the possibility that опе of the rockings coincides with these
absorptions is therefore substantial. Methoxybenzene di5plays опе Ме rocking а!
1180 cm 1. The other is по! assigned unless this mode accidentally coincide5 with
the first or with а СН planar bend.
MethyI ethers display the highest рМе а! 1190:!:: 45 cm 1, mostly centred around
1200 cm l. The high value of 1250 cm l observed in the spectrum of methoxy
methane is outside the above mentioned range. High values are also scored Ьу
MeOCHzOMe (1232 cm I), 2 MeOPhOMe (1231 cm 1), cBuOMe (1228 cm l),
BrCHzOMe (1227 cm l) and 3 MeOPhOMe (1210 cm l). Low rockings have
Ьееп assigned in the spectra of 2 lПОМе (1151 cm 1), МеООМе (1156 cm l)
and Cl z CHCF 2 0Me (1159 cт 1).
The highest value for р'Ме is fumished Ьу BrCHzOMe (1190 cт 1) followed
Ьу МеОМе and ICHzOMe, both absorbing а! 1180 cm l. Тhe 10\vest values зrе
1121 cт l from 2 BrPhOMe and 1129 cт 1 from 2 CIPhOMe. Тhe remaining
observed rocking modes gather around 1155 cm 1. lПе rocking modes of methy1
esters and ethers absorb in a1most similar wavenumber regions.
26 Nor/l!lI/ Vi/тl/iOllS lIт! AbsOIP/ioll Uе,чiОIlS о/ СХ з
ТаЫе 2.9 Absorplion rcgions (cm I) of II1Ctllyl il1 mctllyl
etllcrs
OMc
sa!ura!cd
OMc
unsaturatcd
OMc
aromatic
lla Me
l/oMe
IlsMc
Б"Ме
Б'а МС
Б,Мс
рМс
р'Ме
тМе
3000 ::1: 25
2955 ::1: 35
2845 ::1: 25
1465 ::1: 20
1455 ::1: 20
1445::1: 15
1195::1: 40
1160::1: 30
225 ::1: 40
2985 ::1: 35
2945 ::1: 20
2850 ::1: 30
1470::1: 15
1460::1: 15
1450 ::1: 10
1190::1: 30
1145::1: 25
235::1: 15
2985 ::1: 20
2955 ::1: 20
2845 ::1: 15
1465::1: 10
1460::1: 15
1450::1: 10
1190::1: 45
1150::1:30
R Me nlOlccules
R = R'O (see Seclion 10.1.2).
References
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2./ Me/hy/
27
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28 NоI'IIШ/ Vi/n'a/iolls аш/ A/JSOIP/ioll Regiolls о/ СХз
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69. Е. Tanncnbaum. R.1. Meycrs and W.D. G\vinn, J. ClII'III. 1'11.\'.1'.. 25,42 (1956).
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2.2 TRIНALOGENOMETHYL
lПе СХз group (Х = F, CI, Br and 1) posse55es as тапу normal vibrations as
methyl and, as halogen atoms are much heavier than hydrogen, these modes are
expected а! considerably lo\ver values. lПе band intensities are strongest with the
5tretching vibrations in the sequence F>CI>Br>I. Stated differently, the intensity
correlates more or less with the difference in electronegativity be!\veen the Х and
the С atom.
For most of the R Me molecules the antisymmetric stretching vibrations and
deformation5 ab50rb а! the HW side, and the symmetric mode а! the LW side
of the region in \vhich these vibrations are found. Thus, the antisymmetric modes
generally pos5e5s а higher wavenumber than the symmetric ones. This is not al\vays
true for R СХз molecules with Сзv symmetry where for R СFз the vs{Б а }
absorbs а! higher wavenumbers than У а {Б s }. For molecules with С . symmetry
опе of the anti5ymmetric stretchings does по! always absorb а! the highest wave
number. This \vould, as with methyl, indicate а dissimilarity in the СХ bonds. Уе!
it is по! always straightforward (о assign unambiguou5ly the symmetric and anti
2.2 Triha/ogeпome/hyl
29
symmctric vibrations if thc molecule саппо! Ье studied in the gaseous phase or, if
it сап, docs поl providc dccisive band structurcs. Оп the other hand, becau5e of
thc non cquivalcncc of Ihc СХ bonds, опе саппо! Ьс certain whether а band arises
СlOm cithcr а symmctric or ап antisymmetric СХ з vibration or from ап isolated
СХ' viЬrаtiол. Morcovcr, as with mcthyl, ovcrtones and/or combination bands of
deformations whcthcr or по! intcnsificd тау occur in the slretching mode area,
which obstructs а propcr assignmcnt. Thcreforc in this text the nine СХз vibrations
will Ье dcsignalcd as follows:
I/СХ у'сх у"СХ > БСХ Б'СХ {)"СХ > рСХ р'СХ > тСХ
Using this notation il is quite possibIe that for instance у"СХ represents ап anti
symmelric mode wilh опс molecule although il more approaches the symmetric
mode in another. For СЗV molecules, for схаmрlе R' С=С СХз, the nOlation5
V s , уа, Б s , Ба and р are still appropriate.
2.2.1 ТrifluoromethyI
The three CF stretching modes absorb in broad regions and are considered as
valuabIe group vibrations merely because of their somelime5 moderate bUI mostly
strong intensily. Тhe intensity of the deformations and rockings varies from weak:
ТаЫе 2.10 Absorption regions (cm 1) of a-di- апd а tri-hаlоgсп substitutcd СFз
Total rеgiоп Molecules аЬsоrЫпg Molcculcs аЬsоrЫпg Rсgiоп of
а! high wаvспumЬеrs аl low wаvспumЬеrs rсmаiпiпg
molccules
l/CF 1315::1: 105 FзС СFз (1417) ХзС СFз (X==I, Br, CI, F) 1295 :!: 45
FзС СFz СFз (1370) (1210, 1234, 1249, 1250)
CI СFz СFз (1354)
v'CF 1270::1: 80 FзС СFz СFз (1350) IзС СFз (1190) 1240 :!: 25
Сl(Вr)СН СFз (1265)
v"CF 1 190 ::1: 80 FзС СFz СFз (1268) FзС СFз (1117) 1195 :!: 30
FзС СFз (1250) СI(Вr)СН СFз (1126)
БСF 715::1: 95 Сl(Вr)СН СFз (808) FзС СFз (619) 730 :!: 50
FзС СFз (807) IзС СFз (668)
СlзС СFз (793)
Б'СF 620 ::1: 100 FзС СFз (714) FзС СFз (520) 590 :!: 60
Б"СF 565 ::!: 30 СIСFz СFз (593) FзС СI2 СFз (535) 565 :!: 25
pCF 340 ::1: 120 FзС СFz СFз (460) FзС СFz СFз (220) 355 :!: 35
ВrСFz СFз (438) IзС СFз (303)
IСFz СFз (433)
p'CF 275 ::!: 55 FзС СClz СFз (325) ВrСFz СFз (221) 285 :!: 25
FзС СВrz СFз (321) IСFz СFз (223)
30 Norl/la/ ИЬт/irJ/lS ат' A/)S0l1J/ioll Rcgiolls о/ СХ.I
10 mсdiuП1. lПс СF з torsion is cxpcctcd 'о al)sorb il1 thc I1ciglll}()lIrllO()(1 of 100
СП1 I.
R CFl n101cculcs
R = F2CH [1], FзС СF2 [2, 3], CICF2 [4, 5], BrCF2 [4],
lCF2 [4], CI2CH [6], CI(Br)CH [7], FЗС СС]2 , FзС СВr2 al1d
FзС СI2 [3], F.1C , CI.1C ' ВrзС and I.1C [8].
ТаЫе 2.11 ЛЬsоrptiоп regions (cm l) оС CF.1 in trifluoroacctyl
Tolal regiol1 Moleclllcs absorbing Molcculcs absorbing Region оС
а! high \vavcnumbcrs а! lo\v wavenumbcrs remainil1g
molecules
/JCF 1290:!: 85 F.1 СС( ==O)N(Me )С(== O)CF 3 АgОС(==О) СFз (1206) 1290::1: 60
(1374) NaOC{==O) CF.1 (1213)
МсОС(==О) СFз (1368) ВrCНzС(==О) СFз (1217)
v'CF ШО:J:50 FзС ОС(==О) СFз (1258) MeC(==O) CF.1 (1163) 1220::1: 30
FC(==О) СFз (1254) ВrСН2С(==0) СFз (1168)
РhС(==О) СFз (1180)
v"CF 1165 :J: 55 FзСС(==О) СFз (1219) NаОС(==О) СFз (1140) 1175::1: 30
FС(==О) СFз (1214) МеОС(==О) СFз (1144)
БСF 700 :J: 85 НзSiOС(==О) СFз (785) МсС(==О) СFз (615) 735 ::1: 45
(region оС Бс==о )
Б'СF 590 :J: 80 РhС(==О) СFз (670) НзSiOС(==О) СFз (517) 570 ::1: 20
FзСС(==О) СFз (633) F.1СОС(==О) СFз (520)
АgОС(==О) СFз (606)
Б"СF 515:!: 20 ЕtSС(==О) СFз (536) НSС(==О) СFз (496) 515::1: 15
pCF 355 :J: 130 РhС(==О) СFз (484) НSС(==О) СFз (228) 335 ::1: 80
Н2NС(==0) СFз (435) МеС(==О) СFз (246)
FзСОС(==О) СFз (433)
р'П 230 :J: 40 НzNС(==О) СFз (265) F.1СС(==О) СFз (193) 230 ::1: 25
FзСС(==О) СFз (257)
R СRз molecules
R = R'C(==O);
R' = H [9 I4], o [9 II], Me [15], MeC(==O)CHz , MeC(==0)CD2 ,
FЗС С(==0)СН2 and FзС С(==О)СDz [16], 2 Th CH2 [171,
BrCHz [18, 19], FзС [2, 2Q...-22], FзСС(==О) , Ph , H2N [23 26],
FзСС(==О)NМе , HO [11, 27 34], DO [11,33, 34], MeO [35 37],
ЕtO , FзСО [38], NaO [39 1], AgO [40], HzC==CH O [36],
4 02N PhO , FзСС(==О)О [11, 33], НзSiO and DзSiO [37],
HS [11, 42], EtS , F [1I, 13,14,40,43, 44], Cl [11, 13, 14,42,
45, 46], Br [45, 46], l [47].
R = FC(==S) [48].
2.2 TrillO/ogellome/11Y/ 31
ТаЫе 2.12 Absorptiun regions (cm J) of Q-saturated СFз
TuJal regiun Molecules absorbing Molcculcs absorbing Rcgion of
а! high wavenumbcrs а! low wavcnumbcrs rcmaining
molcculcs
уср 1295::1: fi5 МсСD(ОН) СFз (lзnrJ) СlзС(ОН)С(СFзn (1238) 1300 :1: 40
f'зССН(ОН) СFз (1350) FзССD(ОН) СFз (1255)
FзССН(ОН) CFз (1258)
v'CF 1215::1: 65 DIIN СНz СFз (1275) НСFз (1152) 1210:1: 40
[)2N СН2 СFз (1273)
ВrСНz СFз (1274)
[СНz СFз (1259)
v"CF 1 J 20 ::1: 70 FзС СН(ОН) СFз (1188) НzNСН2 СFз.НСI (1054) 1130:1:40
FзС СНz СFз (1178) Вr СFз (HJ85)
DIIN СНz СFз (1175) FзС СНz СFз (1088)
6CF 695 ::1: 95 (HzN)zC(CF3)Z (785) НО С(МС)2 CFз (602) 660 :1: 50
С1 СFз (783) FзС СD(ОD) CFз (605)
Вr СFз (762)
Б'СF 585 ::1: 65 МсСН(ОН) СFз (650) ВrСН2 СFз (526) 575 :1: 40
(HzN)zC(CF3)Z (638) FзС СН(ОН) СFз (520)
6"CF 530 ::1: 45 НОС(Мс)z СFз (575) С1зС(ОD)С(CFз)z (487) 530 :1: 30
СI СFз (562)
pCF 360 ::1: 125 4 МеS(==О)zОСНz СFз FзС СН(ОН) СFз (237) 325 :1: 65
(484)
Н2NСНz СFз (422) FзС СD(ОН) СFз (240)
DНNСНz СFз (407) FзС СD(ОD) СFз (240)
DzNСНz СFз (398)
p'CF 275 ::1: 115 Н2NСНz СFз (383) FзС СН(ОН) СFз (167) 260 :!: 40
DНNСНz СFз (367) СlзС(ОН)С(СFз)z (169)
DzNСНz СFз (364) FзС СD(ОН) СFз (170)
МеС(0Н)(СF3)2 (170)
TCF 100 ::1: 30
R СFз molecules
R = H [49, 50], D [49], Me [8, 51 54], FЗССН2 [55 57],
HzNC(==O)CHz , HOCHz [5 1], MeOCHz [62],
HzC==CHOCHz [63], 4 MePhS(==0)zOCHz , HzNCHz ,
DHNCHz and DzNCHz [64], СlНзNСНz , FCHz [65, 66],
CICHz [6, 66], BrCHz [65---67], ICHz [65, 66], MeCН(OН) [68,69],
MeCH(OD) , MeCD(OH) and MeCO(OO) [68], MeCН(OMe) [72],
32 Norl1la/ VilJl'a/iolls arlc/ AlJsorp/ioll RegiOlls о/ СХ з
FзССН(ОН) [70, 71, 129], FзССН(ОD) , FзССD(ОН) al1d
FзССD(ОD) [70, 71], FзССН(ОМс) [73], СlзССН(ОН) [74],
ЕtOСН(ОН) , HOC(MC)2 [751, McC(OH)(CF.l) [76],
СlзС(ОН)С(СFз) and СlзС(ОD)С(СFз) [77], (НzN)2С(СFз) and
(D2N)2С(СFз) [78], Cl [79 1], Br [80,81].
ТаЫе 2.13 Absorption rcgions (cm I) of a-un5aturatcd СFз
Total region Molcculcs absorbing
а! 11igll \vаVСПllmЬеrs
Molcculcs absorbing
lo\v \vavcnun1bers
Rcgion of
rcmaining
molecules
vCF 1285:!: 105 a (CF3)2C==NH (1389)
F С=С СFз (1376)
N==N==С(СFз)z (1361)
FзС С=С С=С СFз 1295::1: 50
(1185 and 1232)
N=С СFз (1227)
v'CF 1195::1: 20
1195::1: 20
v"CF 1135:!: 80 а NС СFз (1214)
FзС С=С СFз (1198)
БСF 685:!: 75 cis FзС СН==СН СFз cis FзС СН==СН СFз
(759) (61 О)
FзС С=С С=С СFз 1160::1: 25
(1056)
675 :!: 50
Б'СF 575:!: 65 а FzС==С(ОН) СFз (515)
Б"СF 505:!: 65 а FзС С=С С=С СFз О==С==С(СFз)z (448)
(568)
605 ::1: 35
515 ::1: 35
N==N==С(СFз)z (450)
FzС==С(ОН}) СFз (456)
pCF 405 :!: 95 а cis FзС СН==СН СFз N==N==С(СFз)z (314)
(480, 496)
FзС С=С С=С СFз О==С==С(СFз)z (314)
(494)
425 :!: 50
p'CF 320:!: 40
320 :1: 40
TCF 65 :!: 35
а Absorption regions of СЗV molccule5: vsСFз, vаСFз, БаСFз, БsСFз and р СF з.
R СFз molecules
R = HzC==CH [82, 83], cis and /ralls FзС СН==СН [84],
ЕtOс(==о)сн==сн , НN==С(СFз) [69, 85], N==N==С(СFз) and
О==С==С(СFз) [85], Fz==С(ОН) [86], H C=C [87 90],
O C=C [88 90], FзС С=С [87, 88], FзС С=С С=С [91],
N=C [92, 93], F C=C [90], CI C=C , Br C=C and
I C=C [90,94].
2.2 Trilla/ogeпoтe/hy/ 33
ТаЫс 2.14 AIJsorption regions (cm I) of СFз in substituted Ьспzспсs
Total region Molecules absorhing Molecules absorbing Rсgiоп of
а! high wavcnumbcrs а! low wаvспumЬсr5 rеmаiпiпg
molcculcs
vCF 1305 ::1: 40 2-F, 5 1[2NРh СFз (1343) Ph-ds СFз (1270) 1315:!: 25
2-МсО, 5-0zNРh СFз (1342) 3-FзС, 5-Н2NРh CFз
( 1279)
2-НО(0==)С, 3 FзСРh СFз 3-FзС, 5-НОРh СFз
(1342) (I279)
v'CF 1160 ::1: 30 Ph-ds СFз (IIЗО) 1170:!: 20
2-МсО, 5 02NРh СFз
(I 140)
v"CF 1135 ::1: 30 4-Н2NРh СFз (I J62) 2-НzNРh СFз (I107) 1135 :!: 20
2, 4 Clz, 5-0zNРh СFз (1161) 2 СIРh CFз (1107)
4-0zNРh СFз (1110)
БСF 650 ::1: 70 4 FзСРh СFз (718) 4 ОzNРh СFз (586) 660 :!: 30
3-02N, 4-НОРh СFз (699) 4 НО(0==)СРh СFз
(588)
3-0zN, 4-НzNРh СFз (696) 4 ВrРh СFз (590)
4-НzNРh CFз (601)
Б'СF 590 ::1: 55 3-НОРh СFз (643) 4-НО(О==)СРh CFз 610 :!: 30
(541)
2-Br, 5 НzNPh СFз
(557)
8"CF 525 ::1: 85 3-02NРh СFз (606) 4 ВrРh СFз (441) 540 :f:: 50
3 СI(0==)СРh СFз (592) 4-0zNРh СFз (485)
4-FРh СFз (592) 4-НО(0==)СРh CFз
(487)
pCF 405 ::1: 65 3-Мс(0==)ССНzРh СFз (466) 2-СIРh СFз (340) 400 :f:: 50
2-НО(0== )CCH==CHPh СFз 3-СIРh СFз (342)
(465)
3 НО(0==)ССН==СНРh СFз 3 IРh СFз (345)
(464)
p'CF 310::1: 50 4-0zNРh СFз (358) 3-ВrРh СFз (253) 305 :!: 45
R СFз molecules
R = substituted phenyl (see Section 12.4)
34 Noтlll/ ИlJrаtiО/lS 1111(/ A/)S0l1J/io/l RcgiOl/s о/ СХ3
ТаЫе 2.15 AI)sorplion rcgiuns (Сl11 1) of CFJ alljaccnt 10
N. О. S. Р and Si
N О S Р anll Si
/ICF 1245 :!: 45 1305 :!: 25 1230::1: 50 1210::1: 25
lJ'CF 1210 :!: 40 1250:!: 10 1195:!: 50 1205 :!: 30
l1"CF 1160:!: 60 1185:!: 25 1130:!: 55 1135::1: 55
8CF 750 :!: 50 705 :!: 45 760 :!: 20 730 ::1: 30
Б'СF 600 :!: 50 615 :!: 45 570 :!: 40 565 ::1: 55
Б"СF 560 :!: 60 570 :!: 40 530 :!: 30 555 :!: 35
pCF 410:!: 90 430 :!: 60 310:!: 50 240 ::1: 60
p'CF 310 :!: 70 350 ::1: 60 250 :!: 50 210:!: 80
TCF 60:!: 40 125 :!: 50
R СFз molecules
R = O==N [95, 96], 02N [97 99], FzN [100], FzS==N [101], cis and
/ra/lS FзС N==N [84, 102], CN [103], HO [104], FзСО [105],
FзСОО [106---108], FC(==O)O [109], FзСООО [107, 108J,
FзСОС(==О)О and FзСС(==О)О [38], HS [11Q....113], DS
[113], FзСS [114, 115], FзСSS [114], CIS [116], CISS [117],
FзСSF2 [118], FзS [118], F5S [119], FзСS(==О) [114],
HOS(==0)2 [120], ClS(==O)z , OS(==O)z [121], 2,6 EtzPhNHS
(==0)2 , NCS [169], HzP [122], MezP [123], ClzP [124],
F2P(==0) [125], ClzP(==O) [126], НзSi [127], МезSi [128],
(СDз)зSi [128].
2.2.2 Тrichloromethyl
Because chlorine is heavier than fluorine the stretching vibrations obviously absorb
а! lo\ver wavenumbers compared \vith those of the trifluoromcthyl group. ТЬе
inten5ity of the bands varies from moderate (о strong. Опе easily appreciates
that, in contrast (о similar R СFз molecules with СЗV symmetry, for which the
symmetric СF з stretching vibrations absorb а! а higher value than the antisymmetric
mode, the ССl з antisymmetric stretching vibration absorbs а! а higher value (Ьап
the symmetric mode. lПе intensity of the deformation, however, is normally very
weak.
2.2 Trilla/oge1/0me//1Y/ 35
ТаЫе 2.16 Absorption regions (cm I) of ССlз
Total rt:gion Malcclllcs absorbing Moleculcs absorbing Rcgion of
а! high wavcnumbcr а! low wavcnumbcr rcmaining
mo1cculcs
vCCI 805 ::1: 95 СI2СНС(==0) ССlз (895) МсССlз (713) 815 :f: 55
Cl2C1 IСН(СI) СС1з (870) DСС1з (744)
СlzСIIССlz ССlз (870) СlзSi ССlз (751)
v'CCI 730 ::1: 85 ОСN С(==О) ССlз (8]4) СlзС С(==О) ССlз 730 :f: 60
(661,645)
СIS(==О)z ССJз (813) СI2СНС(==0) ССlз
(648)
СIСНZСН2 ССlз (797) НzС(==О) ССlз
v"CCI 555 ::1: 125 СlзС ССlз (678) СlзС ССlз (430) 540 :f: 90
Н ССlз (668) FзС ССlз (430)
D ССlз (655) 02N ССlз (439)
cCCI 365 ::1: 70 пРrОС(==О) ССlз (433) FзSi ССlз (299) 365 :f: 50
пВuОС(==О) СClз (432) СlзSi ССlз (300)
СIС(==О) ССlз (428) ноq==О) ССlз (302)
c'CCI 325 ::1: 60 СIМе2ССНz ССlз (382) DС(==О) ССlз (268) 325 :f: 45
НС(==О) ССlз (270)
Б"ССI 290 ::1: 65 МеСН(СI)СНz ССlз (353) СlзС ССlз (225) 290 :f: 50
F ССlз (349) DС(==О) ССlз (228)
С1Ме2ССНz ССlз (345) СlzСН ССlз (238)
реСI 225 ::1: 35 СIСНzСНz ССlз (252) McCH(Cl)CHz ССlз 225 :f: 25
(191)
(СFз)зСОН (192)
(СFз)зСОD (193)
p'CCI 150::1: 80 пРrОС(==О) ССlз (230) DС(==О) ССJз (70) 155:!: 45
МеОС(==О) ССlз (217) НС(==О) ССlз (84)
пВuОС(==О) ССlз (209)
TCCI 100::1: 50 100 :f: 50
R ССlз molecules
R = H [50, 130 133, 168J, D [130, 131, 168], Me [54, 13 138],
Et [139, 140], CICHzCHz [139, 141, 142], BrCH2CHz [139, 142],
CICHz [134, 143], MeCH(Cl)CH2 MeCH(Br)CH2 and MeCD(Br)CH2
[142], CIMezCCHz and BrMe2CCHz [142], HOCH2 [58, 59],
C]C(==O)OCHz , CI2POCHz , ClzP(==0)OCH2 , MeCH(OН) ,
CI2CH [134], CICHz CHC1 , CI2CH CHCl and
ClzCH CClz [141], CIC(==O)OC(Me)z , CI2POC(Me)2 ,
НО(СFз)z and DО(СFз)z [77], МеzС(ОН) , HO(0==)C C(OH)2 ,
FзС [5, 8], СlзС [134, 144], HC(==O) and OC(==O) [145, 146,
36 Norl1ltl/ \!iZ,ra/;OIls llIu/ AlJsorp/io/l Regio/ls о/ СХ3
170], CI CHC(==O) , ClзСС(==О) , H NC(==O) [23], HOC(==O)
[147 149], OlC (39, 171], C1C(==0) [147], O==C==N C(==O) ,
McOC(==O) and CO.10C(==O) [147, 150], ЕtOС(==О) [151],
nPrOC(==O) and IIBuOC(==O) [152], СlзСС(==О)ОС(==О) ,
HSC(==O) [153], H C==CH [1541, CI2C==C(CI) , NC [155],
Ph [l5 158], 2 FPh , 2-СIРll , 4-СIРll , 4 CI.1CPh , 2 CI, б
FPh , O N [171], СIЗСS(==О)l [172], HOS(==O)z [159], CIS ,
CIS(==O)l , F [160], Br [132], H.1Si , DзSi , F.1Si and
СlзSi [161].
2.2.3 ТriЬromОП1еthуl
The number of invcstigated nlOlecules is (оо SП1аll (о attach а 1о! of уаlие (о the
ob5erved regions. Moreover, many as5ignments are still uncertain.
ТаЫе 2.17 Absorption rcgions (cm I) оС СВrз
vCBr
II'CBr
v"CBr
БСВr
705 :!: 80
645 :!: 25
410 :!: J60
240 :!: 40
Б'СВr
Б"СВr
pCBr
p'CBr
235 ::1: 25
190::1: 50
165 ::1: 55
145 ::1: 35
The broad region of 1/'CBr is due 10 Ihe 10w values assigned in the spectra of
ВrзС СВrз (558 and 256 cm I), FзС СВrз (282 cm l) and НС(==О) СВrз
(324 cm I). If Ihe5e values are neg1ected, the region of v"CBr is reduced (о 490 :!:
80 cm l. Тhe СВrз torsion рroЬаЫу ab50rbs in the neighbourhood of 100 cт 1.
R СВrз molecules
R = H and o [131, 162], Me [54, 163], HOCHz [59], BrCH2 ,
CI2P(==0)OCH2 , FзС [8], ВrзС [164], HC(==O) [145, 146,
166], HOC(==O) , 02C [39], CIC(==O) [165], NC [167],
ВrзСS(==О)z [172], F .
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2.2 Tri/lO/ogellome//1Y/
39
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2.3 TERTIARY BUTYL
The simplest tBu moleculcs are those of (уре МезСХ (Х = halogen, C=N, С===СН,
etc.). lп the sterically favoured С 3> structure, а hydrogen atom of each methyl group
2.3 Terliary Вшуl
41
is in а planc of symmctry while the two other hydrogen atoms of each Мс group
arc symmetric with rcspcct (о this plane. For instance, X tBu (Х = halogen) is
of Сз,. symmctry so that thc 24 normal vibrations diffcrentiate between 8аl + 4az
+ 12е vibrational modcs. From these, 23 (7а, + 4az + 12е) сап Ье attributed (о the
(Ви substitucnt, 19 (7а) + 12e) of which ате IR active. Тhe remaining vibration is
thc уСХ (а,).
The correlation bctwccn С3У and С, is as follows: 8а) = 8а'; 4а2 = 4а" and 12e
= 12а' + 1 2а", so that with С, symmetry of Х tBu, the 36 normal vibration5 ате
distributcd in 20а' + 16а" vibrational species. Substitution of the IIСХ (а') Ьу а
torsion results in 19а' + 17а" normal vibrations for tBu. MolecuJes with two (Ви
substituents in gauche position, those responding (о D3d symmetry, often occur in
the liquid state. The corrclation D3d (о С ЗV is as follows: alg(R) and az,,(IR) = а,;
eg(R) and ell(ir) = е and aZ g and а," = az. Similarly (о the az vibrations with С3У,
tl1e aZ g and а)" modes are inactive. With molccules bclonging (о а point group
other than С ЗV ( C s , С з , . . .) thc (Ви substituent is often described in terms of С 3У '
Especially for those molccules where the С3У symmetry is mоте от less perturbed
(HO tBu, HS tBu), the е modes do по! split significantly. Тhe az modes, оп the
other hand, are weakly active. The absorptions intensify with descending symmetry
or in the soIid state of the molecule. In practice this often results in 23 vibrations
plus а torsion. Еуеп if thc е vibrations occur as а doublet, the wavenumber values
are normalIy so closely packed that, in considering the tBu substituent, only 24
regions instead of 36 wiII Ье discussed.
Methyl stretching vibrations
УаМе(а", е) УаМе(а", е) уаМе(а', а1) у..Ме(а', е) IIsMe(a', а1)
УаМе(а') УаМе(а') У а Ме(а", az) у..Ме(а")
2980 ::1: 30 2960 ::1: 30 2945 ::1: 45 2905 :1: 45 2885 :1: 35 cт 1
Although the (Ви substituent сап provide six methyl anti5ymmetric stretching
vibrations, generally only three are observed as moderate or strong bands. Тhe а2
vibration is generalIy very weak or inactive. Molecules such as F tBu (3010 cm 1)
and OzN tBu (3006 cт 1) оссиру the HW region while aromatic molecules
usually absorb а! the LW part of the region. For instance, 4-НОРh tВu displays
УаМе а! 2910 cт 1 and 4 tBuPh tBu а! 2905 cm l. Most tBu molecule5 give
these methyl antisymmetric stretching vibrations between 2990 and 2930 cm ':
УаМе 2970:!: 20 2970::1: 15 2950 :1: 20 cт 1
lПе methyl symmetric stretchings are active between 2950 and 2850 cm l.
Aromatic molecules usualIy display these symmetric stretching vibrations between
2915 and 2860 cm l.
42 Norlllo/ Vi/тlliolls ат/ Absorplioll ИсgiОIlS о/ СХз
Mcthyl dcformations
БаМс(а', а\) БаМс(а", с)
БаМс(а')
БаМс(а", а1) Б"Мс(а", с)
БаМс(а')
1470 :1: 25
1465 :1: 25
1460 :1: 25
1460 :1: 25
111е mcthyl antisymmctric deformatiOI1S absorb betwccl1 1495 al1d 1435 сm 1 .
Usually, thc al and с vibrations appcar spectrally as moderatc (о strong bal1ds.
Molcculcs SUcl1 as 01N tBu (1493 сш 1), NC tBu (1486 or 1480 cm l),
P attached (Ви (1485 1475 cm 1) and tBu C=C C=C tBu (1483, 1480
cm l) absorb а! thc HW sidc of the rcgion. Thc latter molccule (1425 СП1 I) and
CI tBu (1438 cm l, ca1culated for the а\ vibration) togethcr provide thc lowest
values. The remaining molccules display БаМс bet\vccn 1480 and 1440 cт 1 in
regions given belo\v :
БаМе 1465:1: 15 1460 :1: 15 (1460::1: 15) 1455:1: 15 cт 1
Although three (2а' + а") methyl symmetric bending vibrations are expected {two
(al + е) in thc case of Сз,. symmetry} often only two emerge.
БsМе(а', а\) БsМе(а', с)
БsМе(а")
1395 :1: 25 1375 :1: 25 cm 1
As far as the al(a') mode is concerned, which absorbes in the range 1395 ::1: 25
cm t, the highest values have Ьееп obscrved for HOC(==O) tBu (1414 cm \),
P attached ,Ви (1400 :1: 10 cm l), OzN tВu (1406 cт 1) and HC(==O) tBu
with 1405 cm \. lПе remaining molecules mostly absorb in the narrow region
1385 :1: 15 cт \. lПе е mode, which is supposed (о split ир into two (а" + а')
counterparts, mostly appears as а single rather than а twin band. The strongest
band БsМе(а") а! the LW side, sometimes accompanied Ьу the а' mode (1375 ::1:
20 cm J), appears in the region 1365 :1: 15 cm l. The higl1est values are displayed
Ьу FzP(==O) tBu and F tBu, both absorbing а! 1374 cт 1, 01N tBu (1373
cт 1) and CN tBu (1372 cт 1). The lowest wavenumber for this mode has
Ьееп observed for DC(==O) tBu (1350 cт 1) and the remaining investigated
molecules absorb in the extremely narrow region of 1365 ::1: 5 cт t, а range which
is much narrower than observed for the same mode for acetyl (Section 2.1.6).
Skeletal stretchings and methyl rocks
Despite the fact that аl1 three СС з stretching vibrations severely couple with the
(six) methyl rocking modc5, six absorption regions more or less overlapping опе
2.3 Ter/iary Blllyl
43
anotl1cr сап Ьс assigncd. Normally, the thrce е modes, each of which is expccted
(о split into а' + а" counterparts, 1.10 по! always appear as doubIets. Тhe а2 mоие,
forbiddcn for С3,' molccules, somctimes emerges as ап iII dеfiпеd ab5orption Ьапd.
1/"ССз(а", е) v,ССз(а', al)
v а СС з(а')
1235 ::1: 60 800 ::1: 90 cт 1
The зпtisуmmсtriс СС3 strctch (а", е) normally appears in (Ье аЬоуе-
mentioncd rcgion with high v31ucs (1293 cm I) for both HzC==C(Me)CH2 tBu
and H2C==C(Me) tBu and also for HOCHz tBu (1288 cm 1). l..ow values,
coincident with the first mcthyl rocking mode, have Ьееп observed for
Cl2P(==S) tBu (1183 cт 1), H tBu (1189 cm I), Ph tBu (1189 cm l) апd 4-
BrPh tBu (1203 cm 1). The remaining investigated molecules display уаССз(а/)
in the region 1240 ::1: 35 cт 1. The v"ССз(а') absorbs iп the region 1220 :I: 40
cт 1. Disregarding some high {Iow} values around 1255 {1185} cm l, this mode
mostly appears in the region 1215 ::1: 25 cm l, often Ьи. поt always соiпсidепt
with УаССз(а") and sometimes with рМе(а', а1),
Sometimes the v.,СС з (а', а,) is of reasonabIe intensity, but normally this viЬrаtiоп
mode absorbs weakly in the region 800 :!: 90 cm 1. Еуеп сопsidеriпg the fact that
after disregarding some high and low values of this rапgе most molecules display
VsCC3 а! 795 :1: 60 cm 1, it is still а too large region for purposes of idепtifiсаtiоп
of the (Ви group.
рМе(а', al) рМе(а", е) рМе(а", az)
рМе(а')
1160::1: 55 1035::1: 55 990::1: 50
рМе(а", е)
рМе(а')
925 :!: 35 cт 1
Most of thc investigated molecules display the first methyl rocking (а', al) iп the
region 1150 ::1: 35 ст 1. The рМе( з' and а") both often emerge iп the region
1035 ::1: 55 сm I as sерзrзtе bands or as опе band of weak or moderate intensity.
Disregarding some high values in the neighbourhood of 1085 cт 1 and the vaJue
984 cт l for H tBu, these rockings mainly absorb in the rеgiоп 1045 :I: 30
cm l. Тhe last three methyl rocking modes appear in the rеgiоп 965:!: 75 cm 1,
which tentatively тау Ье subdivided into 990 :!: 50 cт 1 for the а", az-mode and
925 ::1: 25 сm I for the а', а" (е ) modes.
Skeletal deformations
lПе tBu group gives rise (о five (3а' + 2а ") skeletal deformations аЬ5оrЫпg in
three regions:
44 Norllla/ VilJтliollS ат/ AlJSOIplioll Regiolls о/ СХ3
435 :J: 85
335 :J: 80
рССз(а", е)
рС С з(а')
300 :J: 80 Сl11 1
Б"ССз(а", е) бsССJ(а', at)
(I.С С з(а')
Тhesc modcs поrП1аllу producc bands of \veak or П1сdiшn iпtспsitу. TI1C I1igllcSt
{Io\\'cst} valtle5 for Б"ССз arc obscrvcd around 51 О {355} Сl11. 1. Most of thc
Ь"ССЗ пюdсs ha\'c Ьсеl1 assigncd in tllС rcgion 435 ::1: 65 ст 1. TllC DsССз is
\veakly obscrved in the rcgion 335 :1: 80 Сl11 l \VllCre 1110Ieculcs SUCI1 as (ВиI
al1d tBuBr respcctively arc rcspol1sibIc for tllC low vallles of 259 and 303 cm t.
Rougl11y estimated, because mапу аssigпшепts arc поt availabIe, tl1is mode appears
in the ral1ge 370 :J: 50 СП1 1 for tl1C remaining molecules, which also applics (о
the СС3 rockil1g nlOdes absorbil1g \vcakly in tlle rcgion 300 ::1: 80 cm l. However,
these skeletal dсfоrП1аtiопs are по! significant for idепtifiсаtiоп purposes.
Torsions
If the SУП1mеtrу of the molecule lowers [roт С з " (о C s , the degenerate е mode
split5 ир into а' and а" modes absorbing in rcgions aroul1d 250 cт 1. The third
mClhyl torsion, \vhich is of species а2 for Сз,. or а" for С . nlOleculcs, is weakly
acti\'e around 220 cm ' or much lo\ver.
Тhe follo\ving R tBu compounds have Ьееп taken into account:
R = H [1 7], F [1], CI [1 5], Br [1, 2, 5, 6], I [1, 2, 5],
Et [8], HOCH2CH2 , пВи [9], (BиCH2 [10], CICHz [11, 12],
BrCH2 [13], iPr , iВи and Et(CH)Me [14], HzC==C(Me)CHz ,
MeC(==O)CH2 , HOC(==O)CHz , HzNCHz , HOCHz ,
HC(==0) [15, 16], H2NC(==0) , HOC(==O) [17], NaOC(==O) [48],
McOC(==O) and СDзОС(==О) [18], ЕtOС(==О) , CIC(==O) ,
H2C==CH , H2C==C(Me) , (Bи CH==CH , MezC==CH ,
tBu C=C [19], tВи C=C C=C [4], N=C [20, 21],
Ph [22], 3 and 4 MePh [22], 4 CICHzPh , 4 tBuPh [22,
23], 4 HC(==0)Ph , 4-СIС(==0)Рh , 4 HzNPh , 4 SCNPh [22],
2 , 3- and 4-НОРh [24], 4 MeOPII [22], 4 EtOPI1 [22], 4
BrPh , 4-Py , EtNH [47], MeNHC(==O)NH , EtNHC(==O)NH ,
nPrNНC(==O)NH , nBuNНC(==O)NH and tBuNHC(==O)NH [25],
cHcxNHC(==O)NH [26], R'S(==0)2NH [27], OzN [28], OCN [16,
29], SCN [16, 30], HzN [16], CN [31], HO [1, 16, 32, 33],
oo [32], MeO [16, 31], СDзО [16], ЕtO , HC(==O) and
OC(==O)O [34], MeC(==O)O , EtC(==O)O , CICHzC(==O)O ,
BrCH2C(==0)0 , NCCHzC(==O)O , HzNC(==O)O , (BиOO [35],
tBuO N==N O [36], HS [1, 16, 37, 38], MeS [37], EtS [37,
39], MeSS [40, 41], tBuSS [40, 42, 43], HzP [44], FzP [45],
'"
се
т
'о
'" о
с
.2
oi
.Б
.:;
z
g
<)
'о ос
...
I
'" о
с
О 11
. u
с
.2
ё- u
.J:; с
<: :J
r-i u
...
:ё
сп
45
O OOO CO O O O CC CC OCO C
5 B g
ЗЗЗ ЗЗ ЗЗЗ3 S S
OC COOO CCOOO CCCCOCOCCOC
z ББ =
00000 се CCCC CCOCC
Ir) .... ..... ..... .... ..... tr, 1'1 Ir. .... ..... Ir) ...... ..... (". .... .... .... ..... ..... ..... ("1 ('1
;
ЗSЗ З З=
Z = S rlrINN""
З З З
g
Z = E oo r'rlrl
CC C CC C CC COCC C CC
NNM""'Nrl""''''''''' '''''''''",,'''' rl rlrJ n
g
Z ==
O O OO CCCCC C CCCC COOCC CO=
N N NMM rIM rJ I
COO O O CCO O CC COCCO C
С ОО М МN Ж о rl
== MMM rJrIN
CO O C C CC CC C C C O
M MMMM MM M M M MMM M
CC C CC C C CC CC C C
I N MCN M
OO M MMM aCC OO M
MMMMMMMMM
O OOCCOOCC acc aao accC
NNM NNN NM MNN rl NMM M
OOOO . MMMNN oa MMMNNNrl
MMMMMMMMM
:r v) ::: З :Z ::: ::: v) о о v) 00 О'" "''''
'" .... 11) v) м '" '" ""..,. "'''' ..,.
"
о v) о о о Ба '" '" '" О'" "'''' "''''
-;:; '" ..... ..... "" v) '" о о "'''' "'''' "''''
:r '" '" '" :! ... ... о '" .......,. ""'" "''''
'" '" '"
("1 U " "''' " " ",,, " " N
" .. .. " "
Ъ Ъ:
о
"
u
UUUUUUUUUUUUUUUUUUСUuuuuииuОБUСuиииu
UU UUU U
;;; ::r <:t ....o<..<$ <:t
46 Norllla/ lIi/тlli(lI/s al/d A/)SOrplioll Regiolls о/ СХ.!
CllP [46], F1P(==0) [45], CllP(==O) [46], F2P(==S) [45],
CllP(==S) [46).
References
1. О.Е. Мапп, N. Лсqui lа and O.R. Lidc../. Mol. Spl!c/rosc., 2, 575 (195H).
. М.с. To!Jin.J. Л/II. C//I!/II. 50е., 75,1788 (1953).
3. J.C'. Evans and G.I.-5. Lo. J. Л/II. C/11!1lI. 50С., 88, 2118 (1966).
4. J. Nakovich Jr., 5.0. Shook. ЕА. Miller. D.R. l'arJ1cll al1d R.E. Sacllcr, 5pecl/"Ocllilll.
ЛеШ, P<lrl Л, 35А, 495 (1979).
5. NT. McDcvilt. л.L. Rozek, ЕЕ BCl1tlcy al1d А.О. Davidsol1, J. С//еlll. P/,)'S., 42, 1173
(1965).
6. J.E. Bcnic and S. Sundcr. 5pl!clroellilll. Aela, Part А, 30А. 1373 (1974).
7. В. 5chradcr. J. Pacan ky al1d U. PfeifJcr. J. PI/)'s. С/1eI"., 88, 4069 (1984).
8. К Ohno. К. Taga, 1. Yoshida and Н. Murata, 5peclrocilim. ACla, Part А, 36А, 721
(I980).
9. G.л. Crowdcr and R.M.P. Jais\val,J. Mol. Strиcl., 102, 145 (1983).
10. Н. Matsuura, К Fukuhara, К. Takashima al1d М. Sakakibara, J. Мо/. 5Irиct., 239, 43
(1990).
11. Р. Кlaboe, C,j. Nielscn and D.L. Po\vell, 5pcctroe//illl. Аеш, Part А, 41А, 1315 (1985).
12. G.л. Cro\vdcr and \V.-L. Lin, J. Mol. 5Irиct., 64. 193 (1980).
13. G.Л. Cro\vder. С. Harper and M.R. Jalilian, J. Mol. SlrtlCI., 49,403 (1978).
14. G.Л. Cro\vdcr and L. Gross, J. Mol. 5Irиct., 102,257 (1983).
15. G.л. Cro\vder,J. CI/ст. Soc., Perki" Tra"s., 2,1241 (1973).
16. J.R. Ourig, S.M. Cravcn, J.H. Mulligan and C.W. Hawley, J. CI/em. PI/ys., 58, 1281
(1973).
17. \V. Longucville, Н. Fontainc and G. Vcrgoten, J. Ralllall 5pec//"Osc., 13, 213 (1982).
18. R.M. Moravic and J. Corsct,J. Mol. 5Irиc/., 30,113 (1976).
19. Р. Кlaeboe, О. Bougcard, В. Schradcr, Р. Pactzold and С. von Ploto, 5peclrocllim. Лсtа,
Parl Л, 41А. 53 (1985).
20. К Kumar, 5pcclroellim. Aela, Рап А, 28А, 459 (1972).
21. G.л. Crowdcr,J. PI1)'S. Cl,eт., 75, 2806 (1971).
22. G. Varsanyi, Assigll/lle//ts[or Vibralio"al Spcclra 0[5cvclI H"lldrc(1 Bellzelle Derivalives,
J. \Vilcy and Sons, Ncw York (1974).
23.5. Oobos, А. Szabo and В. Zclci, 5pcclroeЫIll. Acta, Parl Л, 32А, 1401 (1976).
24. R. Soda. 81111. ОС/ll. 50с. Jp"" 34,1482 (1961).
25. У. Mido, 5peclroc//i/ll. ACla, Parl А, 28А, 1503 (1972).
26. У. Mido, 5peclroelli/ll. Асш, Par/ А, 32А, 1105 (1976).
27. М. Goldstein, м.л. Russcll and Н.А. WiIlis, SpcclrocЫIll. Acta, p(//.t А, 25А, 1275
(1969).
28. J.R. Durig, Е Sun and Y.S. Li,J. Mol. Slrиct., 101, 79 (J983).
29. О.Е Kostcr, Spee/roclli/ll. Aeta, Parl А, 24А, 395 (1968).
30. R.N. Кnisclcy, R.P. Hirschmann and У.А. Fassel, 5pcclrocЫm. Acta, Parl А, 23А, 109
(1967).
31. D.л. Edwards, S.M. Tctrick and R.A. Walton, J. Orgallolllel. С/ICI"., 349, 383 (1988).
32. J. Korppi Tommola, 5peclrocllilll. Aela, Parl А, 34А, 1077 (1978).
33. J.G. Pritchard and Н.М. Nclson, J. PI/ys. С//еlll., 64, 795 (1960).
34. У. Omura, J. Corsct and R.M. Moravie, J. Mol. 5Irиcl., 52, 175 (1979).
35. О.С. МсКеап, 5pectrocllilll. Aela. Parl А, 23А, 605 (1967).
36. с.А. Oglc, КА. Vandcrkooi, G.D. Mendenhall, У. Lorprayoon and В.С. Comilsen, J.
2.3 Terliary Bllty/
47
Лт. С/le111. Soc., 104,5119 (1982).
37. D.W. Scottt and J.P. McCullough, J. Ат. CI,CIll. 50С., 80, 3554 (1958).
38. J.P. McCullnugll, D.W. Scott, H.L. Finkc, W.N. Hubbard, М.Е. Gross, С. Katz, R.E.
Pcnnington, J.F. Mcsscrly and а. Waddington, J. Лт. CI/elll. 50С., 75, 1818 (1953).
39. М. Sakakihara, 1. Harada, Н. Matsuura and Т. Shimanouchi, J. Mol. 5tr/lcl., 49, 29
(1978).
40. Н. Sugcta, Speclroclliт. Асш, Parl Л, 31А, 1729 (1975).
41. Н. Sugcta, А Go and Т. Miyazawa, BIIII. С//ст. Soc. Jpll., 46. 3407 (1973).
42. К.а. Лllum. J.л. Crcigl1\on. J.H.S. Grecn, а.1. Minkoff and L.1.S. Princc,5peclrocыm.
Лсra, Parl Л, 24А, 927 (]968).
43. J.H.S. Green, 1).1. Harrison. W. Kynaston and D.W. Scott, 5pcclroc/lilll. Acta, Par/ А,
25А, 1313 (1969).
44. J.R. Durig and AW. Сох, Jr., J. Mol. 5Irllcl., 38, 77 (1977).
45. R.R. Holmcs and М. Fild, 5peclrocllim. Acta, Parl А, 27А, 1525 (1971).
46. R.R. Holmcs and М. Fild, 5pec/rocl/im. Асш, Parl А, 27А, 1537 (1971).
47. S. Konaka, J. Hirosc, А Suwa, Н. Takcuchi, Т. Egawa. К. Siam, J.D. Ewbank and L.
Schiifer, J. Mol. 5Irl1ct., 244, 1 (1991).
48. Е. Spinner, J. CI/ет. 50С., 4217 (1964).
3
Normal Vibrations and
Absorption Regions of CH2X
3.1 HALOGENOMETHYL
Similarly to methy\ the CH2X substituent (Х = F, CI, Br and 1) yie\ds nine
поrrnа\ modes \vhich mау Ье described as fol1o\vs: vaCHz, vsCHz, БСНz, wCHz,
ТСН2, pCHz, иСХ, БСХ and torsion, where У, Б, w, т and р respective\y indicate
for stretch, deformation (bend or scissor), wag, twist and rock. The prcsence of
СН 2 Х in а chemica\ structure usual1y \eads (о the existence of several conformers,
each possessing а different energy content wherc the Х atom takes ир different
positions with respect 'о the rest of the mo\ecule. In practice, multip\e bands are
observed for опе and the San1e vibration.
3.1.1 FluoromethyI
In the 5pectrum of f1uoroethane the 5а' + 4а" modes of CH 2 F in the С . conformation
are observed а! the fol1owing wavenumbers:
а' cm 1 а" cт 1
V s CH 2 2960 vaCH z 3003
БСН2 1479 TCHz 1277
wCHz 1365 pCH z 811
vCF 1103 torsion 243
БСF 415
In CH2F compounds both methy\ene stretching vibrations are a\ways observed
separately, with intensities varying from weak (о medium. The methylene
3./ f/a/ogellomelhy/
49
dcformation produccs а band with moderatc intensity but 3 diffеrепtiзtiоп of БСНzF
and othcr methylcne and/or mcthyl dcformation5 of the molecule is по! зlwзyS
fcasibIc. Thc mcthylcnc wug and twist are also well separated but their intensities
ure mcrely weak (о medium.
Thc CF stretch yiclds the most intense absorption of з11 normal modes of CHzF.
Оп account of its intcnsity and smull absorption region, the band is considcred
(о reprcscnt а group frcqucncy, Ьи. estcrs, cthcrs and alcohols 31so absorb in this
region.
ТаЫе 3.1 Absorption rcgions (cm l) оС CH2F
Total region Molecules absorbing Molcculcs absorbing Rcgion of
а! high wavcnumbcrs а! low wavcnumbers rcmaining
molccules
VaCHz 3000 ::1: 50 C1CHzF (3048) FCHzC(==O)CHzF (2964) 2995 :J: 20
FCH2F (3015)
NaOC(==O)CHzF
vsCHz 2965 ::1: 30 CICHzF (2993) BrC(==O)CHzF (2935) 2955 :J: 20
FCHzCH2F (2984, 2959)
БСН2 1455 ::1: 55 FCH2F (1510) NaOC(==O)CHzF (1412) 1455 :J: 25
MeOCHzF (1496) BrC(==0)CH2F (1413)
g-FСН2СНzF (/458, 1409)
tr-FСНzСНzF (/455, 1415)
wCHz 1350 ::1: 85 FCH2F (1435) /r-FСНzСН2F (/371, 1278) 1365 :J: зо
EtOC(==O)CHzF (1410) g-FСНzСН2F (/376, 1285)
MeOCH2F (1405)
TCHz 1205::1: 90 CIC(==O)CHzF (1295) Ir-FCH2CH2F (/240, 1116) 1235 :i:: 45
g-FСНzСНzF (/244, 1119)
vCF 1050 ::1: 60 MeOCHzF (1104) PhCHzF (990) 1050 :J: зо
MeCHzF (1103) CICHzF (1004)
FCHzC=CCHzF (1008)
pCHz 895 ::1: 95 MeOCHzF (990) PhCHzF (808) 920 :i:: 50
+НзNСНzF (980) McCH2F (811)
FCHzC==CCHzF (986)
БСF 420 ::1:: 150 N=CCHzF (567) FCHzC(==O)CHzF (275) 425 :J: 90
HC=CCHzF (544) EtCHzF (315)
HzC==C(Br)CHzF (318)
torsion 180 ::1: 70 MeCHzF (243) 150:i:: 40
R-СНzF molecules
R = Me [1, 2], Et [2], nPr , пВи and пРе [3], Me(CH2)п (п
= 5, 6, 7, 8, 12) [56], FCHzCHz [4], +НзNСНz , H2NCH2 [5],
50 Nотш/ Vibl'alio"s ат! AlJsolptio" Regio"s о/ CH2X
HOCHz [6---10], OOCH2 [6---8], //. апd g FCHz [11 141, ClCHz [15],
BrCH2 [16], FCH2C1-I(OH) [17], Ox [1.8], СFз [19, 20J,
HC(==O) [21], FC(==O) [22 24], Cl(==O) [2 27], BrC(==O) [24,
25], McC(==O) [28 30], FCHzC(==O) [31], ЕtOс(==о) [32],
NaOC(==O) [33], H2NC(==0) [3 39], H2C==CH [4().....43],
H2C==C(CI) and HzC==C(Br) [44], HC=C [45
47], FCHzC=C [48], C1CHzC=C [57], N=C [49 51], Ph [55],
MeO [52, 58], F [53, 54], CI and Br [53].
References
1. О.с. Smith. R.A. Saunders, J.R. Niclsen and Е.Е. Ferguson, J. Clle/II. P/,yS., 20, 847
(1952).
2. а.А. Crowdcr and н.к. Мао, J. Mol. 5Ir11CI., 18, 33 (1973).
3. G.A. Crowdcr and Н.К. Mao,J. Mol. 5Ir11CI., 23,161 (1974).
4. Р. К1аЬос, D.L. Powell, R. Stoclcvik and У. Ocyvind, ACla CI/cIII. 5ca"d., Ser. А, 36А,
471 (1982).
5. J.A.S. Smith and У.Е Kalasinsk'Y, SpeclrociliIII. ACla, Parl А, 42А, 157 (1986).
6. Е. Wyn Jones and W.1. Orvillc Thomas,J. Mol. 5trllCI., 1, 79 (1967).
7. М. РсrtiШi, J. Murto, А. Кivinen and К. Turunen, Spcclroc/liIII. ACla, Parl А, 34А, 9
(1978).
8. G. Davidovics, J. Pourcin, М. Carles, L. Pizzala and Н. Bodot, J. Mol. Slrllcl., 99, 165
(1983).
9. G. Davidovics, J. Pourcin, М. Monnier, Р. Verlaquc and н. Bodot, J. Mol. 5trllct., 116,
39 (1984).
10. G.A. Crowder and О. Tcnnant, J. Flllorille CI/cIII., 6, 279 (1975).
11. Р. К1аЬое and J .R. Nielscn, J. CI1CIII. PI,yS., 33, 1764 (1960).
12. W.c. Harris, J.R. Holtzcla\v and V.F. Kalasinsk'Y,J. С//ст. P//ys., 67, 3330 (1977).
13. В. Bcagle and О.Е. Brown, J. Mol. SlrIIC/., 54, 175 (1979).
14. L.M. Sverdlov, М.А. Kovner and Е.Р. Кrainov, Vibralio"ul Spectra о/ PolyaloIIIic
MolcClllcs, J.Wiley and Sons, New York (1974).
15. J.R. Durig, J. Liu and T.S. Little, J. PI/ys. CI,eIII., 95, 4664 (1991).
16. J.R. Durig, J. Liu and T.S. Littlc, J. Mol. SlrIICI., 248,25 (1991).
17. G.A. Cro\vdcr and Т. Douglas, J. Flllorille CI,em., 7, 537 (1976).
18. R.A. Nyquist, C.L. Putzig and N.E. Skclly, Applie(1 5pcctrosc., 40, 821 (1986).
19. W.F. Edgcll, TR. Riethof and С. Ward, J. Mol. 5PCCI/"OSC., 11, 92 (1963).
20. а.А. Crowder, J. FllюrillС CI/cIII., 3, 125 (1973/74).
21. Н.У. Phan and J.R. Durig, J. Mol. SlrIICI., 209, 333 (1990).
22. R. Fausto, J.1.C. Tcixcira-Dias and M.N. Ramos, 5peclroclliIII. Acta, Parl А, 44А, 47
(1988).
23. J.R. Durig, Н.У. Phan, J.A. Hardin, R.1. Berry and T.S. Little, J. Mol. 5trllct., 198, 365
(1989).
24. АУ. Кhап and N. Jonathan,J. CI/eIII. P//ys., 52,147 (1970).
25. J.E.F. Jcnkins and J.A. Ladd,J. CI/cIII. Soc. В, 1237 (1968).
26. J.R. Durig, Н.У. Phan, J.A. Hardin and T.S. Littlc, J. CI/elll. PI1YS., 90, 6840 (1989).
27. М. Monnicr, G. Davidovics and А. Allouchc,J. Mol. SlrIICI., 243, 13 (1991).
28. G.A. Crowdcr and Р. Pruettiangkura, J. Mol. SlrIICI., 15, 197 (1973).
29. J.R. Durig, J.A. Hardin, Н.У. Phan and T.S. Littlc, Spcc/rociliIII. ACla, Ра/'/ А, 45А, 1239
(1989).
3.1 f/a/ogeпome//1Y/
51
30. G.A Crowdcr and B.R. Cook, J. CI/е1ll. PJ,yS., 47, 367 (1967).
31. G.A Crowder and Р. Pruettiangkura,J. Mol. 5IruCt., 18,177 (1973).
32. М.А. I aso, М.У. Garcia and J. Morcil1o, J. Mol. Slrucl., 115,449 (1984).
33. Е. Spinncr, J. CJlcm. 50С., 4217 (1964).
34. S. Samdal and R. Seip, J. Mol. 5Iruct., 52, 195 (1979).
35. F.M. Abid, J.M. AI-Katti and M.F. EI Bcrmani, J. Mol. 5Ir/lcl., 67, 169 (1980).
36. О. Troitino, Е. Sanchez Ое La Blanca and М.У. Garcia, 5pcclrocJlim. Лсra, Parl А, 46А,
1281 (19'.10).
37. Е.к. Murthy and G.R. Rao, J. Rama" 5peclrosc., 19,359 (1988).
38. Е.К. Murthy and G.R. Rao, J. Rama" 5pec/rosc., 19,419 (1988).
39. Е.К. Murthy and G.R. Rao, J. Rama" 5pectrosc., 20, 409 (1989).
40. R.D. McLachlan and R.A Nyquist, 5peclrocllim. ACla, Parl А, 24А, 103 (1968).
41. J.R. Durig, Т.1. Geyer, T.S. Littlc and О.Т. Durig, J. Mol. 5Irllct., 172, 165 (1988).
42. J. Nieminen, J. Murto and М. Rasanen, 5pcclrocllilll. ACla, Parl А, 47А, 1495 (1991).
43. J.R. Durig, М. Zhen, H.L. Hcusel, Р.1. Joseph, Р. Growcr and т.s. Little, J. PJIYS. C/lem.,
89, 2877 (1985).
44. Р. К1аЬое, Т. Torgrimscn and О.Н. Christensen, J. Mol. 5Irllcl., 23, 15 (1974).
45. J.c. Evans and R.A. Nyquist, 5peclrocllim. Асш, 19, 1153 (1963).
46. R.A Nyquist and W.W. Muelder,J. Mol. 5Irucl., 2, 465 (1968).
47. R.A Nyquist, Speclrocllim. ЛСlа, Parl А, 27А, 2513 (1971).
48. А Karlsson, Р. К1асЬое, К.-М. Marstokk, Н. M011cndal and С.1. Nielsen, ACla C/lem.
5ca"d., 5er. А, 40А, 374 (1986).
49. R.G. Jones and W.1. Orvil1c Thomas,J. CI/em. 50С., 4632 (1965).
50. а.А. Crowder, Mol. PJ/ys., 23, 707 (1972).
51. J.R. Durig and D.W. Wertz, 5peclrocJliт. Acta, Parl А, 24А, 21 (1968).
52. О.С. МсКеап, 1. Torto and A.R. Morrison, J. Mol. 5Irllcl., 99, 101 (1983).
53. R.G. Joncs and W.1. Orvil1e-Thomas, Spectrocllim. ACla, 20, 291 (1964).
54. 1. Suzuki and Т. Shimanouchi, J. Mol. 5pcclrosc., 46, 130 (1973).
55. а.А Crowder and М.1. Townsend,J. Flllori"e CllCIll., 10, J81 (1977).
56. а.А Crowder and J.M. Lightfoot, J. Mol. 5Irllcl., 99, 77 (1983).
57. А. Karlsson, Р. К1аЬое and С.1. Niclscn,J. Ral1lall 5pcclrosc., 23,167 (1992).
58. J.R. Durig, J. Liu, а.А Guirgis and В.1. Уап dcr Vckcn,5Ir/lcl. CJ,cm., 4, J03 (1993).
3.1.2 Chlol"OmethyI
The methylene symmetric stretching is always well separated from its anti
symmetric counterpart. Nevertheless the weak (о medium absorptions of these
methylene strctching vibrations often disappear within the stronger absorptions
of saturated and unsaturated СН stretching modes. The methylene scissor absorbs,
with mostly medium band intensity, coincident with or а! the LW side of aliphatic
methylene deformations. The methylene wag, often appearing as а moderate to
strong band, is helpful (о the identification of CHzCI compounds. In mапу cases
the wavenumber of this band depends ироп the conformation. lПе methylene twist,
normally appearing as а medium band а! the LW side of the wag, is по! aIways
sensitive to conformational changes of the molecule. lПе intensity of the methylene
rocking vibration is mostly moderate Ьи' the band sometimes matches that of the
C CI stretch, which is awkward in assigning both modes. Norrnally, the rock
is а! the HW side of the C CI stretch. The vsCOC in chloromethyl ethers or
BEи E\тE LJМJVERSJТV LfВRARY
52 NOI"llla/ VilJl'atiolls alld Absorptioll Regiolls о/ CH1X
e5tcrs al50 сап intcrfcre \vitll tllis rock, 50 Iltat Ille lattcr is assigncd а! I1igllcr
\vavenumbcrs. ll1е c c\ strctch is tl1C nlOst cltaractcristic band оС all ПОТПIа!
vibrations оС thc СН2С1 substitucnl. TI1C baI1d is often, Ьи! по! al\vays, sensitive
'о conformalion. ll1е band intcn5ity varics from medium 'о strong, dcpcndiI1g
upon \vhich conformation prcdominatC5. ll1С position оС thc БСС\ oflcn depcnds
upon conformation. This dcformation ca5ily couplcs with the skelclal modes and is
therefore оС minor importance as а diagnostic tool. Tlle band intensity is normally
\veak or sometimes mcdium.
ТаЫе 3.2 Absorplion rcgions (cm I) оС a C saturated CH2C1
ТОlаl rcgion Molcculcs absorbing Molccules absorbing Region of
а! high \vavcnumbcrs а! low \vavenumbers remaining
molccules
V a C H 2 3015 f: 25 MeCFzCHzCI (3039) tBuCH2C1 (2990) 3015 f: 15
McOCHzCHzCl (2990)
V s CH 2 2960 :1:: 20 iPrCH2C1 (2943) 2965 ::1: 15
nPrCHzCl (2945)
БСнz 1430 f: 20 4-FРhС(==0)(СНZ)2С1 (1411) 1435 :1:: 15
EtC(==O)(CHz)zCI (1412)
NCCHzCHzCI (1416)
wCHz 1265 :1:: 50 CIC(==O)CHCICH2C1 (1215) 1280::1: 35
H2C==CHCHCICHzCl (1221)
MeCHBrCHzC1 (1223)
McCHCICHzCl (1234)
TCHz 1195 :1:: 55 McCHzCI (1250) g-МеСFzСН2СI (1141) 1195 :1:: 50
HC==CCHzCHzCI (1247) CICHzCHzCI (1143 and 1233)
pCHz 885 f: 105 НС==ССН2СН2С1 (989) McCHzCI (786) 890 ::1: 70
Ir-СIСНzСНzСl (982) CICHz(CHCI)zCHzCI
CICH2C(Mc )2 CH ZCI (792 and 838)
(978 and 857) (CICHz)4C (794, 818,860)
iPrCHzCI (816)
vCCI 700 f: 70 C1CHz(CHCI)z СН2СI DзССНzСI (631) 705 ::1: 50
(767 and 720) DCHzCHzCI (642)
CICHzCClzCHzCI СI(СНz)зС1 (641 and 679)
(766 and 700)
McCFzCHzCI (760)
БСС1 285 :1:: 80 Ox CH2CI (363) MeCFzCHzCI (205) 290 ::1: 65
C1CHzC(Mc )2 CH Z CI cPrCH2C1 (205)
(363 and 3/6) tBuCHzCI «210)
СI(СНz)зCl (362 and 348)
torsion 140 f: 65 (C1CHz)4 (204, /23, 88) CICHzCHCICHzCI (75, /54) 140 ::1: 55
EtC(==O)CHzCHzCl (201) CICHzC(Mc)zCHzCI
(79 and 193)
3./ f/a/ogelloтel/1Y/
53
R CH2CI molcculcs
R = R'CHz (scc Scction 3.5.3);
R = Mc [1 7J, СDз [1J, iPr [7 9J, cPr [J()"",12J, Ox [12, 13J,
McCHOH , CICHzCHOH , McCHCI [15, 16, 18J, CICH2CHCI [14,
17J, ClzCHCHCI [I7J, СlзССНСI [18J, H2C==CHCHCJ ,
CIC(==O)CIICl , ClzCH [6, 2()"",22], CICH2(CHCl)z [19J,
McCHBr [15], tBu [8, 23J, PhC(Mc)2 , CICHzC(Me)z [24J,
(CICHz)zMcC [118J, (СIСНz)зС [25], MeCFz [26J,
CICHzCClz [17, 24], ClzCHCClz [17], FзС [27, 28J, СlзС [6, 29J.
ТаЫе 3.3 АЬsоrptiоп rсgiопs (cm 1) of CHzCI
attached 'о Ph С==С С=С с==о N,O S
У а СН 2 3005 ::1: 15 3000 ::1: 15 3000:1: 15 3000:1: 15 3035 ::1: 35 3020::1: 15
vsCHz 2970 :1: 15 2955 :1: 15 2960::1: 10 2960 :1: 20 2975 ::1: 30 2950 ::1: 20
БСН2 1450 :1: 10 1435 :1: 20 1430:1: 15 1410:1: 30 1440 ::1: 25 ]400::1: 10
wCHz 1265:1: 10 1265::1: 15 1270:1: 10 1275 :1: 45 13]5:1: 35 1245 ::1: 25
ТСН2 J205 ::1: 20 1185:1: 30 1180:1: 10 1185 :1: 45 1240 ::1: 35 1140::1: 20
Р СН 2 745 :1: 20 905 ::1: 50 905:1: 10 880 :1: 55 960 :1: 60 845 ::1: 40
l/CCI 690 ::1: 30 705 :1: 55 715:1: 25 755 :1: 45 690 :1: 60 700 ::1: 55
БССI 270 :1: 40 310 :1: 80 395 ::1: 55 300 :1: 70 310:1: 60
tоrsiоп 150:1: 65 120 :1: 80 120:1: 85 150:1: 50
R CH2CI molecule5
R = (substituted)phenyl (see Section 12.4);
R = H2C==CH [3()"",35J, HzC==CMe [30J, H2C==C(CHzCI) [36, 37J,
H2C==CCI [38 0, 117], H2C==CBr [40, 41],
cis CICHzCH==CH [42], Ir CICH==CH [43], HC=C [44----46],
OC=C [46, 47], CIC=C [45, 48], FCH2C=C [119],
CICHzC=C [49 51], N=C [52 54], HC(==O) [55, 56J,
MeC(==O) [57 59J, CICH2C(==O) [60, бlJ, 2-ТhC(==0) ,
4 FPhC(==O) [62J, 2, 4 CI2PhC(==O) [63J, H2NC(==0) [64----68J,
MeHNC(==O) [68J, HOC(==O) [68 72J, OOC(==O) [70, 71J,
MeOC(==O) [72 74], СDзОС(==О) [72, 73], ЕtOС(==О) [75
77], tBuOC(==O) , Me(CHz)"oc(==o) [68], HSC(==O) [78J,
FC(==O) [68, 79, 83], CIC(==O) [72, 79----82, 120J, BrC(==O) [64,
79, 120J, OCN , OzN [84], MeO [64, 85----88], DзСО [85,
87, 88J, CICHzO [89J, HC(==O)O [9()"",92], MeC(==O)O [93,
94J, СDзС(==О)О [94J, tBuC(==O)O , PhCH20 , 4 CIPhO ,
FC(==O)O [95J, CIC(==O)O [96J, MeS [64J, PhS , NCS [97,
98J, MeS(==0)2 [99J, FS(==O)z and CIS(==O)2 [100J.
54 NOI"I/la/ VilJтliolls атl AlJSOI]Jtioll Regiolls о/ CH2X
ТаЫе 3.4 Absorption rcgions (cm l) оС CH2CI
attached 10 Si Hg CI, Br and I
У а С Н 2 3000::1: 10 2990::1: 15 3010 ::1: 10 3О50::l: 10
vsCHz 2935 ::1: 15 2940 ::1: 15 2945 ::1: 10 2985 ::1: 05
БСН2 1400::1: 10 1400::1: 10 1400::1: 10 1410::1: 15
WCH2 1210::1:25 J J85 ::1: 15 lJ95::1: 45 1225 ::1: 40
TCHz 1110::1: 40 1110::1: 10 J080::l: 35 1130::1: 20
Р СН 2 790 ::1: 35 795 ::1: 50 720::1: JO 845 ::1: 55
УССI 705 ::1: 25 715::1: 55 685 ::1: 15 720 ::1: 20
БССI 285
torsion
R CH2Cl n101ecules
R = FzP [101, 102, 121], ClzP [103 105], F2P(==0) [102, 106],
ClzP(==O) [105, 107], F2P(==S) [102, 108], ClzP(==S) [105, 107],
(НO)2P(==0) , (HO)(KO)P(==O) and (ЕtO)2Р(==0) [109], НзSi ,
DзSi , FзSi and СlзSi [110], MezHSi and MezDSi [111],
CICHzHg [112], ClНg [113], F [64], Cl [1,64,114, 115], BT [64,
116], I [64].
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3.1 Halogellolllel/lyl
57
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3.1.3 BromomethyI
lПе mcthylene stretching vibrations are ob5erved with band intensitie5 from very
\veak 'О medium.The antisymmetric methyJene stretch appears partJy in the same
region as for unsaturated and aromatic СН stretching modes and the symmetric
stretch sometimes disappears into other aliphatic СН stretching vibrations. lПе
methylene deformation is active, with а medium intensity, а! the LW side of
other aliphatic methylene and/or methyl deformations. Тhe methylene wag is often
recognized Ьу its inten5ity, which varies from moderate to strong. lПе band is
often sensitive to conformation. lПе wavenumber difference5 be\Ween /ralls and
gallc/le conformers mау cven rise ир to 50 cm l. Тhe methylene twi5t is located
with medium intensity а! the LW side of the wag. lПе intensity of the methylene
rock varies from weak to moderate. lf the molecule is in different conformational
states, the wavenumber differences between the rocking modes mау Ье as great
as 100 сm 1. The CBr stretch provide5 the most characteristic band of аll CHzBr
modes of vibration. Normally the band i5 moderate or strong and therefore easy
(о recognize in this part of the 5pectrum. Weak CBr bands usually originate from
various conformational states of the molecule, whereas band separations ир to
100 wavenumbers are sometimes observed between CBr 5tretches of different
conformers. lПе CBr deformation i5 often a55igned as а skeletal deformation.
This weak (о medium band is usually по! important as а diagnostic tool.
58 Noтza/ \'ibraliorrs {1Щ/ AlJsorptioll Regiolls о/ CHlX
ТаЫе 3.5 Absorption rcgions (СП1 I) of (\-с sаtшаtсd СНzlЗr
Total rcgion Molcculcs absorbing Molcculcs absorbing Rcgion of
аl high \vаvспuП1ЬСrs аl low waVCI1U111bcrs rспшil1iпg
molcculcs
IlaCHZ 3020 :!: 30 F)CCHzBr (3049) (McO)zCI-1СНzВr (2994) 3020 ::1: 20
ЕtOС(==О)СН(Вr)СНzlЗr (McO)zC(Mc)CHzBr (2995)
(3043)
I/sCHz 2945 :!: 45 FзССНzВr (2990) BrCHzCHBrCHzBr (2902 2960 ::1: 20
and 2948)
EtOC(==O)CH(Br)CHz Br MeCHBrCHzBr (2929)
(2983)
6CHz 1430:!: 20 СDзСНzВr (1449) ВrзССНzВr (1410) 1430::1: 15
(BrCHz)4C (1411, /4/5,
1422)
wCHz 1250:!: 50 NCCH(Br)CHzBr (1298) Ir-СIСНzСНzСI (1203) 1255 ::1: 35
MeOC(==O)CHzCHzBr HOCHzCHzBr (1215)
(1294)
Вr(СНz)зВr (1293)
TCHz 1175:!: 70 PhCHzCHzBr (1242) g-ВrСНzСНzВr (] 105) 1170 ::1: 55
McOC(==O)CHzCHzBr HzC==CH(CHz)zBr (1108)
(1240)
Вr(СНz)зВr (1239 and 1194) ВrСНzСНlЗrСНzВr (1110
and /I 59)
pCHz 830:!: 115 Вr(СНz)зВr (943 and 853) (BrCHZ)4C (716,780,835) 835 :!: 75
НО(СНz)зВr (912) (McO)zC(Me )CHz Br (745)
I/CBr 635 :!: 85 FзССНzВr (720) Ir BrCHzCHzBr (552) 625 :!: 65
(BrCHz)4C (700 and 6/1)
БСВr 265 :!: 90 g-ВrСНzСНzВr (355) tBuCHzBr (179) 260 ::1: 75
(BrCHz)4C (180 and 235)
lorsion 130 :!: 60 Вr(СНz)зВr (186) (BrCHz)4C (73, 148) 120::1: 30
rr BrzHCCHz Br (80)
R CHzBr molecules
R = Me [1--4], СDз [2], Et [4-----11], nPr [10, 11], МеСН(Вr)СНzСНz ,
CIC(==O)CHzCHz , HzC==CH CHzCHz [12], NCCHzCHz ,
HOCHzCHz , PhOCHzCHz , CICHzCHz and BrCHzCHz [35],
MeCH(Br)CHz , СlзССНz [13, 14], MeOC(==O)CHz ,
CIC(==O)CHz , HzC==CHCHz [12, 15], PhCHz [16], NCCHz [17,
18], +НзNСНz , HOCHz [19 21], MeOCHz [22], EtOCHz ,
PhOCHz , 4 BrPhOCHz , HSCHz [23], MeSCHz [24], FCHz
[25], CICHz [26], BrCHz [1, 3, 26----28], iPr [4, 29, 30],
cPr [33], Ox [32, 33], Et(Me)CH [29), РhСН(Ме) ,
3./ f/a/ogelloтe/11Y/
59
ВrСН1СI'I(ОН) , (MeO)zCH and (СDзО)2СН [43], (EtO)zCH ,
MeCH(Dr) [34, 37, 38), ЕtСН(Вr) [37], NCCH(Br) ,
EtOC(==O)CНCBr) , BrCHzC(Me)z [39), (ВrСНz)з [40J,
(McO)zC(Mc) , BrCHzCHBr [36], BrzHC [41, 42], tBu [31J,
FзС [44----46J, ВrзС .
ТаЫе 3.6 Absorption regions (cm l) of CH1Br
attached 'о Ph с==с с=с С==О N,O,S Si, Hg О, Br
VaCHz 3015 ::1: 20 3000 :!:: 20 3010:!:: 15 30]0 :!:: 20 3035 :!:: 30 30fЮ:!:: 15 :::::3060
vsCHz 2970 ::1: 20 2955 :!:: 15 2965 :!:: 15 2960 :!:: 20 2975 :!:: 20 2945 :!:: 10 :::::2990
БСН1 1435 :!:: 15 1430::1: 15 1425:!:: 15 1410:!:: 25 1415:!:: 25 1380:!:: 10 :::::1400
WCH1 1225:!:: 15 1220:!:: 20 1215:!:: 15 1250 :!:: 45 1240:!:: 40 1120:!:: 15 :::::1210
TCHz IJ90:!:: 25 1160:!:: 30 1150:!:: 10 ]]70 :!:: 40 1145:!:: 45 1060:!:: 10 :::::1130
рС Н 1 880 :!:: 20 870 ::1: 35 865:!: 15 860 :!:: 40 870 :!:: 80 730 :!:: 40 :::::830
vCBr 620 :!:: 20 620::1: 70 630 :!:: 20 635 :!:: 60 620 :!:: 60 590 :!:: 40 :::::620
БСВr 320 ::1: 70 260 :!:: 70 340 :!:: 60 210:!:: 60 220 :!:: 80 :::::175
torsion :::::100
R CHzBr molecules
R = (substituted)phenyl (see Section 12.4)
R = H2C==CH [49 52], HzC==CMe [53, 54], HzC==CBr [55
57]. H1C==C(COOEt) , HzC==C(CHzBr) [58), BrCH1CH==CH ,
HC=C [59----62], OC=C [62, 63], BrC=C [61], BrCHzC=C [64,
90], N=C [65, 68], MeC(==O) [69, 91], BrCH2C(==O) [70],
FзСС(==О) [71, 72], HzNC(==O) [48J, 2 HOPhC(==0) [74],
HOC(==O) and OOC(==O) [75], NaOC(==O) [73], MeOC(==O) ,
ЕtOС(==О) [76, 77], (BиOC(==O) , HSC(==O) [78], FC(==O) [80],
CIC(==O) [48,79, 80J, BrC(==O) [48, 79 1], 02N [82], MeO [83,
89J, MeS(==O)z [84], FS(==O)z and CIS(==O)z [85], Me2HSi and
MezDSi [86], BrCHzHg [87], Cl [47, 48], Br [1,48,88].
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60 Nотш/ VilJтlio/ls аl/(l AIJS011J/io/l RegiollS о/ CH2X
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3.1 f/a/ogeпoтe/hy/
61
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62 Nотш/ Vi/тtliOIlS от/ AlJSOrplioll Regiolls о/ Cl-/2X
3.1.4 IоdошеthуI
Tllc \veak (о mеdiuП1 absorptioJ\s of tllc П1еtllуlСJ\С strctcl1iJ\gs, wl1icll oftcn coincidc
\vith otllcr СН strctclling vibrations, are dif1icult (о assign unambiguously. TllC
mctllylene scissoriJ\g vibration absorbs а! the LW side of аliрlшtiс mcthylcne
dеl'оrП1аtiопs \vitll а wcak (о J\lOderatc intcnsity. Witll ап intcJ\sity varying from
mcdium [о strong, the П1сtllуlспе \vag is often scnsitivc (о rotational isomerism,
yielding band separations ир (о 80 \vavenumbers, although normally the differenccs
are much smallcr. Tlle t\vist, wl1ich occur with weak intcnsity а! tlle LW side of the
\vag, is Iikcwise sensitive 'о conformational changes of the molcculc. The П1еthуIепе
rock give5 ri5e (о \veak or nlOdcrate absorptions and is sometimes dif1icult to
detect among other rocks or аroП1аtic out-of plane dеfоrП1аtiопs. The СI stretch
often yiclds а сопfоrП1аtiоп sепsitivе band with а П1еdiuП1 (о strong intensity. А
\veak intensity normally indicates that (Ье moleculc is по! inclined (о stick (о that
conformation. lПе СI stretch and the methylene wag are thc t\VO most characteristic
ТаЫе 3.7 AbsorptioJ\ rcgions (cm I) of CHzl
Total rcgion Molecules absorbing Moleculcs absorbing Region of
а! I1igh wavenumbcrs а! low \vavenumbers remaining
molccules
vaCHz 3015 :!: 35 CICH21 (3050) HzNC(==O)CHzl (2980) 3015 ::1: 25
CHzl2 (3046) HzC==CHCHzl (2980)
FзССНzl (3044)
vsCHz 2960 :!: 25 F)CCHzl (2985) ICHzHgCHzl (2935) 2960 ::1: 20
HOC(==O)CHzl (2985) Me2HSiCHzI (2936)
Бснz 1395 :!: 45 Ir-Н2С(==О)СНzl (1440) ICH2HgCH21 (1350) 1410::1: 25
McCHzl (1439) СН212 (1352)
HzC==CHCHzl (1437) MezHSiCHzl (1374)
wCHz 1165 :!: 115 H2NC(==O)CH21 (1280) ICH2HgCHzI (1059 and 1050) 1195 ::1: 65
ICHzC(==O)CHzl (1268 Me2HSiCH21 (1080)
and 1248) CHzlz (1106)
TCHz 1100:!: 100 cPrCHzl (1197) ICH2HgCH21 (1000) 1120::1: 70
MC2HSiCH21 (1012)
CHzlz (1030)
pCHz 760 :!: 100 McOCHzl (860) ICHzHgCHzl (660 and 672) 785 ::1: 60
HOC(==O)CHzl (850) CHzlz (717)
Сl(СНz)зl (849) HzNC(==O)CHzl (720)
vCI 560 :!: 100 СFзСНzl (660) HzNC(==O)CHzl (465) 555 ::1: 65
NaOC(==O)CHzl (653) CHzlz (485)
HOC(==O)CHzl (635) g ICHzCHzl (485 and 507)
БСI 220 :!: 100 g-IСНzСНzl (313) CHZl2 (] 25) 220 ::1: 70
MezHSiCHzl (131)
g ICH2CHzl (134)
torsion :::::120 :::::120
3.] f/a/ogeпoтeI/IY/
63
bands of аН CHzI normal modcs. Not only the СI slretch Ьи! a]so the CH z wag, twist
and rock ahsпrb in а rangc which is about 50 cm ) lower Ihan for the comparabIe
R CHzBr molccules. Thc CI dcformation, somctimes referrcd 10 as а skeJelal
dcformation, is по! significant as а diagnostic tool.
R CHzI molcculcs
R = Mc [1----4], СDз [3, 4], Et [2, 5 8], nPr [1, 6, 8],
пВи [40], C]CI.lzCHz , ICHzCHz [1, 6, 9], I(СНz)з [41],
HOC(==O)CHz , PhCHz [10], HOCHz [11, 12], MeOCHz [13],
ICHz [1, 14, 15], iPr [2], cPr [16], Ox [16, 17], FзС [18,
19], MeC(==O) [20], ICHzC(==O) [21], HzNC(==O) [22 25],
HOC(==O) and NaOC(==O) [26], ЕtOс(==о) , H2C==CH [27,38],
H2C==C(Me) [28], HC=C [29], ICHzC=C [39], N=C [3Q...-32],
MeO [33], MezHSi and MezDSi [34], ICHzHg [35], CI [36J,
I [36,37].
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64 Norma/ \Ii/Jraliolls тlll AlJsorptio/l Regio/ls о/ CH2X
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27. R.D. McL.1cIIIan and R.A. Nyquist, Speclroc//illl. АсШ, PtI/.t А. 24А, IU3 (1968).
28. F. Nоrthаш. J. Olivcr and G.A. Cro\vdcr, J. Mol. 5peclrosc., 25, 436 (1968).
29. J.c. Evans and R.л. Nyquist. Spcclrocllim. ACla, p(//.t А, 19, 1153 (1963).
30. R.G. Jones and J. OI\'ilIc-ТllOшаs, J. Cllem. Soc., 4632 (1965).
31. J.R. Durig and D.W. Wertz, SpeCll"ocllim. Acta, 24, 21 (1968).
32. GA. Cro\vdcr, 10101. PJ/ys., 23. 707 (1972).
33. О.С. МсКсап, 1. Torto and A.R. Morrisson, J. Mol. SlrIICI., 99, IO] (1983).
34. К. Ohno, К. Suchiro and Н. Murata, J. Mol. SlrIICI., 98, 251 (1983).
35. У. Iшаi and К. Aida, SpeclrocJ/im. ACla, Pllrt А, 28А, 517 (1972).
36. R.G. Joncs and \V.J. Оrvillе-Тhошаs, Spec/l"Ocllilll. ЛСIII, 20, 291 (1964).
37. Т,д, Ford, J. Мо/. Speclrosc., 58, 185 (1975).
38. J.R. Durig. О. Tang and T.S. Liltle, J. Ramall Speclrosc., 23,653 (1992).
39. А. Karlsson, G.D. Bauza, Р. Кlaboc, C.J. Niclscn and О. Siilzle, J. Ral1lll/l 5pcclrosc.,
23, 391 (1992).
40. G.A. Cro\vdcr and М. Jalilian, J. Mol. Slrllcl., 33, 127 (1976).
41. G.A. Cro\vdcr and S. Ali, J. Mol. SlrIIC/., 27, 43 (1975).
3.2 OXYMETHYL
3.2.1 Hydroxymethyl
Ethanol i5 ап example of а 5imple compound containing а CHzOH fragment
in the 5tructure. Тhe 21 normal vibrations differentiate between 13а' plus 8 а"
vibrational mode5 in the С . conformation. After subtraction of 8 methyl vibrations
(5а' + За") and аСС stretching vibration (а'), 7а' + 5а" normal vibrations remain,
so that they сап Ье a55igned to the modes of vibration of CHzOH:
а': vOH, v s CH 2 , БСНz, wCH 2 , БОН, vCO and Б-СО;
а": VaCH2, TCHz, РСН2, ОН and torsion.
Тhe ОН stretching vibration
lп the a550ciated 5tate the ОН stretching vibration absorbs as а strong, broad band
in thc region З300 :i: 120 cm l. It is the most characteristic absorption of аll
СН 2 ОН normal vibration5. Тhi5 broad band, caused Ьу intermolecular hydrogen
bridges, di5appears in dilute solutions or in the gaseous state, and returns as the
undisturbed ОН 5tretching vibration round аЬои! 3620 cт l in the form of а sharp
peak. Compounds such as EtOCHzCHzOH (3420 cm l), NCCHzCHzOH (3415
cm l), МеОСН2СН20Н (3410 cm l) and HC(==O)CHzOH (3410 cm l) absorb
а! the HW side of the above-mentioned region. А! the LW side опе finds the
ОН ab5orption5 of polyol5 and amino-a1cohols insofar as they are по! sterically
hindered. Neverthelcss most of the primary a1cohols absorb in the region 3370 ::1:
50 cm l .
3.2 Oxyтe/hyl
65
Methylcnc strctching vibrations
Thc l.laCHz vibration is found in the region 2945 ::1: 45 cm 1 for such compounds as,
for instance, C1zCHCHzOH and FzCHCHzOH (2988 cm I), and for FCHzCHzOH
(2967 cm l) а! thc HW side (the l.laCHzF absorbs in the neighbourhood
of 2995 cm l) and McC(==O)CHzOH (2900 cm l, coincident with vsMe),
HzC==C(Mc)CHzOH and 2 CIPhCHzOH (2918 cm l) а! the LW side of the above-
mentioned region. The remaining studied compounds absorb а! 2940 cm l, а range
situatcd distinctly lowcr than that of vaCHzX (Х = F, Cl, Br, 1 and CN), with а
band intensity that fluctuates bctween weak and mcdium.
The vsCHz is active in thc range 2885::1: 45 cт 1 with, for instance, МеСН20Н
(2928 cm l) and FCHzCHzOH (2924 cm l) а! the HW side and such compounds
as MeNHCHzCHzOH and HzNNHCHzOH а! 2840 cт 1 а! the LW side. General1y
опе finds the v.,CHz in primary alcohol5 in the region 2880 ::1: 20 cт 1 with а band
intensity which varies from weak to medium. lПа! i5 аЬОи! 80 cm 1 lower than the
vsCHzX (Х = F, Cl, Br or 1), which appears in the neighbourhood of 2960 cm l.
Methylene deformation
The БСН z vibration absorbs in the region 1445 ::1: 35 cm 1 with а band intensity
which varies between weak and medium. Compounds such as HC=CCHzCHzOH
(1474 and the second deformation а! 1426 cm l), iPrCH(NHz)CHzOH and
iРrСН2СН(NН2)СНZОН (1468 cm 1 together with the Ме deformation) absorb
in the HW region. The deformations оС 2 CIPhCHzOH (1410 cm l) and
MeC(==O)CHzOH (1416 cm 1, together with Ба and Б Ме) repre5ent the lower
values of this region. Most оС the primary alcohols show this deformation а! 1445
::1: 20 cm l.
ОН in plane deformation
lПе associated ОН in plane deformation is assigned in the region 1400 ::1: 40
cm 1. This absorption possesses а weak to moderate intensity and arises mo5tly
as а broad band оп which other deformations, such as methylene wagging and
twisting vibration5, are superimposed. In addition, this vibration couples easily
with the wag and twist and therefore it is difficult to decide which vibration plays
the biggest part in this absorption, so that по! infrequently the methylene wag i5
assigned in the above mentioned range. lПе БОН is sensitive 'о conformation and
shifts to the 10wer wavenumbers (1200 cт 1) in dilute solutions or for the gaseous
form. Compounds such as EtCH==CHCHzCHzOH and H2C==C(Me)CHzCH20H
produce this БОН а! 1440 cт 1 Ьи! the value for ICHzCHzOH is 1370 cm l. А
measuremcnt in solution or а deuteration of ОН gives а supplementary 5ecurity for
this assignment.
66 Norllla/ VilJ/'atiol/s аlll/ Abso/]Jlioll Uegiolls о/ CH2X
Mcthylenc \vagging vibration
Tl1is \vag is по! a1\vays easi1y dctccted in tl1C rcgion 1335 :!:: 55 cт 1, Wl1icl1
partly coincidcs witll the absorption rcgions of ОН dcformation and mcthylenc
t\vist, thc normal vibrations \vith \vhich tlle \vag rcadily is couplcd. Thc band
inten5ity varics bet\vecn \veak and medium. In additiol1, this vibration сап Ье
scn5itivc (о tlle сопfоrпшtiопаl state so tlшt every factor is prcsent (о prcvent
ап unambiguous assignment. Ncg1ecting the as5ignmcnts а! low wavenumber in
the spectra of HC(==O)CHzOH and MeC(==O)CHzOH (аЬои! 1280 cm I), these
\vaggings are locatcd in the more favourabIe region of 1365:!:: 25 cm l.
Methylene twisting vibration
Problems similar 'о tho5e witll the CH z wag and ОН in p1ane deformation arise
\vith the as5ignment of the СН 2 twist, which is weakly (о moderate1y active in
the region 1240::1: 60 cт 1. Mo1ecules such as D 2 C==CHCH z OH (1190 cт 1),
HC=CCH2CHzOH (1189 cm l) and EtC=CCHzCH20H (1186 cm l) absorb at
low \vavenumbers. lПе remaining compounds give this twist in the region 1240
:!:: 40 cm 1, and this band is mostly sensitive (о conformational changes. lп the
unbonded state this TCHz absorbs а! 30 cт 1 10wer \vavenumbcr.
The СО stretching vibration
lПе СО stretching vibration absorbs moderatcly (о strongly in the range 1045 ::1:
45 cm / and is, as for the ОН stretch, а highly characteristic absorption for the
primary a1cohols. Тhe СО stretch of the mo1ecules ХзССНzОН (Х = F, СI and Br)
(1090 cm l) and HOCHzCHzOH (1087 and 1043 cт 1 for the other уСО) absorbs
оп the HW side of this region. 2 Unsaturated primary a1coho1s absorb оп the LW
side, that is 1025:!:: 25 cm l, \vith а few representatives: HzC==CHCHzOH (1028
cm I), PhCHzOH (1016 cm I), 2 FuCHzOH and 2 ThCHzOH (1010 cт 1). Тhe
remaining molecules give this absorption in the region 1055 :!:: 25 cm l, so that
primary a1coho1s are easi1y characterized Ьу this mode of vibration.
Methy1ene rocking vibration
lПе methylene rocking vibration gives rise (о absorptions in the region 890 ::1:
90 cm 1 with band intensitie5 varying from weak (о moderate. Оп the HW
side МеСН(NОz)СНzОН (980 cm l) and OzNCHzOH, OzNCHzCHzOH and
С12СНСН20Н (976 cm 1) absorb. Оп the LW sideone finds the rock of MeCHzOH
(804 СП1 I), HC(==O)CHzOH (813 cт 1), MeC(==O)CHzOH (813 cт 1) and
PhCHzOH (815 cm I). Most of the compounds produce this rock а! 895 ::1: 65
cт 1, so that this absorption does по! score well as а group vibration.
3.2 Oxyme/hyl
67
ОН out of planc dcformation
The "'(ОН absorption is activc in Ihe rcgion 640 :1: 70 cm l. lПе band inlcnsily
varics from wcak 10 mcdium, rarc]y strong. Usually this band is very broad and
casy (о rccognizc. Somctimcs Ihc схас! wavenumber is difficult 10 locate because
othcr bands arc supcrimposed оп it. Just as УОН and БОН, the ,ОН is sensitive (о
conformalion and dilution. NCCHzCH20H displaY5 thi5 vibration а! 579 cm l,
McC(==O)CHzOH and FzCHCHzOH in the ncighbourhood of 575 cm 1 and
HOCHzCBr(NOz)CHzOH а! 708 cm l, bul most of Ihe investigated molecuJes
absorb in thc region 635 ::1: 35 cm l. lп thc unbonded slale Ihis fOH di5appears
(о make way for thc free torsion in thc vicinity of 300 cm 1 [24J.
СО in plane deformation
The БСО with а range of 475 ::1: 80 cm l is по! а model of а good
group vibration. Тhe intensity of this band is weak or moderale. This broad
region contains bands caused Ьу the following compounds: HC=CCHzOH
(551 cm I), H2NNHCHzCHzOH (546 cm I), МеОСН2СН20Н (539 cm I),
MeNHCHzCHzOH (535 cm l) and HzC==C(Me)CHzOH (534 cm I). Тhe out
siders оп the LW side are HC(==O)CHzOH (397 cm l) and MeC(==O)CHzOH
(409 СП1 I). For the remaining molecules the СО in p]ane deforrnation is
concentrated in the region 465::1: 55 cm l.
ТаЫе 3.8 Absorption regions (cm I) оС the normal vibrations оС associatcd
CH20H
Vibration С . Region Vibration С . Rcgion
уон а' 3300 ::1: 120 TCHz а" 1240:1: 60
VaCHz а" 2945 ::1: 45 уСО а' 1045:1: 45
У., СН 2 а' 2885 ::1: 45 рСН2 а" 890 :!: 90
Бен, а' 1445 ::1: 35 ')ОН а" 640 :!: 70
БОН а' 1400::1: 40 Б С О а' 475 ::1: 80
wCHz а' 1335 :1: 55 torsion а"
The following R CHzOH compounds have Ьееп taken into account:
R = R'CHz (see Section 3.5.4)
R = Me [1 ], iPr , cPr [7, 8], Ox , EtCH(Me) , MeCH(NH2) ,
EtCH(NHz) , iPrCH(NHz) , iРrСНzСН(NНz) , МеСН(N02) ,
MeCН(OН) , ЕtСН(ОН) , 'Bи , HOCH2CBr(N02) ,
HOCHzCBr(NOz) , MezC(NHz) , PhzCH [25], FzCH [9],
ClzCH [9], ЕtС(СНzОН)z , FзС [3, 1Н3], СlзС [11, 12],
68 Nотш/ Vibmlio/ls аш! AlJsolplio/l Regiolls о/ CH2X
ВrзС [11], HC(==O) (14, 15], McC(==O) , HOC(==O) [10],
MeOC(==O) and СDзОС(==О) [10], HzC==CH and 02C==CH
[16], H2C==C(Mc) , cis апd Imlls nPrCH==CH , HC=C (17, 18],
02N , Pll [23], 4 EtPh , 3 IЮСНzРll , 2 , 3 and 4-FзСРh , 4-
McOPh [19], 4 EtOPll , 4 NCPh [23], 2 and 4 FPll [20, 21], 2
C1Ph , 3-1Pll , 2 Fu [22], 2 Th , 2 HC(==0)Fu 5 , 2 HOCHzFu
5 .
References
1. У. Mikawa, J.W. Brascll and R.1. Jakobsen,Speclrociliт. Ас/а, Pт.t А, 27А, 529 (1971).
2. J.R. Durig, W.E. Bucy, С.1. Wuпеу and L.A Carreira,J. PI/)'s. CI/ст., 79, 988 (1975).
3. О. Scllrcms and W.A.P. Luck, J. Mol. 5Irllct., 80, 477 (1982).
4. H.F. Hamcka,J. Mol. 51/"llct., 226, 241 (1991).
5. R.A Sha\v, Н. Wicser, R. Dutler and А Rauk, J. Ат. ClICIII. 50С., 112, 5401 (1990).
6. А.1. Barncs and Н.Е. Наllаm, Tralls. Faraday Soc., 66, 1932 (J970).
7. Р. Кlaboe and D.L. Po\vcll, J. Mol. SIПlсt., 20, 95 (1974).
8. Н.М. Badawi, М.Е. Abu-Zcid and У.А. Youscf, J. Mol. Strllcl., 240, 225 (1990).
9. М. РсrttШi, Spcclrocllim. Асщ Parl А, 35А, 37 (1979).
10. Н. Hollcnstcin, R.W. Schtir, N. Sch\vizgcbcl, а. Grassi and Hs. Giinthard, 5peclrocililll.
Acta, Parl А, 39А, 193 (1983).
11. J. Travert and J.c. Lavaley, Speclrocllim. Acta, Party А, 32А, 637 (1976).
12. М. Pcrttilti, 5pecl/"Ociliт. АСIa, Parl А, 35А, 585 (] 979).
13. J.R. Durig and R.A. Larscn, J. Mol. Slrllcl., 238, 195 (1990).
14. Н. Michclscn and Р. К1аЬое, J. Mol. 5/Пlсt., 4, 293 (1969).
15. У. Kobayashi, Н. Takahara, Н. Takahashi and Н. Higasi, J. Mol. 5trиct., 32, 235 (1976).
16. В. Silvi and J.P. Perchard, 5peclrocllim. Лс/а, Parl А, 32А, 11 (1976).
17. R.A. Nyquist, Spcclrocilim. Acta, Parl Л, 27А, 2513 (1971).
18. J. Travcrt, J.c. Lavallcy and О. Chencry,5pcct/"Ocllim. ACla, Part А, 35А, 291 (1979).
19. S. Chakravorti, А.К. Sarkar, Р.к. Mallick and S.B. BaneIjce, II/l/iall J. P//)'s., В, 568,
96 (1982).
20. S. Tariq, N. Ali and Р.К. Уеrrnа, /lIdiall J. Pllrc Арр/. PI/ys., 21, 220 (1983).
21. S. Tariq and Р.К. Уеrmа, IlIdiallJ. P//ys., В, 578, 356 (1983).
22. L. Strandman-Long and J. Murto, Speclrocilim. ACla, Parl А, 37А, 643 (1981).
23. а. Varsanyi, Assigllll/ellls [о, Vibraliolla/ Spcctra o[Sevell Hlllldrc(/ Bellzellc Deriva/ives,
J.Wilcy & Sons, Ncw York (1974).
24. N.M.D. Bro\vn, В.1. Мсспап and G.M. Taggart, Speclrocllim. Acta, Pт.t А, 48А, 939
(1992).
25. S. Chakravorti, R. Ое, Р.К. Mallick and S.B. Banerjce, Spcctrocilim. АСIa, Part А, 49А,
543 (1993).
3.2.2 Methoxymethy1
Compounds such as XCHzOMe (Х = F, С1, Br and 1) be10ng (о the point group
С . in which the 21 normal vibrations are divided among 13а' and 8а" species of
vibration. When the СХ stretching vibration (а') has Ьееп replaced Ьу а torsion
(а"), the norma1 vibrations of CHzOMe are divided among 12а' and 9а" vibration
type5, which сап Ье described a5 follows:
3.2 Oxyтe/hyl
69
а': I/ Mc, I/..CI.lz, у,Ме, Б Ме, БСН z , БsМс, wCHz, р'Мс, уаСОС, vsCOC and
two skclctal deformations,;
а": уаМс, v"CH z , баМС, TCHz, рМс, pCH z and thrcc torsions.
Of thcsc, cight arc ascribcd (о vibrations of methy\ and six to vibrations of
mct\1y\enc, whilc thc other sevcn bclong 'о thc СОС antisymmctric and symmetric
stretchings, skclctal deformations and torsions.
Met11Y\ and methyIcne stretching vibrations
As а mattcr of course the absorption regions of l/аМе (3000 :!: 25), I/ Me (2960
::1: 30) and vsMe (2830 ::1: 10 cm l) strong\y overlap those of l/ a CH z (2945 :!: 40)
and vsCHz (2900 ::1: 60 cт 1). lПе sharp separatc peak with medium inten5ity of
vsMe is а usefu\ identification mark for methy\ ethers. Iп gcneral, the СН stretching
frequencies of CHzOMe are ordered as fol1ows:
УаМе 2:: Y Me 2:: vaCH z > vsCHz 2:: vsMe
The high va\ues for the methylene stretching vibrations within XCHzOMe (Х
= F, С\, Br, 1) compounds have по! Ьееп taken into account here (see Section 3.1).
Metl1yl and methy\ene deformations
It is по! easy to distinguish c\early the methy\ and methylene deforrnation5, which
appear with medium intensity in the range 1455 :!: 30 cm l, with the ехсерйоп of
БСН z (1496 cm l) in the spectrum of FCHzOMe. Typical for CHzOMe is the
high va\ue for Б.,Ме (1445 :!: 15 cm 1) in comparison with 6 s Me of the 5aturated
hydrocarbons (1375 ::1: 15 cт 1).
Methy\ene wagging and twisting vibrations
The methy\ene wag and twist mostly absorb in the regions 1350 :!: 55 and 1270
::1: 40 cm 1 respective\y, with band intensities being weak to moderate. Тhe \ow
values for ICHzOMe and BrCHzOMe, in which the influence of the ha\ogen cIearly
appears, have по! Ьееп taken into ассоип! (see Section 3.1).
Methyl rocking vibrations
The methyl rockings are active in the ranges 1195 :!: 35 and 1160:!: 30 cm 1 with
ап intensity that тау vary from weak (о strong. lПе areas overlap each other Ьи!
in most cases the two rocks do по! coincide а! опе and the same wavenumber.
70 Norl1la/ Vi/JI'aliolls arld Absorp/ioll Regiolls о/ CH2X
СОС stretcl1il1g vibrations
lПе most сlшrасtеristiс norl1lal vibration of CHzOMc is uшlоubtсdlу thc
СОС antisyттetric strctcl1ing vibration, con5idered as I/CI'Iz O, which appcars
strongly in the ral1ge 1110 :!: 70 cm l. FCHzOMe absorbs strol1gly а! 1175 cm l
and МеОСН20Ме а! 1042 cт 1 (tllc other antisymmetric stretch appcars а! 1111
cm l). If these values are Icft t1nconsidercd, the above mentioncd range will narrow
(о 1120::1: 40 cт 1. Vasfckova е/ а/. [26] find for both уаСОС 1150::1: 10 and 1050
:!: 10 cт 1 in the spectra of 55 examincd compounds with the protecting group
MeOCHzO . lПе antisyтmetric stretch provides а good group frequency, wl1ich
is furtller distinguished Ьу thc great intcnsity with wl1ich thc vibration prcsents
itself. This does по! preclude proceeding \vith caution, considering that the CF and
S==O stretching vibrations also absorb strongly in this area.
lПе СОС symmctrical stretch, corresponding with yMe O, is located in the
range 930 :!: 40 cт 1, with ап intensity that might Ье moderate (о strong Ьи!
is significantly less than the intensity of tlle antisymmetrical stretch. High values,
in the neighbourhood of 963 cт l, are revealed in the spectra of CICHzOMe and
HOCHzCHzOMe. Мапу compounds sho\v this СОС symmetric stretch in the range
930:!: 30 cт 1, for exaтple MeO(CHZ)1I0Me (11 = 3 5) [10], so that the I/sCOC
does по! си! (оо poor а figure as а group vibration.
Mcthylene rocking vibration
lПе pCH z in the spectra of RCHzOMe compounds manifests itself in the broad
region 905 ::1: 90 ст 1, \vith moderate intensity. Нigh values (995 ст 1) are found
in the spectra of MeOCHzCI and MeOCH 2 F and the lowest value in the spectrum
of MeCHzOMe (815 cт 1), Ьи! the pCH z of тапу RCHzOMe col1lpounds is
found in the region 900 ::1: 50 cm l. Sometimes а difference of opinion occurs in
assigning this pCHz. In the spectra ofHC=CCHzOMe (1006/895), N=CCH 2 0Me
(1016/888) and МеСН 2 ОМе (1014/815 cm l) thc highest wavenumber is assigned
(о the РСН 2 and the lo\vest to уСС instead of the contrary.
Skeletal deformations
lПе two skeletal deforтations are weakly (о moderately active in the regions 480
::1: 100 and 365 ::1: 100 cm l. The former represents the C O C deformation
and the latter ап external deformation.
R CHzOMe compounds
R = Me [1 7], СDз [5], HOCHz , MeOCHz [7 9], MeO(CHZ)II (11 =
2--4) [10], MeC(==O)OCHz , MeOCHzCHzOCHz [8], MeSCHz [9],
CICHz , BrCH2 and ICHz [11], СFз [12], MeC(==O) ,
MeOC(==O) , HC=C [13 15], DC=C [13], N=C [15 I7],
MeO [18 21], MeS [22, 23], EtS [22], F [24, 28], CI [16,20,
24, 25], Br [24, 27], I [24J.
3.2 Oxyтelhy/
71
Vibration
ТаЫе 3.9 Absorption regions (cm l) of the norrnal vibrations of
CHzOMe
Rcgion
Rcgion
Vibration
,/"Мс
Y Mc
l/aCI-1z
vsCI-1z
v.,Me
ЬаМс
Ь;,Мс
ЬСН,
БsМ;
wCHz
TCHz
3()ОО ::1: 25
2960 ::1: 30
2945 ::1: 40
2900 ::1: 60
2830::1: 10
1465 ::1: 20
1455 ::1: 20
1450::1: 15
1445::1: 15
1350 ::1: 55
1270 ::1: 40
рМе
р'Ме
УаСОС
j/,COC
pCHz
skclctal dcf.
skclctal dcf.
torsion
torsion
torsion
1195 :!: 35
1160:!: 30
1110:!: 70
930 :!: 40
905 :!: 90
480 :!: 100
365 :!: 100
225 :!: 40
145 :!: 35
References
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(1972).
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C/lem. 50С. JP/l., 50, 650 (1977).
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50С. JP/I., 50, 2272 (1977).
12. Y. S. Li, F.O. Сох and J.R. Ourig, J. P/,yS. C/lem., 91, 1334 (1987).
13. А. Bjorseth and J. Gustavsen,J. Мо/. 5Irllct., 23,301 (1974).
14. W.A. Seth Paul, J.P. Tollenaere, Н. Mceuscn and F. Нбflсr, 5pectrochim. Acta, Parl А,
30А, 193 (1974).
15. S.W. Charles, F.C. Cullen, G.I.L. Jones and N.L. Owcn, J. C/leт. 50С., Faraday Traпs.
2,70,758 (1974).
16. R.G. Jones and W.J. Orvil1e-Thomas, J. С//еl1l. Soc., 692 (1964).
17. R.G. Joncs and W.J. Orvil1e Thomas, 5pectroclliт. Асш, 20, 291 (1964).
18. К. Nukada, 5pectrocllim. Асш, 18,745 (1962).
19. J.E. Katon and Р.О. MiI1er, Арр/. 5pectrosc., 29, 501 (I975).
20. H.R. Linton and E.R. Nixon, 5peclroc/lil1l. Acta, 15, 146 (1959).
21. М. Sakakibara, У. Yonemura, Н. Matsuura and Н. Murata, J. Мо/. StrиCI., 66, 333
(1980).
22. Н_ Matsuura, Н. Murata and М. Sakakibara,J. Mol. Slrиcl., 96, 267 (1983).
23. Н. Matsuura, К. Кimura and Н. Murata, J. Мо/. Slrиcl., 64, 281 (1980).
24. О.с. МсКеап, 1. Torto and AR. Morrisson, J. Мо/. StrIlCt., 99, 101 (1983).
25. H.F. Hameka, J. Мо/. 5/rиc/., 226, 241 (1991).
72 NOI"/lla/ Vi/тt/iolls alld AlJSOIP/ioll Regiolls о/ CH2X
26. S. Vasickova. У. Pouzar, 1. Ссту, Р. Drasar and М. Havcl, ColI. Czecll. С//еlll. COIll/lIIII/.,
51,90 (1986).
27. В.1. Уап dcr Vckcn, а.А. Guirgis, J. Liu and J.R. Durig, J. Ralllllll Specl/"Osc., 23, 205
(1992).
28. J.R. Durig, J. Liu, а.А. Guirgi5 al1d В.1. Уаl1 dcr Vckcl1,5I/"l1c/. CI/('/II., 4, 103 (1993).
3.3 SULFUR-BONDED METHYLENE
3.3.1 МеrcарtОП1еthуl
Methanethiol [1 3, 6, 11] has 12 fuпdашепtаl vibrations which, according (о С .
sуmшеtrу, are distributed among 8а' and 4а" vibration types. In addition (о (Ье
eight vibrations of mcthyl al1d а torsion опе finds:
ga5 (n1Onomer)
solid (dimer)
vSH (а')
2605
2543
БSН (а')
802
802
vCS (а')
710
703
А slight increa5e of the absorption frequency of tlle SH stretching vibration in
the gas phase proves that thiols form hydrogen bridges, altl10ugh considerabIy less
strongly than alcohols. Ethanethiol, in the more stable Iralls conformation, possesses
а plane of sушmеtry and therefore belongs to the point group C s . The 21 normal
vibrations are divided into 13а' and 8а" species of vibration. Leaving aside (Ье
eight vibrations of methyl (5а' + 3а") and а СС stretching vibration (а'), 7а' and
5а" normal vibrations rешаiп for the CHzSH fragmcnt:
а': v.,CHz, vSH, БСНz, wCHz, БSН, vCS and БСS;
а": vaCH z , TCHz, pCHz and 2 torsions.
Methylene stretching vibrations
The /laCHz occurs moderately (о strongly in the region 2960 ::1: 25 cт l with, for
example EtCHzSH (2950 cm l) and also MeCHzSH and HSCHzCHzSH, which
both absorb а! 2970 cm l.
The /lsCH z vibration is moderately (о strongly active in the region 2900 ::1:
45 cm l with MeCHzSH (2940 cm l) а! the HW side; the lower limit is
по! unambiguously determined Ьу compounds such as MeNHC(==O)CH2CHzSH
(2855 cm l) and MeCHzSH (2872 cm l).
These ranges are more or less 15 cт ! higher than those of the methylene
stretchings of CHzOH but considerably lower than thosc of CHzX (Х = halogen).
з.з SIl//lIr bollded тel/ly/eпe
73
The SH stretcl1ing vibration
With а rangc of 2570 ::1: 30 cm 1 the vSH is the most charactcristic band in the
spcctra of thiols [34, 35]. McCHzSH and HzC==CHCHzSH, measured in the gas
phase, form thc uppcr Icvcl with 2600 cт 1, and they absorb in the vicinity of
2570 cт I as а liqllid. As lowest valuc, 2545 cт l is noted in thc spectra of
MeC(==O)NHCHzCHzSH, McNHC(==O)CHzSH and McSCHzSH. Iп most of the
compounds this SH strctch is found in the narrow range 2565 :f: 10 cm l. Тhe
intensity is mostly wcak and is vcry wcak evcn with butanethiol. Only for dithiols
with four or fcwcr carbon atoms сап thc intcnsity Ье called moderate to strong.
Methylene deformation, wagging and twisting vibrations
The vibrations are active in the ranges:
БСН z
1435 ::1: 25
wCH z
1260 ::1: 45
TCHz
1200 ::1: 60 cт l
mostly as moderate (о strong bands, although the twist might also turn out rather
weak. The lowest value for the wag (1220 cm l) is being found in the spectra of
IrallS HSCHzCHzSH and MeSCHzSH Ьи! most of the compounds show this wag
in the range 1270::1: 30 cm l. In the spectra of MeCH 2 SH and EtCH 2 SH the twist
occurs around 1250 cт 1, Ьи! absorbs approximately 100 cm 1 lower in the spectra
of CICHzCHzSH, BrCHzCH2SH, HSCHzCHzSH, PhCHzSH and MeSCH 2 SH.
SH deformation
The SH deformation is weakly (о moderately active in the region 840 :f: 55 cm 1
and is scnsitive to conformational changes in the molccule. For MeCH 2 SH опе
finds this vibration а! 870 cт l and for HSCH2CH2SH а! 890 and 800 cm l. Оп
the other hand, gтlc/le EtCHzSH, HzC==CHCH 2 SH and PhCHzSH are re5ponsible
for the lower values around 790 cm l.
Methylene rocking vibration
lПе methylene rock in the CHzSH fragment appears а! relatively low \vave
numbers (750::1: 35 cm l) in comparison with the rock in CHzHal, CH20 ,
CHzN and CHzC compounds, so that ап assignment is po5sible еуеп
when other methylene groups are present. The second methylene rock as5igned in
the spectrum of HSCH z CH 2 SH (gatlc/ze: 972; tralls: 942 cm l) falIs out5ide this
area.
CS stretching vibration
The vCS is sensitive (о conformation and mostly gets assigned as а moderate (о
strong band in the region 675 ::1: 45 cm l. High values (720 cm l) are reached in
74 Noтт/ VilJтlio"s a"d AlJsorplio" Regio"s о/ CH2X
thc spectra of IIШls-I'ISСНzСН2SН [27 29] and lI'a"s-ЕtСН2SН [15], altllOugll for
tl1e first {Iast} СОП1рОUlld also 693 and 655 [25] or 680 alld 660 [26] { 705 сП1 I
[12 14, 16---19]} \vould Ье. 111e lo\vest value ( 635 cт 1) is fOtllld in t11C spectrum
of MeNHC(==O)CHzSH, so that thc I/CS conccntrates itsclf а! 670 ::1: 35 cm l.
CS dеfоrП1аtiоп
Thc Б-С S is active in tllC unfriendly rallge оС 330 ::1: 90 СП1 1 and, morcover,
nlOstly а! \veak intensity. Gallc/le-ЕtСНzSН is responsibIe for tl1e higl1 value (417
cm l) \vhercas Ira"s-ВrСНzСНzSН, \vith 245 cm l, scorcs low. For most оС the
molecules this skeletal dсfоrП1аtiоп is situated а! 350 ::1: 50 cm 1 Ьи! also СОТ this
vibration IIШ1S and garlc/le conformers do по! produce the same values.
ТаЫе 3.10 Absorption region5 (cm l) of the normal vibrations of
CH2SH
Vibration С . Region Vibration С . Region
vaCHz а" 2960 :1:: 25 БSн а' 840 ::1: 55
l/sCHz а' 2900 :1:: 45 pCHz а" 730 ::1: 35
vSH а' 2570 ::1: 30 vCS а' 675 ::1: 45
Б СН 2 а' 1435 ::1: 25 Бсs а' 330 ::1: 90
wCHz а' 1260:1:: 45 torsion а" 200 ::1: 50
TCHz а" 1200::1: 60 torsion а" 130 ::1: 45
R CHzSH compounds
R = Me [ 12], Et [11 19], HSCHzCHz , HOC(==O)CHz [22],
MeOC(==O)CHz , MeNHC(==O)CH2 and MeC(==O)NHCHz [23],
HOCHz , HSCHz [2 29], CICHz and BrCHz [20], iPr [21],
HOC(==O) [22], MeNHC(==O) [23], MeOC(==O) , ЕtOС(==О) ,
02C , HzC==CH [33], Ph [30, 31], 2-Fu [36], MeS [32].
References
1. Н. Siebert, Z. Allorg. Allg. С/le/II., 271, 65 (1952).
2. I.W. Мау and E.L. Расе, Spcc/rocllim. Acta, Part А, 24А, 1605 (1968).
З. О. Saur, J. Travert, J.-c. Lavalley and М. Chabanel, C.R. Acad. Sci., 5cr. С, 291С, 227
( 1980).
4. D.W. Scott, H.L. Finke, J.P. McCullough, М.Е. Gross, к-о. William5on, а. Waddington
and Н.М. Huffman, J. АlIl. C/IClll. 50С., 73, 261 (1951).
5. O.W. Scott and J.P. McCullough, J. АlIl. CI,еlll. 50С., 80, 3554 (1958).
6. А.1. Bames, Н.Е. Наllаm and J.D.R. Howells, J. CI/C/II. Soc., Faraday Trans 11 68, 737
(1972).
7. W.O. George, J.H.S. Green and 0.1. Harrison, 5pcclrocllim. Acta, Par/ А, 24А, 367
( 1968).
з.з SlIlfilr bo"ded тelhy/eпe
75
8. D. Smith, J.P. Dcvlin and D.W. SCO\\, J. Mol. Spectrosc., 25, 174 (1968).
9. J.R. Durig, W.E. Bucy, C.J. Wurrcy and L.A. Carreira, J. PIIYs. ChclIl., 79,988 (1975).
10. Н. Wolff and J. Szydlowski, Саll. J. Chem., 63, 1708 (1985).
11. R. Fausto, J.J.c. Teixcira-Dias and P.R. Carey, J. Мо/. S/r/lct., 159, 137 (1987).
12. D.W. Sco\\ and M.Z. EI Sabban, J. Mol. 5peclrosc., 30,317 (J969).
13. к-а. Allum, J.A Crcighton, J.I-I.S. Green, а.1. Minkoff and L.1.S. Princc, Spcctrocllilll.
ACla, Part А, 24А, 928 (1968).
14. Т.Н. Joo, К. Kim ашl M.S. Kim, J. P/1YS. ClICт., 90, 5817 (1986).
15. R.E. Pcnnington, D.W. Sco\\, H.L. Finke, J.P. McCullough, J.F. Mcsscrly, I.A.
Hosscnlopp and О. Waddington, J. Ат. Cllc/ll. 50С., 78, 3266 (1956).
16. Т. Torgrimsen and Р. Кlaboe, Лсta Cllem. 5ca//d., 24, 1139 (1970).
17. М. Hayashi, У. Shiro and Н. Murata, BIIII. Cllem. 50С. Jp//., 39, 112 (1966).
18. а. Radinger and Н. Wi\\ek, Z. P/1YS. Clleт., Abt. В, 458, 329 (1940).
19. I.F. Tro\\er and H.W. Thompson,J. ClIC/ll. 50С., 481 (1946).
20. М. Hayashi, У. Shiro, М. Murakami and Н. Murata, 8111/. CI,ClIl. 50С. JplI., 38, 1740
(1965).
21. O.W. Sco\\, J.P. McCullough, 1.F. Messerly, R.E. Pcnnington, /.А. Hosscnlopp, H.L.
Finke and а. Waddington, J. Ат. Cllem. 50С., 80, 55 (1958).
22. N. Saraswathi and S. Soundararajan, J. Мо/. 5tr/lct., 4. 419 (J969).
23. а. Zuppiroli, С. Perchard, М.Н. Ваroп and С. de Loze, J. Мо/. Str/lcl., 69. 1 (1980).
24. S.K. Nandy, О.К- Mukherjee, S.B. Roy and G.S. Kastha,llldiaIlJ. PI,ys., 47, 528 (1973).
25. О. Welti and О. Whi\\aker, J. ClIC/II. 50С., 4372 (1962).
26. М. Ikram and О.В. Powcll, 5pcctrocllim. Acta, Parl А. 28А, 59 (1972).
27. М. Ohsaku and Н. Murata, J. Мо/. 5trllct., 52, 143 (1979).
28. М. Hayashi, У. Shiro, Т. Oshima and Н. Murata, B/lI/. Cllem. 50С. Jpll., 38,1734 (/965).
29. с.к. K\von, к- Kim, M.S. Kim and Y.S. Lec,J. Мо/. Slrllc/., 197, 171 (1989).
30. к- Doerffel and В. Adler, Wiss. Z. Tccll. Hocllscll. Cllem. Lelllla Merseb//rg, 10, 7 (1968).
31. Р.К. Mallick, S. Cha\\opadhyay and S.B. BanncIjce, I//diall J. P//re Appl. P/,ys., 11,609
(1973).
32. М. Ohsaku, У. Shiro and Н. Murata, B//II. CI,CIll. 50С. Jp//., 45, 3035 (1972).
33. C.S. Hsu, 5peclrosc. Lett., 7, 439 (1974).
34. N. Mori, S. Kaido, К. Suzuki, М. Nakamura and У. Tsuzuki, 8//1/. Cllelll. Soc. Jp"., 44,
1858 (1971).
35. G.F. Bolshakov, Izv. Vyssll. Ucllebll. Zaved. Neft Gaz, 23, 39 (1980).
36. М. Senecha1 and Р. Saumagne, J. Cllilll. PIIYs., 69, 1246 (1972).
3.3.2 MethyIthiomethyl
Compounds such as XCHzSMe (Х = halogen) show а plane of symmetry in the traпs
солfоrmаtiоп and therefore Ьеlолg to the point group С . Ьу which the 21 norma1
vibrations are being divided among 13а' алd 8а" species of vibration. Replacing
the СХ stretching vibration (а') Ьу а torsion (а") leads to 12а' and 9а" vibrations
for the CHzSMe frаgmелt:
а': Y Me, vsMe, vsCH z , Б Ме, БСН z , БsМе, wCHz, р'Ме, vaCSC, vsCSC and two
skeletal deformations;
а": УаМе, vaCH z , БаМе, TCH z , рМе, pCHz and three torsions.
76 NOI"/IIa/ Vi/Jтliolls alld Abs0l1Jlioll Regiolls о/ CH2X
Mct\lyl and n1ctl1ylenc stretclling vibrations
lПс five СН stretcl1ing vibratiol1s are activc bctwccn 3000 and 2850 сш 1 and
it is по! siшрlе (о assign thc individual vibrations. AltllOugll тапу analysts ошit
further specifications, а c\assification of thesc СН strctcllil1g vibratiol1s gcncralIy is
as folIo\vs:
УаМе :::: Y Me :::: IIaCH2 > IIsMe :::: V s C H 2
in which thc шеtl1уl sушmеtriс stretch appears most strong\y and the other
stretching vibrations exhibit moderatc intensity.
Methyl and methy\enc deformations
Although the areas of tlle t\VO methyl antisymmetric deformations part\y over
\ар, often I\vo bands appear in the ranges 1440 ::1: 15 and 1425 ::1: 15 cm l. The
methy\ene scissors is weakly (о moderately active а! 1405 ::1: 30 cт ], which is 50
\vavenumbers lo\ver than the range of the CHz scissors in RCHzOMe compounds.
lПе methyl sуmшеtric deformatiol1 (1320 ::1: 10 cm l) absorbs 125 сш l \ower
than the corresponding vibration with RCHzOMe molecules and сап Ье counted
among the good group vibrations. Unfortunate\y the intensity is шоst\у inadequate.
Methylene \vagging and t\visting vibrations
lПе methylene wag (1250 ::1: 55) and twist (1200 ::1: 80 cm l) absorb respective\y
100 and 70 \vаvепuшЬеrs 10\ver than with methoxymethyl сошроuпds. The
absorption regions are de\imited Ьу the folIo\ving compounds: MeOCHzSMe (w:
1305; т: 1280), EtOCH 2 SMe (w: 1302; т: 1273), MeSCHzSCHzSMe (w: 1195
and ]2]8; т: 1132 and ] 165), MeSCHzCHzSMe (w: ]285 and ]268; т: 1120 and
] ] 95).
Methy\ and methylene rocking vibrations
The methyl rocks get assigned а! 1000 ::1: 35 (а') and 940 ::1: 30 cт 1 (а"). Тl1e
highest value of the рМе is Iocated in the spectrum of MeSCHzCHzSMe (1035
cm l) and the lowest value of the р'Ме in that of nPrCHzSMe (916 cm I). Most
of the analysed compounds show these methyl rocks in the regions 995 ::1: 30
and 950 :!: 20 cm t. With its range of 815::1: 75 cт l and шоstlу а weak band
intensity, the methylene rock is по! ап example of а good group vibration and is
moreover sensitive (о conformation. Not considering the values for MeOCH2SMe
(888 cm I), EtOCHzSMe (877 cm l) and MeSCH2CHZSMe (740 cm l), this
vibration occurs in the area 815 ::1: 50 cm l.
з.з Sи//иr-bollded тe//ly/eпe
77
CSC stretching vibrations
It is по! aJways straightforward (о diffcrentiate betwccn thcse а' stretching
vibrations. Thc two arcas overlap each other and the different conformers do по!
show thc same wavcnumbcr. Ncvcrthcless the CSC antisymmetric stretch (725 :!::
50 cm l) is associatcd with vS Me and thc symmetric stretch (680:!:: 45 cm l)
rather with thc vCHz S. Thc intcnsitics are weak (о moderate, rarcly strong.
SkeIctal deformations and torsions
The two skeletal deformations, of which thc first is ап essentially external vibration
and the second the CHz S Me deformation, are also sensitive (о conformation
and mostly result in а weak band in the regions 370 :!:: 50 and 250 :!:: 40 cm l. In
аll probability the torsions тМе, TSMe and TCH2SMe will Ье noted а! 190 :!:: 30,
145 ::1: 35 and 75 :1: 30 cт 1.
ТаЫе 3.11 Absorption rcgions (cm l) of thc norrnal vibration5
of CHzSMc
Vibration Rcgion Vibration Rcgion
УаМе 2990 ::1: 10 рМс 1000 :!:: 35
Y Me 2970 ::1: 10 р'Мс 940 :!:: 30
VaCHz 2960 ::1: 15 pCHz 815 :!:: 75
vsMc 2920 ::1: 10 vaCSC 725 :!:: 50
vsCHz 2885 ::1: 30 vsCSC 680 :!:: 45
Бамс 1440 :1: 15 skclctal dcf. 370 :!:: 50
Б'мс 1425 ::1: 15 skclctal dcf. 250 :!:: 40
Бен? 1405 ::1: 30 torsion 190:!:: 30
БsМ; 1320 ::1: 10 torsion 145 :!:: 35
wCHz 1250 ::1: 55 tor5ion 75 :!:: 30
TCHz 1200 ::1: 80
R CHzSMe compounds
R = Me [1 10], DзС [9], nPr [11], MeOCHz [13], MeSCH2 [13
15], MeS(CHz)ll (11 = 2----4) [16], CICHz and BrCHz [12], iPr [25],
N=C [19], Ph [17, 18], MeO [20, 21], EtO [21], HS and
DS [22], MeS [15, 23, 24], MeSCHzS and MeSCHzSCH2S [23,
24].
References
1. М. Haya5hi, Т. Shimanouchi and S. Mizu5hima,J. Cllem. PJ,yS., 26, 608 (1957).
2. М. Ohsaku, У. Shiro and Н. Murata, BIIII. CJ,eт. 50С. JPI/., 45, 954 (1972).
3. М. Ohsaku, У. Shiro and н. Murata, BIIII. С//ст. Soc. Jpll., 46, 1399 (1973).
78 Noтza/ \libтlio/ls IIIlС/ Absol1J1io/l Regiolls о/ CH2X
4. D.W. Sco\\ and J.P. McCullollgh, J. Ат. ClICIIl. 50С., 80, 3554 (1958).
5. D.\V. Sco\\ ,lI1d M.Z. EI-Sabllan, J. Мо/. 5[1CClrosc., 30, 317 (1969).
6. D.W. SCO\\, H.L. Finkc, J.P. McCullougll. М.Е. Gюss, К.О. WilliаП1S0П, а. Waddil1gton
and Н.М. HutTтal1, J. Ат. О/ст. 50С., 73. 261 (1951).
7. W.O. Georgc, J.H.S. Grccn and О.1. Напisоп, Spcc/roc/lim. Ас/а, Part А, 24А, 367
(1968).
8. R. Fausto, J.1.c. Tcixcira-Dias and P.R. Carcy, J. Мо/. 5/ПlС/., 159, 137 (1987).
9. М. Sakakibara. Н. Malsuura, 1. Harada and Т. SI,iП1аI10uс!li, BIIII. C/1CIIl. 50С. J[1/1., 50,
111 (1977).
10. J.R. Durig. M.S. Rollil1s and Н.У. Phan, J. Mol. 5lrllct., 263, 95 (1991).
11. М. Ohta. У. Oga\va, Н. Matsuura, 1. Harada al1d Т. Shimal1ouchi, BIIII. C/1CIIl. 50С. JP/I.,
50, 380 (1977).
12. Н. Matsuura, N. Miyauchi, Н. Murata and М. Sakakibara, BIIII. С//{.'т. 50С. JP/I., 52,
344 (1979).
13. У. Oga\va, М. Ohta, М. Sakakibara, Н. Matsuura, 1. Harada and Т. Shimanouchi, BIIII.
C/re;;'. 50С. JP/I., 50, 650 (1977).
14. М. Hayashi. У. Shiro, Т. Oshima and Н. Murata, BIIII. C/leIIl. 50С. JP/I., 39, 118 (1966).
15. О. Welti and О. \Vhi\\aker,J. C/lem. Soc., 4372 (1962).
16. Н. Matsuura, 1. MatsunlOto and Н. Murata, 5pcclroc/lim. Acla, Part А, 36А, 291 (1980).
17. К. Docrffel and В. Adler, IViss. Z. TCC/I.Hoc/1SC/I. ClleIIl. Le/ll/Q-Mcrsebllrg, 10, 7 (1968).
18. К.а. Allum, J.A Creighton, J.H.S. Grcen, а.1. MinkotI and L.1.S. Prince, 5pcctroc/liIIl.
ACla, Рап А, 24А. 928 (1968).
19. S.\V. Charles, F.c. Cullen and N.L. O\ven,J. Мо/. StПlсl., 34, 219 (1976).
20. Н. Matsuura, К. Кimura al1d Н. Murata, J. Мо/. 51П1сt., 64, 281 (1980).
21. Н. Matsuura, Н. Murata and М. Sakakibara,J. Мо/. 5tПlсt., 96, 267 (1983).
22. М. Ohsaku, У. Shiro and Н. Murata, BIIII. О/ст. Soc. JplI., 45, 3035 (1972).
23. М. Ohsaku, BIIII. О/ст. 50С. JplI., 47, 965 (1974).
24. М. Ohsaku, У. Shiro and Н. Murata, BIIII. С/lCI/1. 50С. JP/I., 45, 113 (1972).
25. N. Nogami, Н. Sugeta and Т. Miyaza\va, BIIII. C/leIIl. Soc. JP/I., 48, 2417 (1975).
3.3.3. Thiocyanatomethyl
Ethyl thiocyanate possesses 24 normal vibrations which are divided for the С .
conformation into 15а' and 9а" species of vibration. After subtraction of eight
methyl vibrations (5а' + 3а") and а СС stretching vibration (а') the remaining
normal vibrations (9а' + 6а") have (о Ье assigned (о CHzSCN:
а': vsCH z , vC=N, БСНz, wCHz, vaCSC, vsCSC, БSСN, Б СS, БСSС;
а": vaCH z , TCH z , pCHz, ,SCN, , CS and torsion.
Methylene vibrations
In the ranges of У а СН 2 (2969 ::1: 20) and vsCHz (2930 ::1: 10 cm t) the high values
(3035 and 2970) of CICH 2 SCN have по! Ьееп listed (see Section 3.1.2).
The regions of the mcthylene deformations тау Ье compared with those of
other sulfur-bonded mcthylene compounds (see Sections 3.3.1 and 3.3.2). If the
low value (1157 cm l) in the spectrum of CICHzSCN is left aside, the methylene
з.з SIl/fi,, bollded тel/zy/eпe
79
twist restricts itsclf (о 1220 ::1: 25 cm l. The high value (868 cm l) for the pCHz
in the samc spcctrum also has по! Ьесп taken into account.
Thc C=N strctching vibration
Thc C=N stretching vibration produccs the most characteristic band in the spectra
of thiocyanatcs. This remarkabIc group vibration appcars а! 2155 :1: 10 cm l,
sharp and intensc, in constrast (о that of isothiocyanates, which is also active in
this ncighbourhood Ьи! with а typical broad structure (see Scction 3.4.4).
CSC stretching vibrations and skeletal dcformations
The antisymmetric CSC stretch, which is associated with the S CN stretching
vibration, appears weakly (о moderately а! 685:1: 15 cm 1, and the symmetric CSC
stretch, corresponding with the CHz S stretching vibration, absorbs moderately
to strongly in the range 635 ::1: 25 cm l.
lПе CH 2 SCN group provides five skeletal deformations and а torsion, in which
two R C S (R==C) skeletal deformations must Ье considered as extemal
deformations. Тhese skeletal deformations absorb weakly (о moderately and, in
the absence of а plane of symmetry, the difference between in plane and out-of
plane disappears. The torsion in Me CHzSCN is found around 230 cm l; the
torsions of larger molccules are expected (о Ье much lower.
ТаЫе 3.12 Absorption regions (cm l) ofthc nOm1al vibrations of CH2SCN
Vibration С . Region Vibration С . Rcgion
У а СН 2 а" 2960 ::1: 20 vsCSC а' 635 :1: 25
vsCHz а' 2930 ::1: 10 БS СN а' 465 :1: 15
vC=N а' 2155::1: 10 fS CN а" 410:1: 10
Бснz а' 1420 ::1: 20 C S skelet.dcf. а' 320 r 20
wCHz а' 1255 ::1: 25 C S skclet.def. а" 290 :1: 20
TCHz а" 1200 ::1: 45 CSC skelct.def. а' 150:1: 20
pCHz а" 780 ::1: 20 torsion а"
vaCSC а' 685 ::1: 15
R CH,SCN molecules
R = M; [1 5], Et [1], nPr [1], Ph [6], HC=C and OC=C [9],
CI [7,8].
References
1. R.P. Hirschmann, R.N. Кniseley and У.А. Fassel, Speclrocllim. Acta, 20,809 (1964).
2. а.А. Crowder,J. Мо/. 5trllc/., 7,147 (1971).
80 Norllla/ VilJralio"s а/l(/ A/JSOIIJ/io" Regio"s о/ CH2X
3. О.Н. Ellestad and Т. Тощriтsсп,J. Mol. Strllct., 12,79 (1972).
4. J.R. Durig. J.F. Sullivan and H.L. Hcuscl,J. P/,yS. CI/СIII., 88, 374 (1984).
5. а.О. Braalllcn and А Gatial, Sp<,clrocllilll. АсЫ. Parl А, 42А, 615 (1986).
6. СА. Sjogrcn, Acla CI/<'III. 5cтrd., Ser. А, 38А, 657 (1984).
7. а.А. Cro\\'dcr,J. CI/<'III. P/,YS.. 47, 3080 (1967).
8. а.А. Сю\vdеr, T<,x.J. 5ci., 26. 565 (1975).
9. Т. Midtg:l3ld. а. Gundcrsen and С.1. Nielsen,J. Mol. Slrllct., 176, 159 (1988).
3.4 NIТROGEN-BONDED METHYLENE
3.4.1 Aminol11etllyl
Molecules such as MeCH 2 NH z possess а plane of symmetry in the /ralls
conformation and belong 'о the point group C s . lПе 24 normal vibrations must
Ье divided among 14а' and 10а" types. When the eight vibrations (5а' + 3а") of
methyl and а vCC (а') are left ои! of consideration, the other 15 (8а' + 7а") сап
Ье assigned (о the CHzNHz fragment:
а': vsNH z . vsCHz. БNНz. БСН 2 , wCH z , vCN. wNHz, skeletal deformation;
а": vaNHz, vaCH z , TCHz, T/pNH z . pCH z and two torsions.
Amine stretching vibrations
lПе amine stretching vibrations cause t\VO wcak (о moderate absorptions with
approximately equal intensity. Although the NHz group is less subject (о the
formation of hydrogen bridges than the ОН group, this doublet appears much
sharper and а! 25 cm 1 higher wavcnumbers in dilute solutions and а! 50 cm 1
higher \vavenumbers for а gas. In the associated state vaNHz occurs а! 3365 ::1: 20
cm 1. FЗССН2NНz absorbs а! 3385 cт 1, n alkanamines а! 3365::1: 5 cт l [31]
and FCHzCH2NHz а! 3345 cm l. lПе region 3285::1: 20 cm 1 is characteristic
for vsNHz with PhCHzNHz а! 3300 cm l, n alkanamines а! 3280 ::1: 5 cm l and
FCH 2 CH z а! 3267 cm l. А! the LW side of this band опе often finds а weaker
absorption а! 3180 :1: 20 cm l. This might Ье ап overtone of the NH z scissors
inten5ified Ьу Ferrni resonance interaction witll vsNHz and therefore is sometimes
also as5igned (о this symmetric 5tretching [25].
Methylene stretching vibrations
With the cxception of FзССНzNН2 (v a а! 2987 and у . а! 2960 cт 1) the methylene
antisymmetric stretching is found а! 2930 ::1: 15 cт 1 and the symmetric stretching
а! 2870 :1: 20 cm l.
3.4 Ni/rogeп boпded Me/hy/eпe
81
Amine dcformation
Iп thc associated state the NHz scissoring vibration appears as а modcrate (о strong
band in thc rcgion 1610 :1: 15 cm l, а vibration which is found а! 1623 cm l in
thc spcctrum of methanamine [24]. This band is considerabIy broader than the
sharp aromatic ring stretching modes in the neighbourhood of 1600 cm ! and
moves 25 cт 1 lowcr in solution. lПе CHzNHz fragment, combined with ап
unsaturatcd or aromatic part of а moleculc, shows this NHz scissors а! the lower
side of the region а! approximately 1600 cт 1, as for instance HC=CCHzNH z
(1597), HzC==CHCHzNHz (1604), PhCHzNH z (1603) and 2 FuCHzNHz (1603
cm l).
Methylene deformations
The area 1450 ::1: 20 cm l for the methylene deformation is delermined Ьу
HzNCHzCHzNHz (1469 and 1456 cm l) and HC=CCHzNH z (1435 cm I). Most
of the CHzNHz compounds absorb in thc region 1450:1: 10 cт 1 with moderate
intensity.
The methylene wag absorbs with а weak (о moderate inten5ity in the region
1360::1: 25 cm l, as defined Ьу FзССНzNНz (1384) and PhOCHzCHzNНz (1336
cт 1).
The weak (о moderate band а! 1290 ::1: 45 cт ! is mostly assigned to the
methylene twist Ьи! also partly (о the amine twist [3, 5, 6, 13]. lПе highest values
are found in the spectra of RCHzNHz compounds in which R is ап aromatic or
unsaturated fragment such as 2 FuCHzNHz (1335), HC=CCH2NНZ (1330), or
H2C==CHCHzNHz (1328 cт 1) and the lowest in that of 1 butanamine with
1245 cm l, а value which тау Ье assigned (о the amine twi5ting vibration as
well.
Amine twisting vibration
lПе amine twist or rock, which is more or less connected with the CN stretch and
the methylene twist, appears in the spectra of CHzNHz compounds in the region
1215 ::1: 70 cт 1 with а weak intensity and is по! significant for identification
purposes. HzC==CHCHzNHz shows this twist а! 1280 cm 1, EtCH2NНZ а! 1275
cт 1 Ьи! HzNCHzCHzNHz at1254 cm 1 [11] or а! 1182 and 1148 cm 1 [7].
CN stretching vibration
lПе CN stretch, somewhat connected with the amine twist, арреш as а moderate
10 strong band in the region 1075::1: 25 cm l, which is for the most part deterrnined
Ьу HzNCHzCHzNHz with 1096 and 1054 cm l.
82 Norma/ VilJra/iOl/s Ш/([ AlJSOlptioll Regiolls о/ CH2X
Methylcne rocking vibration
lПе methylenc rock ab50rbs а! 890 ::1: 55 cm 1 Ьи! is diПicult 'о obscrvc wl1en
superimposed оп thc \vidc NHz wag band. lп contrast, I1igll values such as 943
cm 1 in the 5pectrum of HC=CCHzNH z are easily assigned.
Amine \vagging vibration
In the associated state, primary amines display а typicaI diffuse 5trong band in the
region 845 ::1: 50 cm 1, due 'о the NHz wagging mode. Diamincs witl1 slюrt chains
such as H2NCHzCHzNHz (894 and 82/), НzN(СНz)зNНz (862) and FзССНzNНz
(880 cm l) are respon5ible for the high value5. The remaining рriшаrу amines
produce thi5 wagging mode а! 830 ::1: 35 cm l; the ones with long chains are
respon5ible for the lo\vest values, for example Me(CH2)"NHz (11 > 8): 800 ::1: 5
cm l. lп solution or for а gas, the hydrogen bridges disappear and the amine wag
ab5orb5 sharply а! 770 ::1: 30 ст 1. In the solid state а! low tешреrаturе, however,
the wag moves 'о higher \vavenumber5 (920 ::1: 40 ст 1).
Skeletal deforrnation and torsions
lПе C N skeletal deforrnation is generally weakly active а! 390 ::1: 75 cm l,
with а high value for HzNCHzCHzNHz (464 and 330) and а low value for
HzC==CDCHzNН z (315 cm l). lПе NHz tor5ion is found а! 255 ::1: 40 cт l
and the CHzNHz torsion mау Ье expected lower than 200 cm l.
ТаЫе 3.13 Absorption rcgions (сm l) of thc normal vibrations of CHzNHz
Vibration С . Rcgion Vibration С . Region
vaNНz а" 3365 ::1: 20 T/pNHz а" 1215 ::1: 70
vsNHz а' 3285 ::1: 20 vCN а' 1075 ::1: 25
vaCHz а" 2930 ::1: 15 pCHz а" 890 ::1: 55
vsCHz а' 2870 ::1: 20 wNHz а' 845 ::1: 50
БNН, а' 1610::1: 15 C N dcf. а' 390 ::1: 75
БСн; а' 1450 ::1: 20 torsion а" 255 ::1: 40
wCHz а' 1360 ::1: 25 torsion а" <200
TCHz а" 1290 ::1: 45
lПе following R CHzNНz compound5 have Ьееп taken into account:
R = Me [1, 26], Et [1 ], Pr [1, 5, 6], iPrCHz , tBuCHz ,
PhCHz [23], HzNCHzCHz HzNCHz [7 1l], PhOCHz [23], 4
MeOPhOCHz [23], ОзSСНz [12], FCHz [13], CICHz [14],
BrCHz [15], iPr , PhzCH [30], (Bи , FзС [16], HzC==CH and
HzC==CD [17 19, 27, 28], HC=C [20,21], Ph [22, 23], 2 Fu [29].
3.4 Nilrogell bo1lded Me/hy/elle
83
References
1. Н. Wolff and Н. Ludwig, Вст. BII//sellges. P/IYS. C/lem., 71,1107 (1967).
2. N. Sato, У. Hamada and М. Tsuboi, 5peclroc/lim. ACla, Part А, 43А, 943 (1987).
3. L.AE. Batista Ое Carvalho, А.М. Amorim Оа Costa, M.L. Duarte and J.J.c. Teixeira
Dias, 5peclrocIIim. ACla, Part А, 44А, 723 (1988).
4. J.R. Durig. W.B. Bcshir, S.E. Godbey and Т.1. Нizcr, J. Rama// 5pcclrosc., 20,311
(] 989).
5. J.J.c. Tcixcira Dias, L.A.E. Batista Ое Carvalho, АМ. Amorim Оа Costa,
I.M.S.Lampreia and E.F.G.Barbosa, 5pcclrocIIim. ACla, Parl А, 42А, 589 (1986).
6. О. Ramis and О. Busca,J. Мо/. 5Irllcl., 193, 93 (1989).
7. A-L. Borring and К. Rasmussen, Speclrocllim. Ас/а, Parl А, 31А, 889 (1975).
8. А Sabatini and S. Califano, 5pCClroC/lilll. ACla, 16,677 (1960).
9. У. Omura and Т. Shimanouchi, J. Мо/. Speclrosc., 57, 480 (1975).
10. L. Scgal and F.V. Eggcrton, Appl. Spcclrosc., 15, 112 (1961).
11. М. Giorgini, M.R. Pellct, а. Paliani and R.S. Cataliotti, J. Ralllaп 5pcclrosC., 14, 16
( 1983).
12. К. Ohno, У. Mandai and Н. Matsuura,J. Мо/. Slrllcl., 268, 41 (1992).
13. J.AS. Smith and V.F. Kalasinsky, 5peclrocllim. ACla, Parl А, 42А, 157 (1986).
14. М. Nakata and М. Tasumi, 5peclrocIIilll. Асщ Parl А, 41А, 341 (1985).
15. М. Nakata and М. Tasumi, 5peclrocIIilll. ACla, Part А, 41А, 1015 (1985).
16. Н. Wolff, О. Нот and Н.-а. Rollar, 5peclroc/lilll. ACla, Parl Л, 29А, 1835 (1973).
17. A.L. Уеrrnа and Р. Vcnkatcswarlu,J. Мо/. SpCClrosc., 39, 227 (1971).
18. В. Silvi and J.P. Perchard, SpeclrocIIim. Acla, Parl А, 32А, 23 (J976).
J9. J.R. Durig, J.F. Sullivan and с.М. Whang, 5peclrOC/lim. ACla, Parl А, 41А, 129 (1985).
20. У. Hamada, М. Tsuboi, М. Nakata and М. Tasumi,J. Мо/. Spectrosc., 107, 269 (1984).
21. N.V. Riggs, AlIst. J. CI,em., 40, 435 (1987).
22. S. Chattopadhyay, IIl(lia// J. P/,yS., 41, 759 (1967).
23. О. Varsanyi, Assig//mcl/Is [о, Vibraliolla/ Speclra о[ 5cve// H/I//drcd Be//zelle Dcrivalives,
J.Wiley & Sons, New York (1974).
24. Р. Pulay and F. Тбrбk, J. Мо/. Slrllcl., 29, 239 (1975).
25. Н. Wolff, U. Schmidt and Е. Wolff, Spectrocllilll. ACla, Parl А, 36А, 899 (1980).
26. У. Hamada, К. Hashiguchi, АУ. Нirakawa, М. Tsuboi, М. Nakata and М. Tasumi, J.
Мо/. 5peclrosc., 102, J23 (1983).
27. У. Hamada, М. Tsuboi, М. Nakata and М. Tasumi,J. Mol. Spcclrosc., 106,164 (1984).
28. К. Yamanouchi, Т. Matsuzawa, К. Kuchitsu, У. Hamada and М. Tsuboi, J. Мо/. 5Ir/lcl.,
126, 305 (1985).
29. Н. Senechal and Р. Saumagne, J. СЫт. P/,yS., 69, 1246 (1972).
30. S. Chakravorti, R. Ое, Р,к. Mallick and S.B. BancIjee, 5pCClrocIIi11l. ACla, Part А, 49А,
543 (1993).
31. С.1. Pouchert, Т/lе A/dl'ic/I Library о[ FT IR Speclra, Aldrich Chemical Сотрапу, first
edn. (1985).
3.4.2 AmmoniomethyI
Et NH! belongs (о the point group C s . lПе 27 norma1 vibrations are divided into
16а' and l1а" types. If the eight vibrations (5а' + 3а") of methyl and а уСС (а')
are left ои! of consideration, 10а' and 8а" vibrations remain for the CHzNH!
part:
84 NOI'I/la/ VilJl'alio//S lIт/ AlJSOIIJlioll Regiolls о/ CH2X
а': I/ NЩ, IlsNHj. vsCHz, Б NЩ, БsNЩ, БСНz, wCHz, vC N, p'NHj,
Б С N;
а": vаNЩ, llaCHZ, БаNЩ, TCHz, рNЩ, pCHz, тNЩ and torsion CHzNНj.
Since most of the 5pcctra are run in ап alkali halide matrix, the diffсrспtiаtiоп
of types of vibration is of minor iшроrtапсе. Morcover, the strong ion interactions
disturb the sушmеtry, 50 that the selection rules are по longer applicable. The
undisturbcd шеthапашiпiuш ion [1 6] shows 12 (5аl + az + 6е) fundamcntal
vibrations according to СЗ,. sушmеtrу, Ьи! 18 vibrations (11а' + 7а") in С .
symmetry, where the al vibrations change into а', the az vibrations in а" and
the е vibrations split ир into а' and а" species. Even the difference between а' and
а" di5appear5 o\ving 'о the tran5ition into the С. conformation.
Typical for the amine 5alts and the amino acids is the very broad aminium band
in the range between 3600 and 2000 cm l with superimposed оп it, the NHj and
CHz stretching vibrations, plus а serie5 of typical ab5orptions due 'о the following
interactions [6,8]:
:::::270Q-..-:::::2600 cm l: NH+ ... N (association)
:::::260Q-..-:::::2500 cm l: NH+ ... Br (interaction with КВr)
:::::240Q-..-:::::2000 cm l: NH+ ... CI (HCI salt)
:::::220Q-..-:::::2000 cm l: БаNНj + тNЩ (combination band)
Stretching vibrations
Тhe ехас! wavenumbers of the stretching vibrations are difficult (о locate. А! best,
the stretching vibrations are found as small minima оп the wide aminium band.
lПе aminium anti5ymmetric 5tretching vibrations absorb а! :::::100 cm 1 higher than
those of methyl and methylene, Ьи! the symmetric ones coincide with the lattcr.
Тhe highest values for the aminium апti5уmшеtriс stretching vibrations are found
in the Raman 5pectrum of MeCH2NН) NoЗ- (3240 and 3115 сm 1) апd the lowest
in that of +НзNСНzСНzNЩ (3030,3000 and 3027, 2982 cm I). The following
regions off good po55ibilities:
vаNЩ
v NНj
vsNЩ
vaCH z
vsCHz
3150 ::1: 50 3055::1: 60 2960::1: 50 2930::1: 30 2860::1: 60
Arninium deformation5
lПе range5 of the NЩ antisymmetric deformation5 and the СО2" antisymmetric
stretch overlap each other in 5uch а way as to make it difficult (о a5sign
the two vibration5 unambiguou5ly in the spectra of amino acids. Moreover, in
the area 170Q-..-1200 cm l the amino acids display а typical broad absorption
оп which the aminium and the methylene deformations as well as the СО:;-
stretching vibration5 are superimpo5ed. lПе aminium antisymmetric deformatio s
3.4 Nilrogeп-boпded Me/hy/ene
85
of OZCCH2CHzNHj are assigned а! 1650 and 1630 cm 1 [15] or а! 1565 and
1548 cm l [16). High values for the same vibrations are assigned in the spectra
of НОЗРСН2NНj (1650 and 1622) and НОзРСНzСНzNНз (1635 and 1628
cm 1). Thc symmctric dcformation attains the highest values in the spectra of
OZCCH2NIIC(==O)CHzNHj (1575) and OzCCHzNHC(==O)zCHzNHj (1560
cm I). Most of the invcstigatcd compounds display aminium deformations in the
regions:
БаNНj Б NНj БsNНj
1610 :i: 25 1585:!: 25 1505:!: 25
The CN stretching vibration and NHj rocking modes
Although the CN stretch and the NHj rock сап couple, this stretching vibration is
unambiguously assigned in the neighbourhood of 1050 cm l. For the NHj rocks,
three ranges are taken into account:
pNH 3 p'NНj/vCC vCC/p'NНj
1150 ::1: 50 1070:!: 65 1015 :i: 85
In the spectra of dipolar ions, the two rocking modes are assigned in the two
ranges \vith the highest wavenumbers and ап external stretching mode in the range
witl1 the lowest wavenumber. For the NН з rocks of amine salts the two regions
with the lo\vest wavenumbers are suitabIe for analysis.
Skcletal deformations and torsions
With dipolar ions the absorption а! 480 :i: 55 cm 1 is assigned 'о the NHj twisting
vibration and that а! 340 ::1: 30 cт 1 (о the skeletal deformation. 'П the spectra of
amine salts, оп the contrary, the band а! 470 :i: 20 cm 1 belongs to the skeletal
deformation and the опе а! 305 ::1: 55 cm 1 to the NН з twist.
lПе data are col1ected from the spectra of fol1owing R CHzNHj compounds:
Amine salts:
R = Me [7], Et , Me(CH z )" (п = 6, 8 and 10) [8], FзС , +НзNСНz [6,
9 14], HzC==CH [17], FCHz , CICHz and BrCHz .
Dipolar iопs:
R = OzCCHz [15, 16], ОзSСНz [15, 18, 34], НОзРСНz [15],
OzC [18 26, 33], OzC [27], OzCCHzNHC(==O) and
OzCDzNHC(==O) [27], OzCCHzNHC(==O)z [28],
ОзSСНzСНzNНС(==О) [29], НОзРСНzNНС(==О) [30],
НОзР [31,32].
86 Norl1la/ VilJraliolls ти/ AlJsorplioll Regiolls о/ CH2X
ТаЫе 3.14 Absorption regions (cm l) of thc поmшl vibrations
of CHzNHj
Vibration Aminc salts Dipolar ions Gencral
vaNH 3135:1:: J05 3135:1:: 105
v'NH" 3045 :1:: 70 3045 :1:: 70
а 2960 :1:: 50 2960 :1:: 50
v s NH 3
VaCHz 2930 :1:: 30 2930 :1:: 30
V s CH 2 2860 :1:: 60 2860 :1:: 60
БаNН+ 1610:1:: 25 1605 :1:: 45 1605 :1:: 45
Б'NН 1585 :1:: 30 1575 :1:: 55 1575 :1:: 55
а 1500 :1:: 20 1525 :1:: 50 1525 ::1: 50
БsNН з
Бснz 1465 :1:: 30 1455 :1:: 20 1465 ::1: 30
wCHz 1340 :1:: 25 1360 :1:: 30 1350 :1:: 40
TCHz 1295 :1:: 50 1300 :1:: 40 1295:1:: 50
vCN 1055 :1:: 30 1040:1:: 25 J050 ::1: 35
pNНj 1070 :1:: 65 1150 :1:: 50 1100:1:: 100
p'NНj 1015 :1:: 85 1070 :1:: 65 1030:1:: 105
рС Н 2 845 :1:: 45 865 :1:: 55 860 :1:: 60
тNНj/БССN 470 :1:: 20 480 :1:: 55 480 :1:: 55
БССN/тNНj 305 :1:: 55 340 :1:: 30 310:1:: 60
torsion 190:1:: 50 170:1:: 60 175 :1:: 65
References
1. I.A. Oxton and О. Кnop, J. Мо/. SlrlICI., 37, 59 (1977).
2. Е. Caslcllucci, J. Mol. Slr/lCI., 23,449 (1974).
3. А. Тhcoret and С. Sandorfy, Spcclrocilim. ACla, Parl А, 23А, 519 (1967).
4. А. СаЬапа and С. Sandorfy, Speclrocllim. ACla, 18, 843 (1962).
5. Е.А.У. Ebs\vorth and N. Shcppard, Speclrocllil1l. ACla, 13, 261 (1959).
6. J. BeUanato, Spcclrocililll. ACla, 16, 1344 (1960).
7. Т.1. O'Leary and I.W. Levin, J. PI1)'S. С/,Сl1l., 88, 4074 (1984).
8. С. Siguёпzа, Р. Galcra, E.Otcro-Аепllе and P.F. Gonzalcz-Diaz, Speclrocilim. ACla, Parl
А, 37А, 459 (1981).
9. R.J. Murcinik and W. Schcuermann, SpCClrosc. LCIt., 3, 281 (1970).
10. R.1. Mureinik and W. Robb, Spcclrocilim. Ас/а, Parl А, 24А, 377 (1968).
11. R.D. McLachlan, Spectrocilil1l. Acta, Parl А, 30А, 985 (1974).
12. R.W. Berg and К. Rasmusscn,Speclrosc. Lell., 4, 288 (1971).
13. I.A. ОХlOп and О. Кnop,J. Мо/. SlrlICI., 43,17 (1978).
14. О.В. Powell, Spcclrocilil1l. Acla, 16,241 (1960).
15. С. Garrigou-Lagrange, Саl/. J. CIIC1I/., 56, 663 (1978).
16. R.S. Кrishinan and R.S. Katiyar, BIIII. Cllem. Soc. Jpll., 42, 2098 (1969).
17. R. Rcricha and Р. Svoboda, Collecl. CZCCll. C/ICm. COl1lmllll., 41,1014 (1976).
18. U. Slahlbcrg and Е. Stcger, Speclrocllil1l. ACla, Parl А, 23А, 475 (1967).
19. К. Machida, А. Kagayama, У. Saito, У. Kuroda and Т. Uno, Speclrocilim. ACla, Par/ А,
33А, 569 (1977).
20. J. Herranz and J.M. Dclgado, Speclrocilim. Acla. Parl А, 32А, 821 (1976).
21. С. Dcslrade, С. Garrigou Lagrangc and M. T. Forcl, J. Мо/. Slrllc/., 10,203 (1971).
22. 1. Laulicht, S. Pinchas, О. Samucl and 1. Wasscrman,J. PI,ys. CllCIlI., 70, 2719 (1966).
3.4 Ni/rogeп-boпded Me/hy/eпe
87
23. R.K. Кhаппа, М. Horak апd E.R. Liррiпсоtt, Spcctrocllim. ACla, 22, 1759 (1966).
24. S. Suzuki, Т. 5himanouchi апd М. Tsuboi, 5pcclrocllim. ACla, 19, 1 J 95 (1963).
25. О.М. Dodd, Speclroclliт. ACla, 15, 1072 (J959).
26. М. Tsuboi, Т. Опishi, J. Nakagawa, Т. Shimапоuсhi апd 5.1. Mizushima,5pcclrocIli1ll.
Acla, 12, 253 (1958).
27. С. Dcslradc, Е. Dupart, М. Joussot-DuЫеп апd С. Garrigou Lagrange, Сап. J. Cheт.,
52, 2590 (1974).
28. С. Dcstradc and С. Gаrrigоu-Lagrапgе, J. Мо/. Slr/lCI., 31, 301 (1976).
29. С. Gаrrigоu-L,grапgе, Н. Jспsсп апd М. Cotrait, J. Mol. 5lr/lcl., 36, 275 (1977).
30. М. Cotrait, М. Аvigпоп, J. Рrigепt апd С. Gаrrigоu-Lagrапgс, J. Мо/. Slr/lct., 32, 45
(J 976).
31. С. Gаrrigоu Lagrапgе апd С. Destrade, J. Cllim. PJ/ys., 67, 1646 (1970).
32. С. Gаrrigоu-Lagrапgс апd С. Dcstradc, C.R. Acad. Sci., 5er. С, 280, 969 (1975).
33. S.F.A КеШе, Е. Lugwisha, J. Eckcrt апd N.K McGuirc, 5peclrochim. Acla, Parl А,
45А, 533 (1989).
34. К. Оhпо, У. Мапdаi апd Н. Matsuura, J. Мо/. Slr/lcl., 268, 41 (1992).
35. С. Brissettc апd С. Sапdоrfy, Сап. J. CJICт., 38, 34 (1960).
3.4.3 IsocyanatomethyI
lПе most characteristic group vibrations of the isocyanates are the out-of
phase stretch (vaN==C==O) and the N==C==O out of plane deformation. lПе
vaN==C==O is easily observed as ап intense broad absorption in the region 2270
::1: 20 cт 1, in contrast with the sharp peak of the nitriles in the same area. In
contrast, the in phase stretch (vsN==C==O) is active in the region 1420 ::1:: 20
cm 1 with а weak to moderate intensity. Both stretching vibrations give rise to а
typical combination band in the neighbourhood of 3700 cm l. lПе characteristic
broad band with medium intensity with the appearance of а 'У' is assigned to the
N==С==О.
ТаЫе 3,15 АЬsоrptiоп regions( cm 1) of thc normal vibrations of
CH2N==C==0
Vibration С . Rcgion Vibration С . Rcgion
vaCHz а" 2960 ::1:: 20 vCN а' 725 ::1: 75
vsCHz а' 2915 ::1:: 15 NСО а" 605 ::1:: 25
vaNCO а' 2270 ::1:: 20 БNСО а' 575 ::1: 25
БСнz а' 1455 ::1: 25 CCN ext. sk. dcf. а" 435 ::1: 25
vsNCO а' 1420::1: 20 CCN cxt. sk. def. а' 350 ::1:: 50
wCHz а' 1325 ::1:: 25 CNC sk. dcf. а' 155::1: 25
TCHz а" 1260::1: 30 torsion а"
pCHz а" 870 ::1:: 80
R CHzN==C==O molecules:
R = Me [1, 2], Et [4], Pr [5], CICHz , HzC==CH [3], OCN(CH2)5 ,
CI .
88 Norllla/ Vibraliolls alld Absorplioll Regiolls о/ CH2X
RcfCI'ences
1. R.P. Hirschmann, R.N. Knisclcy and У.А. Fassel, Spccl/'Ocllilll. Acta, 21, 2125 (1965).
2. J.F. Sullivan. О.Т. Durig, J.R. Durig and S. Cradock,J. P/,)'s. С/,еlll., 91, J770 (1987).
3. Т. Torgrimsen, Р. К1аЬос and F. Nicolaisen,J. Мо/. SIr/lCI., 20, 213 (1974).
4. R.A. Nyquist and G.L. JC\vctt, Арр/. Speclrosc., 46,841 (1992).
5. R.A. Nyquist, О.А. Luoma апd C.L. Putzig, Арр/. Spectrosc., 46, 972 (1992).
3.4.4 Isothiocyanatomethyl
In the spectra of isothiocyanates, the out-of phase stretch (l/aN==C==S) mзkеs its
appearance as а very strol1g broad absorption in thc region 2105 :1: 20 cm l, with
а shoulder а! the HW side (2160 :1: 25) with ап intensity wlJich reaches th3t of
the fundamental vibration. Oftel1 а shoulder is 31so observed зt the LW side (2025
:1: 25 cm 1) . This characteristic absorption is easy to distinguish from the sharp
peak of the thiocyanates (see Section 3.3.3). lПе in phase stretch (vsN==C==S)
is only weak1y active а! 1060:1: 35 cm 1 and coupled with the C N stretching
vibration. Тhe latter mау Ье considered as а vC NCS and absorbs therefore at
low wavenumbers (610 :1: 35 cm 1). 111 the spectrum of MeNCS the two NCS
stretching vibrations are assigned а! 2113 and 1090 cm 1 [1,2].
ТаЫе 3.16 Absorption rcgions (cm 1) оС the поrmа1 vibr3tions of
CH2N===C===S
Vibration С . Region Vibratiol1 С . Rcgiol1
VaCHz а" 2960 :1: 30 vCN а' 610 :1: 35
vsCHz а' 2915 :1: 15 ,NCS а" 530:1: 15
vaNCS а' 2105:1: 20 CCN cxt. sk. def. а" 470::1: 30
БСН2 а' 1445 :1: 20 БNСS а' 435 ::1: 15
wCHz а' 1335 :1: 15 CCN ext. sk. def. а' 380 :1: 30
TCHz а" 1260 :1: 30 CNC sk. deC. а' 140 ::1: 40
vsNCS а' 1060 :1: 35 torsiol1 а"
pCHz а" 865 :1: 75
R CHzN==C==S molecules:
R = Me [2.....4], Et , MezNCHz , HzC===CH [5, 6] and Ph [5].
References
1. J.R. Durig, J.F. Sullivan, H.L. Hcuscl and S. Cradock, J. Мо/. SIr/lCI., 100, 241 (1983).
2. J.R. Durig, J.F. Sullivan, О.т. Durig and S. Cradock, Сап. J. C/IC1Il., 63, 2000 (1985).
3. J.R. Durig, H.L. Heuscl and J.F. Sullivan, Speclrocllim. ACla, Parl А, 40А, 739 (1984).
4. R.N. Кnisclcy, R.P. Hirschmann al1d У.А. Fasscl, Speclrocllilll. ACla, Parl А, 23А, 109
(1967).
5. N.s. Нат and J.B. Willis, Speclrocllim. ACla, 16,279 (1960).
6. Т. Torgrimscn, Р. ЮаЬое and F. Nicolaisen,J. Мо/. Slrиcl., 20, 213 (1974).
3.5 Carboп-boflded Me//ly/eпe
89
З.S CARBON-BONDED МЕТНУLЕNЕ
3.5.1 EthyI
Molcculcs of 'урс X E! (Х= F, CI, Br, 1) possess 18 normal vibrations which are
dividcd in 11 а' and 7а" vibration types. After substitution of vCX (а') Ьу а torsion
(а"), the 18 normal vibrations (10а' + 8а") for ethyl according to С., symmetry are:
а': Y Mc, vsMc, VsCH2, Б Ме, БСН2, Б,Ме, WCH2, р'Ме, vCC, БС С ,
а": уаМс, УаСН2, БаМе, ТСН2, рМе, рСН2 and two torsions.
The two methyl rockings and the уСС arc mixed vibrations. lПе out of-plane рМе
mау Ьс correlated with the band а! 1100:1: 95 cm l. The in-plane р'Мс and the
уСС are strongly coupled and give risc 'о ап absorption in two regions, considered
as: р'Ме/уСС (1080::1: 80) and уСС/р'Ме (910 :1: 100 cm l).
ТаЫе 3.17 Absorption rcgions (cm l) of а-С saturatcd СН2СНЗ
Total region Molecules absorbing Molecules absorbing Region of
а! high wavenumbcrs а! low wavenumbcrs rcmaining
moleculcs
УаМе 2980 ::1: 20 McCHClEt (2997) 2975 ::1: 15
cPrEt (2994)
Y Mc 2965 ::1: 25 СlзС Еt (2989) MeCCl2Et (2944) 2965 ::1: 15
У а СН 2 2935 ::1: 35 С1СН2ПlzЕt (2900) 2945 :1: 25
FCH2CH2Et (2905)
VsMe 2900 :1: 60 Mc E! (2962) IСН2Е! (2840) 2900 :1: 40
BrCH2Et (2846)
V s CH 2 2865 ::1: 25 1СН2Е! (2840) 2870 ::1: 20
BrCH2Et (2846)
ХСН2СН2Е! (2846)
(Х = F, CI)
БаМе 1465 ::1: 10 1465 :1: 10
Б Ме 1450::1: 15 BrCH2Et (1435) 1455::1: 10
CICH2Et (1442)
БСН2 1450 ::1: 30 Me Et (1476) MeCCI2Et (1427) 1455::1: 15
H2NCH2CH2Et (1475) СlзС Еt (1430)
БsМе 1375 ::1: 15 3 Br Ph CH2Et (1390) EtC{==O)NHCH2Et (1369) 1379 ::1: 6
FCH2CH2Et (1387) 4 F Pb C(==O)CН2Et (1370)
WCH2 1330 ::1: 35 H2NCH2CH2Et (1364) MeCHCIEt (1299) 1340 :1: 20
cPr(Et)2 (1302)
НзSiСН2СН2Еt (1307)
ТСН2 1245 ::1: 45 MeCHCIEt (1290) НзSiСН2Еt (1207) 1250 ::1: 35
НС=ССН2СН2Е! (1290) DзSiСН2ЕI (1208)
MeC(==O)NHCH2Et (1289) MeSiН2CH2Et (1212)
рМе 1125 ::1: 65 Me E! (1190 and 1158) MeSiD2CH2Et (1062) 1110 :1: 40
ВrСН2СН(Ме)Еt (1169) MeSiH2CH2Et (1067)
р'Ме/ 1055 ::1: 45 02NCH2Et (1097) IСН2Е! (1010) 1055::1: 35
УСС МеС=ССН2Е! (1094) (collliпlled)
90 Norma/ Vibl'alio"s arrd Absolplio" Regio"s о/ Cl-/2X
ТIIЫе 3.17 (collli/ll/c/f)
Total rogion Molocuks absorblltg Mokculos "ЬsоrЫпg Rogiolt of
31 high wаVОПUП11,сrs а. lо\у \VavcnUl11bcrs rсшаiпiпg
П10Iсс"ks
vCCJ 940 :!: 60 ВrCН2СЩМо)ЕI (1000) ICH2E1 (880) 935 ::1: 45
р'Ме DзС Е\ (999) BrCH2Et (886)
McCCI2E\ (999) 2-IЮ Рh С(==О)СН2Еt (880)
McSiD2CH2EI (885)
рС Н 2 780 :!: 55 НзSiСН2ЕI (Ir:830; g:824) ICH2E1 (727) 760 :!: 30
McCCI2EI (810)
skclct. dcf. 390:!: 100 McCCI2E1 (490) ICH2Et (290) 405 :!: 65
FCH2CH2EI (473) BrCH2Et (312)
torsion Мс 230 :!: 105 Mc E! (333 зпd 223) СlзС ЕI (130) 225 ::1: 45
lors;on Е! 120:!: 30 120:!: 30
R ЕI n101ecules
R = R'CH2 (see Section 3.5.5)
R = Me [1 7, 84], DзС [5, 6], EtCH(Me) [8], BrCH2CH(Me) [9],
cPr [10], 02CCHOH [11], MeCHF [12], MeCHC1 [13 15],
EtCHCl [15), MeCHBr and MeCНI (14), CICH2CHCI and
BrCH2CHBr [16], I Et cPr [31], 'Bи [17], MeCCI2 [18----22],
MeCBr2 [23], СlзС [22,24].
ТаЫс 3.18 Absorption regions (cm I) of a C unsaturated СН2СНЗ
ТОlзl rcgion Molcc"los absorblng Molcculcs absorbing Rcg;on of
а! high wаvспuП1ЬСrs at low \vavcnumbcrs rcmaining
П10kсulсs
УаМе 2980 :!: 20 N=C EI (3000) РЬ Е! (2966) 2980::1: 10
Y Mc 2970 :!: 30 N=C EI (2998) 2960 ::1: 20
HC=C E! (2988)
У а СН 2 2940 :!: 20 N=C Et (2958) 2935 ::1: 15
H2C==CH EI (2952)
VsMc 2915 :!: 45 N=C Et (2958) H2C==CBr EI (2878) 2910::1: 30
HC=C EI (2945)
V s CH 2 2885 :!: 45 HC=C EI (2925) H2C==CBr Et (2848) 2885 ::1: 35
Бамс 1465:!: 10 OC=C EI (1471) Et C=C Et (1457 and /460) 1465 ::1: 05
Б мс 1455 :!: 10 HC=C EI (1462) Et C=C Et (1447 and /450) 1455 ::1: 05
БСН2 1440 :!: 10 H2C==CН E! (1450) N=C EI (1431) 1440::1: 05
БsМе 1380:!: 10 N=C EI (1386) Et C=C EI (1374) '380::l: 05
wCH2 1340 :!: 25 Иl1 ЕI (1363) 1330::1: 15
ТСН2 1265 :!: 10 HOCH2CH2C=C E! (1273) Me C=C E! (1259) 1265 ::1: 05
рМе I130:!: 50 H2C==CH E! (1177) Mc C=C E! (1088) 1120::1: 30
р'Мс/уСС 1085 :!: 45 H2C==CH E! (1128) 1065 ::1: 25
VCC/p'Me 975 :!: 35 2-Th Еt (946) 980 ::1: 30
рСН2 800 :!: 25 Иl1 Еt (821) 790 :t 10
skclc\. dcf. 345 :!: 45 H2C==CH EI (306) 360 ::1: 30
tors;on Мс 255 :!: 35 255 ::1: 35
torsion Е!
3.5 Carboп-boпded Me//ly/eпe
91
R Et moleculcs
R = HzC===CH [25 27], N=C HC==CH [28], HzC==CCI and
HzC==CBr [29], 2 lП [3О], Ph [80], HC=C [32, 33, 34],
DC=C [32], McC=C [35, 36], EtC=C [37], HOCHzCHzC=C ,
N=C [34, 38].
ТаЫе 3.19 Absorption regions (cm I) of С(===О)-, 0- and S bound СН2СНЗ
С(==О)Е! ОЕI SEt
УаМе 2985::1: ]5 2985 :1: 10 2985 :1: 15
Y Mc 2970 ::1: 30 2965 :1: Z5 2965 :1: 10
VaCHz 2930 ::1: 25 2940 :1: 20 2940 :1: zo
VsMe 2900 ::1: 40 2910:1: 30 2920 :1: 25
VsCHZ 2880 ::1: 60 2885 :1: 30 2880 :1: 30
БаМе 1470::1: 15 ]465:1: 15 ]465:1: 15
Б Ме 1455::1: 15 ]445 ::1: 20 1450::1: 10
Бсн, 1425 ::1: 20 1475 :1: 20 1430:1: ]5
Бsм';- 1380::1: 15 1385:1: 15 1380 :1: 10
WCHZ 1340::1: 40 1350 :1: 40 1280 :1: 30
TCHz 1265 ::1: 25 1285:1: 45 1250:1: 20
рМе 1130::1: 60 1165:1: 30 'О75 ::1: 30
р' Ме/УСС 1050 ::1: 50 1120::1: 40 1035 :1: 25
УСс/р'Ме 920 :1: 80 875 ::1: 65 975 :1: 25
pCHz 805 ::1: 30 790 :1: 50 765 :1: 35
skelet. def. 375 ::1: 85 390 ::1: 85 350 :1: 40
lorsion Ме 220 ::1: 30 240 ::1: 40 245 :1: 35
torsion Е! 130 ::1: 70 150::1: 50 185:1: 30
R Et molecules
R = R'C(==O) (see Seclion 7.1.6), R'O (see Section 10.1.3), OzNO [82],
ClzP(==O)O and ClzP(==S)O [81], Н(ЕtO)Р(==О)О [83], R'S (see
Section 11.1.2)
ТаЫе 3.20 Absorption regions (cm I) оС N , p , Si and Halogen-bound СНzСНз
N Si Наl
УаМе 2980 ::1: 20 2985 ::1: 15 2975 :1: 15 2990 :1: 20
Y Me 2965 ::1: 25 2975 ::1: zo 2965 :1: 15 2965 :1: 25
VaCHz 2940 ::1: 20 2940 :1: 20 2950 :1: 20 30]0:1: 05
VsMe 2880 ::1: 40 2915 ::1: Z5 2915:1: 25 2895 :1: 25
VsCHZ 2850 ::1: 40 2885 :1: Z5 2885 :1: 15 2945 :1: 25
БаМе ]465 ::1: 20 ]460:1: 15 1465:1: 10 1460:1:: ]5
Б Ме 1455::1: 10 1455 :1: 15 1445 ::1: Z5 1445:1: ]5
Бснz 1450 :1: 20 1415::1: 10 1415:1: 10 1455 :1: 25
БsМе 1375 :1:: 15 1375 :1: 15 1380 :1: 05 138] :1: I1
wCH, 1320 ::1: 35 1255 :1: 25 1240:1: 10 1285:1: 80
ТСН; 1265 ::1: 25 1240::1: 15 1225 :1: 20 1195:1: 80
рМе 1125::1: 60 1050 :1: 30 10Z0 :1: 10 1110:1: 60
р'Ме/уСС 1055 ::1: 55 1035 :1: 20 1020 :1: 10 1045 ::1: 25
УСС/р'Ме 955 :1: 40 980 ::1: 20 970:1: 10 923 :1: 50
pCHz 800 ::1: 20 770 :1: 50 745 :1: 30 775 :1: 40
skelet. def. 400 ::1: 95 310:1: 30 320 :1: 30 340 :1: 80
lorsion Ме 210:1: 30 230 :1: 35 265:1: 15
torsion Е!
92 Noтт/ Vibтliolls alld AbsOIP/ioll ИеgiОIlS о/ CH2X
R Et nlOlecules
R = H2N [39], +НзN [40], EtNH [41], McC(==O)NH and
EtC(==O)NH [42], McNHC(==O)NH [43, 44], PllS0zNH [45],
MezN [46], 02N [47, 48], OCN [49], SCN [50 52], CN [53J,
Nз [54], (Et2N)zPN [55J, HzP al1d 02P [561, MczP [57],
F2P [58], CI2P [59, 60], F2P(==O) [6IJ, ClzP(==O) [62J,
FzP(==S) [63], ClzP(==S) [64], НзSi and DзSi [65], MeSiHz ,
MeSiDz , EtSiНz and EtSiDz [66], MezSiН and MC2SiD [67],
F [68, 69], CI [13, 7 75], Br [69,73,76, 79], I [69,75,77,78].
References
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63. J.R. Durig, R.D. Jоhпsоп, Н. Nапаiе апd Т.1. Hizer, J. C/1Cm. P//ys., 88, 7317 (1988).
64. J.R. Durig апd T.J. Hizer, J. Ramall 5pectrosc., 18, 415 (1987).
65. к-м. Mackay апd R. Walt, 5peclrocllim. Acta, Parl А, 23А, 2761 (1967).
66. Н. Matsuura, к- Оhпо, Т. Sato апd Н. Murata, J. Мо/. 5lrиcl., 52, 13 (1979).
67. к- Оhпо, К. Suerhiro and Н. Murala, J. Мо/. 51Тl/CI., 98, 251 (1983).
68. а.А Crowder апd Н.К- Мао, J. Mol. 5Irllc/., 18, 33 (1973).
69. О.С. Smith, R.A Sаuпdеrs, J.R. Niclsen апd Е.Е. Fсrgusоп, J. С//Сl1l. P//ys.,20, 847
(1952).
70. R.G. Sпуdеr апd J.H. Sсhасhtsсhпеidеr,J. Mol. 5ресtюsс., 30, 290 (1969).
71. L.W. Daasch, с.У. Liапg апd J.R. Niclsen, J. C/IC1Il. P//ys., 22, 1293 (1954).
72. F.A Miller and F.E. Кiviat, 5peclrocllim. Acta, Parl А, 25А, 1363 (1969).
73. S. Mizushima, Т. Shimапоuсhi, 1. Nakagawa апd А Miyake, J. C/1CIII. P/rys., 21, 215
(1953).
94 Noтт/ И/тlliо"s т!(/ AlJsOIplio" Regio"s о/ CH2X
74. S. Suz\lki and АВ. Dсшрstеr, J. Mol. 5/rllct., 32, 339 (1976).
75. N.т. McDcvitt, AL. Rozck, ЕЕ IЗспtlсу and АД Davi(lsun, J. С//ет. PI,yS., 42, 1173
(1965).
76. R. Gaufrezs and М. Bcjaud-Bianchi, 5peclroclliт. Асш, J>art Л, 27А, 2249 (1971).
77. а.А Cro\vdcr, J. Mol. 5pcctrlOsc., 48, 467 (1973).
78. J.R. Dlllig, J.W. Thompson, V.W. Tllyagesan and J.D. Witt, J. Мо/. 5Irt1ct., 24, 41
(1975).
79. F.F, Bentley, N.T. McDcvitt and AL. Rozck. 5pectroclliт. ЛСlа, 20. 105 (1964).
80. а. Varsanyi. Assiglll1lellls [о, ИЬrаliОllаl5реСI/"Q о/ SL'I'ell HIIIIIlrc(/ BCIIZCIlC Dcrivalivcs,
J.Wilcy & Sons Nc\v York (1974).
81. R.A. Nyquist. W.W. Mucldcr and M.N. Wass, 5pcclroc/lil1l. ACla, Parl А, 26А, 769
(1970).
82. J .R. Durig and T.G. Shcchan, J. Ral1lall 5pectrosc., 21, 635 (1990).
83. S.A. KatcYllba, N.I. Monakhova, L.кh. Ashraful1ina and R.R. Shagidullin, J. Mol.
5I/"11С/.. 269, 1 (1992).
84. Р. Dcrreumaux, М. Dauchez and а. Vergoten, J. Мо/. 5Irllcl., 295, 203 (1993).
3.5.2 Тrichloroethyl
lПе simplest molecules with а СНzССlз structure unit are ХСНzССlз (Х =F,
CI, Br and 1). lПе 18 normal vibrations are distributed over l1а' and 7а" vibration
types according 'о С . symmetry. Substitution of the уСХ (а') Ьу а torsion (а")
fumishes the 10а' + 8а" norrnal vibrations of СНzССlз :
а': vsCHz, БСНz, wCHz, уСС, у'СС! (or v;ССl з ), II"CCI (or vsССl з ), Б С С,
БССI (or БsСС1з), Б"ССI (or Б;СС1з), p'CCI (or р'ССl з );
а": vaCH z , TCHz, vCCI (or vаСС1з), pCHz, Б'ССI (or БаССl з ), рССI (or рСС1з)
and !\vo torsions.
The trichloroethyl group, just like the trichloromethyl group, is characterized Ьу
the three strong absorptions of the CCI stretching vibrations. The normal vibrations
of trichloromethyl are treated in Chapter 2 (see Scction 2.2.2).
ТаЫе 3.21 Absorption regions (cm l) of the norrnal vibrations
of СНzССlз
Vibration Region Vibration Region
lI a CH z 2970 ::1: 20 v"CCI 545 ::1: 45
II s CH z 2935 ::1: 20 CC ext. sk. def. 500 ::1: 70
БСнz 1435 :1: 20 БСССI 380 ::1: 30
wCHz 1340 :1: 30 Б'СССI 355 ::1: 30
TCHz 1270:1: 30 Б"СССI 305 ::1: 40
уСС 1045 ::1: 25 pCCI 245::1: 15
IICCI 795 :1: 35 p'CCI 195::1: 35
II'CCI 740 :1: 60 torsion 120::1: 30
pCHz 765 :1: 70 torsion
3.5 Carboп-bollded Melhy/elle
95
R СНzССlз molcculcs
R = Mc [1, 3], McCXH , (BиCXH and MezXC (Х = CI, Br)
[2], CICH2 [1, 2, 4], BrCHz [1, 2], CJ2CH [4], HO [5,
6], CIC(==O) O , ClzPO , ClzP(==O)O , СlЗССН20Р(==О)О ,
CI [7, 8J.
Refcrences
1. А Goursot-Leray, М. Carles Lorjou, G.Pouzard and H.Bodot, 5pcc/rocllim. ACla, Part А,
29А, 1497 (1973).
2. М. Carles Lorjou, А. Goursot-Leray and Н. Bodot, 5pcctroclli1ll. ACla, Parl А, 29А, 329
(1973).
3. К. Ohno, К. Taga, 1. Yoshida and Н. Murata, 5peclrocllim. ACla, Parl А, 36А, 72] (1980).
4. АВ. Dempster, К. Рпсе and N. Sheppard, Spcclrocllim. ACla, Parl А, 27А, 1563 (1971).
5. М. PerttiIa, 5pcctrocIIim. ЛСlа, Parl А, 35А, 585 (1979).
6. J. Travert and J.c. Lavalley, 5pcc/rocIIim. Acta, Parl А, 32А, 637 (1976).
7. S. Suzuki and АВ. Dempster, J. Мо/. 5Ir/lcl., 32, 339 (1976).
8. а. Аllеп and Н.1. Bemstein, Сап. J. ClICm., 32, 1124 (]954).
3.5.3 ChloroethyI
lПе 18 normal vibrations of chloroethyl are divided into 10а' and 8а" species of
vibration, which are composed of 12 vibrations for methylene, а СС and а ССI
stretching vibration, two skeletal dеfопnаtiопs and two torsions:
а': vsCHz (2), БСН z (2), wCHz (2), уСС, vCCI, Б С С, БС С СI;
а": УаСН2 (2), TCHz (2), pCHz (2) and two torsions.
This colIection contains the nine попnаl vibrations of CHzX (see Section
3.1.2), the six vibrations of methylene, опе СС stretching vibration, опе extemal
C C deformation and опе CHzCHzCI torsion. Тhe four mеthуlепе stretching
vibrations are often described as four individual СН stretchings. Likewise it is поt
always possible (о assign the absorptions of the two wags and the two twists because
they are coupled (о опе another. In this work the higher wavenumbers are assigned
(о the wagging modes, the Iower (о the twists. The ССI stretch, generalIy with
strong band intensity, is the most characteristic band, Ьи! the notabIe CHzCI wag
is also helpful for identification purposes. lПе CHzCI vibrations are especially
sensitive (о the conformationa1 state of the molecule (Section 3.1.2). Self-evidently,
more accurate absorption regions for the R CHz vibrations are availabIe in the
more relevant tables.
96 Norllla/ VilJ,'alio"s аl/(/ Absol"p1io" Regio"s о/ CH2X
ТIIЫе 3.22 WavellU1l1bcrs оС tllc \vaggil1g al1d twislil1g vibratiol1s of а fcw
RCHzCHzCI compoul1ds
R wCHz wCHzCI rCI-1z TCHZCI
HO 1380 1300 1247 1165
McO 1386 1299 1255 1218
H2N 1385 1290 1254 1156
СlзС 1342 1280 1254 1171
CICH2 1357 1315, 1280 1258 1194, 1150
BrCHz 1355 1308 1243 1144
Mc 1339 1291 1266 1227
NC 1333 1302 1218 1170
HzC==CH 1324 1260 1243 1200
Ph 1320 1282 1242 1195
o 1305 1263 1258 1213
CI (g al1d Ir) 1315, 1304 1292, 1264 1143, 1125 1207, 1233
Br (g and Ir) 1299, 1284 1260, 1259 1127,1111 1190,1203
R CHzCHzCI molecules
R = o [1], Me [2 10], Et [7, 9, 10], MeC(==O)CHz ,
MeOC(==O)CHz , EtOC(==O)CHz , CIC(==O)CHz ,
CH2==CHCHz [11), N=CCHz , PhCHz [12], HOCHz , iPrOCHz ,
PhOCHz , ClS(==O)zCHz , CICHz , BrCHz and ICH z [13],
MeCH(Cl) , СlзС [14----16], EtC(==O) , CIC(==O) [17],
HOC(==O) , HzNC(==O) , 4 XPhC(==O) [18] (Х = F, CI, Br),
CHz==CH . [11, 19], HC=C , N=C [20-----24], Ph [12, 25],
HzN [26], НзN+ , OCN , HO [27 31], OO [27 29], MeO [32],
ЕtO and CICHzCHzO [30], CIC(==O)O , 4 BrPhO , HS [33],
MeS [34], EtS and CICHzCHzS [42], NaOS(==O)z , F [35],
Cl [36----41], Br [36,39].
References
1. J.S. Francisco, Z. Qingshi and J.I. Stcinfeld, 5pec/rocIJim. Acta, Part А, 38А, 671 (1982).
2. J.K Bro\vn and N. Shcppard, Tra/Js. Faraday 50С., 50, 1164 (1954).
3. С. Komaki, 1. Ichishima, К. Kutanani, Т. Miyazawa, Т. Shimanouchi and S.Mizushima,
BIII/. С//ст. 50С. JP/J., 28, 330 (1955).
4. У.А Pozdyshcv, YU.A. Pcntin and У.М. Tatevskii, Opt. 5peclrosc., 3,211 (1957).
5. N.T. McDcvitt, AL. Rozek, F.F. Bcntlcy and АО. Davidson,J. C/leIII. P/l)'S., 42,1173
(1965).
6. К. Radcliffc and J.L. Wood, Tra/Js. Faraday 50С., 62, 1678 (1966).
7. R.G. Snydcr and J.H. Schachtschncidcr, J. Mol. 5pectrosc., 30,290 (1969).
8. К. ТапаЬс and S. Sаёki,J. Mol. 5Irllcl., 27, 79 (1975).
9. А.1. Bames, M.L. Evans and Н.Е. Наllаm, J. Мо/. 5Ir11CI., 99,235 (1983).
10. У. Ogawa, S. lmazcki, Н. Yamaguchi, Н. Matsuura, 1. Harada and Т. Shimal1ouchi, Bиl/.
ClICIII. 50С. JP/J., 51, 748 (J978).
3.5 Carboп-bollded Me/hyleпe 97
ТаЫе 3.23 Absorption regions (cm 1) of the normal vibrations of CHzCHzCI
ТоlзJ rcgion Molcculcs absorbing Molccules absorbing Rcgion of
з1 high wavcnumbcrs а\ low wavenumbers most
moJccuJcs
VaCHZCI 3010 ::1: 20 N=CCHZCHZCI MeOCHzCHzCI (2990) 3010:1: 10
(3030)
CIC(==O)CHZCHZCI
(3030)
VaCHz 2975 ::1: 35 BrCHzCHzCl (3010) 2965 :1: 25
CICHZCHZCI (3005)
vsCHZCI 2960 ::1: 20 E\CHZCHZO (2945) 2965 :1: 15
VsCHZ 2910 ::1: 50 g N=CCHZCHZCl EICHzCНZO (2861) 2905 :1: 35
(2960)
Бснz 1450 ::1: 20 EICHZCHZCI (1469) g OCHZCHZO (1430) 1450:1: 15
McCHzCHzCI (1468) g-ВrСНzСН20 (1430)
БСНzСI 1430 ::1: 20 4-F PhC(==O)CНzCНzO 1435:1: 15
(1411)
EtC(==O)CHzCH20 (1412)
N=CCHZCHzCI (1416)
wCHZ 1335 ::1: 55 McOCHzCНzCI (1386) BrCHzCHzO (Ir:1284; с:1299) 1350 :1: 30
HZNCHZCHZCI (1385) CJCHZCHZCI (":1304; с:1315)
wCHZCI 1280::1: 35 PhCНZCНZCI (1245) 1285 :1: 30
ТСН2 1205 ::1: 95 HZNCHZCHZCI (1290) BrCHzCHzO 1240 :1: 40
(Ir:lll1; с: 1127)
CJCHZCHZCI
(Ir:1125; с:1143)
TCHzCI 1195::1: 55 HC=CCHzCHzCI BrCH2CHzCHZCI (1144) 1190:1: 45
(1247)
уСС 1050 ::1: 60 EtCHzCHzCI (1110) СlзССНzСНzСJ (990) 1050 :1: 50
pCHzCI 910 ::1: 80 HC=CCHzCHzCI 4-Х Рhq==О)СНZСНZО 905 :1: 55
(989) (830)
Ir-СIСНzСНzСI (982) (Х = F, CI, Br)
pCHz 795 ::1: 90 g CICHZCHzCI (880) ОзССНzСНzСJ (705) 800 :1: 60
Ir-N=ССНZСНZCl
(878)
уССI 700 ::1: 60 Ir N=CCHzCHzCI CICHZCHZCHZCI (679, 641) 705 :1: 50
(755)
Ir-СJСНzСНZСl Ir DCHzCHZO (642)
(754, 709)
Бс с 440::1: 120 N=CCHZCHZCI HzC==CHCHzCHzCI (329) 400 :1: 70
(Ir:494; с:565)
Бс с CI 295 ::1: 70 CICHZCHZCHZCI Ir-СIСНzСНZСI (300, Z25) 280 :1: 50
(362, 348)
torsion CHzCI 155 ::1: 50 g N=CCHZCHZCI g-ВrCНZСНZО (107) 155:1: 35
(202)
torsion
98 Norl1la/ иы"ltiоIlss тиl AbsOIP/ioll Regiolls о/ CH2X
11. а.А. Cro\vdcr. J. Mol. 51",ct., 10, 290 (1971).
12. J.E. Saundcrs. J.1. L\lcicr and J.N. Willis Jr, 5pccl/"Ocllil1l. Acta, Part А, 24А, 2027
(1968).
13. J.A. ТhщЬjоmsrud, О.Н. Ellestad, Р. Кlaboc and Т. Torgril11sen, J. Мо/. SI",ct., 15,61
(1973).
14. А. Goursot-Leray, М. Carlcs-LоIjоu, а. ouzard and Н. Bodot, 5pcclrocllil1l. ЛСlа, Part
А, 29А, 1497 (1973).
15. М. Carlcs-LоIjоu, А. Goursot-Lcray and Н. Bodot, 5pec/rocllil1l. Лс/а, Part А, 29А, 329
(1973).
16. АВ. Del11pslcr, К. Price and N. Shcppard, 5pcclrocllilll. Лсtа, Pll/.t Л, 27А, 1563 (1971).
17. J. Som. О. Bhaumik, О.К. Mukhcrjcc and G.S. Kastha, IlIdia" J. Рш'е Арр/. PI,)'S., 12,
149 (1974).
18. W.A. Scth Paul, В. Уап der Vekcn and М.А Hem1an, Са". J. 5pcclrosc., 27, 21 (1982).
19. О.А Cro\vdcr and N. Smyrl, J. Mol. 5/r/lcl., 8, 255 (197 J).
20. К. Tanabc,J. Мо/. 5t"'CI., 25, 259 (1975).
21. Е. Wyn-Jones and W.1. Orville-Thomas, J. Сlю". 50С., 101 (1966).
22. M.F. ЕI BCm1ani and N. Jonathan,J. CI/cl1l.50c., 1712 (1968).
23. Р. К1аЬое and J. Grundnes, 5pcClrOcllil1l. Acta, Par/ А, 24А, 1905 (1968).
24. Т. Fujiyama, B/lII. CI,CI1l. 50С. Jp",,, 44,3317 (1971).
25. АМ. North, R.A. Pctllrik and АО. Wilson, 5pectrocllil1l. ACla, Parl А, 30А, 1317
(1974).
26. М. Nakata and М. Tasumi, 5pcclrocllil1l. Асш, Part А, 41А, 341 (1985).
27. Е. Wyn-Joncs and W.1. Orville Thomas,J. Мо/. 51"'CI.,1, 79 (1967).
28. а. Davidovics, J. Pourcin, М. Carles, L. pizzala and Н. Bodot, J. Мо/. 51"'CI., 99, 165
(1983).
29. М. РеrttШi, J. Murto and L. Halonen, 5pectrocllil1l. Ас/а, Part А, 34А, 469 (1978).
30. H.F. Hameka,J. Мо/. 5t"'CI., 226, 241 (1991).
31. Р. Buckley, Р.А Giguere and М. Schncider, Саll. J. CI,CI1l., 47, 901 (1969).
32. Н. Matsuura, М. Копо, Н. Iizuka, У. Ogawa, 1. Harada and Т. Shimanouchi, B/lII. CI,CI1l.
50С. JP/l., 50, 2272 (1977).
33. М. Hayashi, У. Shiro, М. Murakami and Н. Murata, B/lII. C/leт. 50С. Jp"" 38, 1740
(1965).
34. Н. Matsuura, N. Miyauchi, Н. Murata and М. Sakakibara, B/lII. CllCт. 50С. JP/l., 52,
344 (1979).
35. J.R. Durig, J. Liu and T.S. Little, J. P/,yS. CI,el1l., 95, 4664 (1991).
36. К. ТапаЬе, 5peclrocllil1l. Acta, Parl А, 28А, 407 (1972).
37. У. Duchesnc and А. Уап Ое Vorst, J. Mol. 51",ct., 2, 47 (1968).
38. К. ТапаЬе, 5pcclrocllil1l. ACla, Par/ А, 30А, 1901 (1974).
39. К. ТапаЬс, J. Hiraishi and Т. Tamura, J. Мо/. 5t/"lICI., 33, 19 (1976).
40. S. Suzuki and АВ. Dcmpster, J. Мо/. 5tr/lc/., 32, 339 (1976).
41. S. Mizushima, Т. Shimanouchi, 1. Nakagawa and А Miyake, J. C/lel1l. PI,yS., 21, 215
(1953).
42. S.D. Christescn, J. Ramall 5pec/rosc., 22, 459 (1991).
3.5.4 HydroxyethyI
Molecules of (уре XCHzCHzOH (Х = F, CI, Br and 1) in the /ralls conformation
belong (о the point group C s . lПе 21 normal vibrations are divided over 13а' and
8а" species of vibration. Substitution of уСХ (а') Ьу а torsion (а") gives the 12а'
+ 9а" vibrations of hydroxycthyl.
3.5 Carboll bollded Me//ly/eпe
99
а': УОН, 1-',СНz (2), БСН z (2), БОН, wCHz (2), vCO, уСС, 6ССО, 6 C C;
а": vaCHz (2), TCH z (2), pCHz (2), ,ОН and two tоrsiопs.
Thc 12 normal vibrations of thc associatcd hydroxymcthyl have alrcady Ьееп
studicd (scc Section 3.2.1): уОН, vaCHzOH, vsCHzOH, 6CHzOH, 60Н, wCHzOH,
TCHzOH, усо, pCHzOH, fOH, Б СО and torsion CHzOH.
For thc six vibrations of mcthylenc (vaCHz, v.,CH z , БСНz, wCH z , TCH z and
pCHz), morc appropriatc tabIcs with absorption regions of R CHz compounds
are availablc.
The remaining normal vibrations are: а СС strеtсhiпg vibration, ап external
C C skcletal deformation and а hydroxycthyl torsion.
The СС stretching vibration, which is also rcferrcd (о as C C O in-phase
stretching, exhibits а weak (о medium band а! 1015 :i: 35 cm l, and is coupled
with the stronger C O stretching or C C O out of-phase stretching mode. Тhe
skeletal C C dcformation is ап external vibration which, for the investigated
compounds, appears weakly (о moderatcly in the region 340 :i: 60 cm '. lПе
free ОН torsion of a1cohols in the unbonded state mау Ье correlated with а weak
absorption in the neighbourhood of 300 cm l.
ТаЫе 3.24 Absorption regions (cm ]) of associatcd
CHzCHzOH
Vibration Rеgiоп ViЬrаtiоп Rcgion
I-'ОН 3300 ::1: 120 TCHz 1210:!: 80
vaCHz 2980 ::1: 45 уСО 1065 :i: 25
vaCHzOH 2950 ::1: 30 уСС 1015 :i: 35
v.,CHz 2920 ::1: 45 pCHzOH 900 :i: 60
vsCHzOH 2885 ::1: 45 pCHz 820 :i: 70
Бсн,он 1450::1: 25 ,ОН 630 :i: 60
БСН; 1435 ::1: 25 ССО sk. def. 475 :i: 75
БОн 1405 ::1: 35 CC ext. sk. dcf. 340 :i: 60
wCHzOH 1360 ::1: 30 tоrsiоп
wCHz 1260::1: 90 tоrsiоп
TCHzOH 1240::1: 60
R CHzCHzOH molecules
R = Me [1], Et [2], MeC(==O)CHz , HzNCH2 , PhOCH2 , CICHz ,
BrCHz , OzCCHz [3], HzC==CH , H2C==C(Me) , EtCH==CH ,
2 Тh , 4 MeOPh , HC=C [4], N=C , EtC=C , H2N , +НзN ,
MeNH , EtNH , HzNNH , HOCHzCH2NHC(==S)C(==S)NH [17],
OzN , HO [5,6, 7], MeO , EtO , HS , MeS , F [ 12], CI [9,
10, 13 15], Br [9, 14, 16], I [9, 16].
100 Norтa/ VilJra/iolls alld Absorp/ioll Regiolls о/ CH2X
Rcferences
1. К. Fukusl1in13 and В.1. Z\volinski,J. Мо/. Speclrosc., 26, 3(,8 (1968).
2. а.А Сю\vdеr and М.1. To\vnscnd,J. Мо/. 51I"/1CI., 42, 27 (1977).
3. М. Morssli, а. Cassanas, L. Bardct, В. Pauvart and А Terol, 5реСII'ОСЫ1ll. ACla, 47А,
529 (1991).
4. а.А. Cro\vdcr and E.W. Loya,J. Mol. 51rr1С/., 62, 297 (1980).
5. Н. Matsuura and Т. Miyaza\va, BIIII. С//С/II. 50С. Jpll., 40, 85 (1967).
6. W. Sa\vodny, К.К. Nicdenzu and J.W. Da\vson, 5pectroclli1ll. Acta, Part Л, 23А, 799
( 1967).
7. Н. Matsuura, М. Нiraishi and Т. Miyaza\va, 5pectrocili1ll. Acta, Part А, 28А, 2299
(1972).
8. О. Schrems and W.A.P. Luck, J. Мо/. 5Irllct., 80, 477 (1982).
9. Е. Wyn-Joncs and W.1. Orville-Thomas, J. Mol. 5Irllcl., 1,79 (1967).
10. G. Davidovics, J. Pourcin, М. Carlcs, L. Pizzala and Н. Bodot, J. Мо/. 5/rrlct., 99, 165
(1983).
11. М. РеrttШi, J. Mur1O, А Кivinen and К Turunen, 5pectrocili1ll. Acta, Part А, 34А, 9
( 1978).
12. а. Davidovics, J. Pourcin, М. Monnier, Р. Verlaque and Н. Bodot, J. Мо/. 51rr1ct., 116,
39 (1984).
13. H.F. HaD1eka,J. Мо/. Slrrlct., 226, 241 (1991).
14. Р. Bucklcy, Р.А Giguere and М. Schneider, Call. J. C/le1ll., 47, 901 (1969).
15. М. Per1tilii, J. Murto and L. Halonen, 5pec/rocili1ll. ACla, Part А, 34А, 469 (1978).
16. L. Ноmапеп, 5pectrociliт. ACla, Parl А, 39А, 77 (1983).
17. Р. Geboes, Н. HofD1ans, Н.О. Desscyn, R. Dommisse, АТ.Н. Lenstra, S.B. Sanni, М.М.
Smits and Р.Т. Bcurskcns,5peclrocIli1ll. Ас/а, Parl А, 43А, 35 (1987).
3.5.5 n Propyl
lПе simplest compounds with 3 n propyl unit in the structure are MeCHzCHzX
(Х = h310gen). The 3N 6 = 27 normal vibrations are divided into 16а' + 11а"
types of viЬrзtiоп. Substitution of the СХ stretching vibration (а') Ьу а torsion (а")
yields the 27 normal vibr3tions (15а' + 12з") for n propyl:
а': II Me, vsMe, vsCH z (2), Б Ме, БСН z (2), БsМе, wCH z (2), р'Ме, уСС (2),
skeletal deformations (2);
а": УаМе, vaCHz (2), БаМе, TCHz (2), рМе, pCHz (2) and torsions (3).
Consequently, П рroруI hзs nine vibr3tions more with respect to ethyl: vaCHz,
vsCHz, БСН z , wCHz, TCHz, pCH z , уСС, Б С С and torsion CHzCHzMe.
lПе four СН antisymmetric stretchings in propyl ехЫЫ! moder3te (о strong
absorptions between 2990 and 2900 cm l, which тау fuse together into опе
band. The three СН symmetric stretchings are moderately (о strongly active,
coincident or not, between 2940 and 2840 cm l. lПе methylene scissors and
the methyl antisymmetric deformations also tend (о amalgamate, Ьи! the methyl
symmetric deformation appears totally free а! аЬои! 1375 cm l. lПе methylene
wags and twists give separate зЬsоrptiопs Ьи! for lack of data in relation (о the
i
3.5 Carboп boпded Me//ly/eпe 101
band slructurc, thc wags are assigned а! higher wavenumbers Ihan the Iwists. Тhe
notation p'Mc/I/CHz Mc and vCHz Me/p'Me Шustrаlеs that the two vibrations
are strongly couplcd. Thc absorplion frequency of thc methylene rockings depends
largely ирап thc surroundings. Ciampe1li and Tosi found values around 739 cm l
for thc pCH z in saturatcd hydrocarbons with а propyl unit [51].
ТаЫе 3.25 Absorption rеgiопs (cm l) of СНZСН2СНЗ
TOlul rсgiоп Mulcculcs absorbi"g Mo!cculcs absorbi"g Rcgio" оС
аl high wavc"umbcrs а! low wavc"umbcrs mosl
molecules
VaMc 2975 ::1: 15 "PrCI (2990) 2970:!: 10
V Mc 2965 ::1: 15 п PrC! (2978) 2960 :J: 10
пРrСНzСl (2974)
VaCHzEt 2965 ::1: 40 пРrС! (3005) "PrSH (2925) Z960 :J: 25
пРrВr (3003) пРrОН (2929)
пРrF (2995) пРrNНz (2933)
VaCHzMc 2935 ::1: 35 "PrCHzCI (2900) 2945 :J: 25
"PrCHzF (2905)
VsCHzEt 2905 ::1: 55 "PrCI (2958) "PrNHz (2850) 2900 :J: 40
пРrF (2944) "PrSH (2855)
vsMc 2890 ::1: 50 4 X Ph C(==O)"Pr "Pr! (2840) 2890 :1:: 40
(2934)
(Х = F, Cl, Br, ОН) "PrBr (2846)
VsCHzMc 2865 ::1: 25 "PrCI (2887) "Pr! (2840) Z865 :J: 15
"PrF (2883) "PrBr (2846)
"PrCH2X (2846) (Х = F, CI)
Бамс 1465::1: 10 1465:!: 10
Б Ме ]450::1: 15 пРrВr (1435) 1455 :1:: 10
"PrCI (1442)
БСН2МС 1460 ::1: 20 "PrCHzNHz (1475) "РrСН2SiНз (1443) 1455:!: 10
"PrNHz (1470)
"PrCHzCl a"d "PrCl
(1468)
БСНzЕt 1430 ::1: 30 пРrNНz (1456) 4 X Ph C(==O)"Pr (1405) ]435:!: 15
"PrNDz (1455) "РrSiНз (1411) (Х = F, CI, Br)
"РrCНzSiНз (]415)
"PrSiHzMc (1416)
Бsмс 1375 ::1: 15 3-Вr Рh "Рr (1390) EtC(==O)NH"Pr (1369) 1379:!: 06
"PrCHzF (1387) 4 F Ph C(==0)"Pr (1370)
WCHzMc 1335 ::1: 30 пРrСНzNНz (1364) пРrСНzSiНз (1307) 1340 :J: 20
WCHzEI 1270::1: 85 "PrNHZ (1353) "Pr! (Ir:1186; g:1202) ]290:!: 40
пРrОН (1340) "PrBr (Ir:1228; g:IZ33)
TCНzMc 1245 ::1: 45 "PrCHzC=CH (1290) "РrSiНз (1207) 1250:1:: 35
McC(==O)NH"Pr (1289) пРrSiDз (1208)
"PrSiHzMe (]212)
TCHzEt 1215 ::1: 65 nPrNHz (1274) nPrt (]]58) 1225 :J: 35
( coпlillllCll)
102 NО/"l/Ш/ VilJraliolls ти/ Absorplioll Regiolls о/ CH2X
ТаЫе 3.25 (colllillllc(l)
Total rcgion Molcculcs absorl>ing Molcculcs absorbing Rcgion оС
а! I\igl\ wаvспuПlЬСrs at low wavcnul11bcrs Пlоst
Пlоlссulсs
рМс 1105:!: 45 nPrC=CMc (1143) nPrSiD2Mc (1062) 1 105 ::1: 35
nPrSiHzMc (1067)
р'Мс/ 1055 :!: 45 nPrNOz (1097) nPr\ (1010) 1055::1: 35
VCHz Mc nPrC=CMc (1094)
VCHz Et 995 :!: 65 nPrCHzNHz (1060) EIC(==O)NHnPr (931) 995 ::1: 45
nPrCHzCI (1051) nPrC=N (943)
VCHz MCI 925 :!: 45 nPrCHzNHz (970) nPrl (880) and nPrBr (886) 925 ::1: 35
р'Мс nPrCHzF (970) 2 HO Ph C(==O)nPr (880)
nPrSiD2Mc (885)
pCHzEI 810::1: 85 nPrSH (1r:890; g:881) пРrSiНз (Ir:728; g:787) 835 ::1: 45
nPrSH (Ir:736; g:780)
nPrSCN (782)
pCHzMe 780 :!: 55 пРrSiНз (tr:830; g:824) nPr1 (727) 760 ::1: 30
C C C skclct.dcC. 380 ::1: 95 nPrCHzF (473) nPrl (290) 400 ::1: 60
nPrF (465) nPrBr (3JZ)
C C cxt. sk. def. 270 :!: 95 nPrC=CH (175) 280 ::1: 85
nPrC=N and пРrSiDз (188)
lorsion Мс 225 :!: 45 nPrC(==O)H (270) nPrCI (187) 220 ::1: 30
lorsion Е! 120:!: 30 120 ::1: 30
torsion nPr
R nPr molecules
R = Me [52, 53], tBuCHz [1], СlзСС(==О)СНz [2], HC=CCHz [3,
4], N=CCHz [5], HzNCHz [6---8], MeNHC(==O)NHCHz [9],
HOCHz [10], iPrSCHz [Щ, FCHz [12], CICHz [13, 14],
BrCHz [14, 15J, ICHz [14, 16], НзSiСНz and DзSiСНz [17],
HC(==O) [18], CIC(==O) and BrC(==O) [19], 4 XPhC(==O) (Х
= F, СI and Br) [20], 3 OzNPhC(==O) , 2 HOPhC(==O) [21,
23], 4 HOPh C(==O) [23], Ph , 3 BrPh [22], HC=C [24,
25], MeC=C [26], N=C [27 29], HzN and DzN [6, 3()"",
32], MeC(==O)NH and EtC(==O)NH [33], MeNHC(==O)NH [9],
OzN [34], HO [35], СlзС(==О)О [2], HS [3 39], EtS [40],
iPrS [11], NCS [41], F [42], CI [13,14,43--48, 50], Br [14, 15,
43----47, 49], I [14,16,43,45, 46], НзSi and DзSi [17], MeSiНz and
MeSiDz [17].
References
1. а.А. Cro\vder and R.M.P. Jaiswal,J. Mol. 5/rllct., 102, 145 (1983).
2. У. Mido, N. Komatsu, J. Morcillo and М.У. Garcia, J. Мо/. 5/r//ct., 172, 49 (1988).
3.5 CaI'boп boпded Me//ly/eпe
103
3. R.F. Kendall, 5pectrocIlim. Ас/а, Par/ Л, 24А, 1839 (1968).
4. а.А. Crowder, J. Mol. 5trиcl., 172, 151 (1988).
5. а.А. Crowder, J. Мо/. 5trllc/., 200, 235 (1989).
6. Н. Wolff and Н. Ludwig, Ber. ВШlsе"gеs. P/1YS. Chem., 71, 1107 (1967).
7. J.1.c. Tcixeira-Dias, L.AE. Batista Ос Carvalho, АМ. Amorim Оа COS1a, I.M.S.
Lampreia and E.F.G. Barbosa, Spectrocllilll. Асш, Parl А, 42А, 589 (1986).
8. а. Ramis and а. Busca,J. Мо/. Slrllct., 193,93 (1989).
9. У. Mido, F. Fujita, Н. Matsuura and К. Machida, 5peclrochim. Acta, Parl А, 37А, 103
(1981).
10. а.А Crowder and M.J. Townsend, J. Mol. 5Irиct., 42, 27 (1977).
11. М. Ohsaku, Н. Murata and У. Shiro, 5peclroclliт. ACla, Parl А, 33А, 467 (1977).
J2. а.А. Crowder and Н.К Mao,J. Мо/. 5trиct., 23,161 (1974).
13. А.1. Bames, M.L. Evans and Н.Е. Наllаm, J. Мо/. 5Ir/lcl., 99, 235 (1983).
14. У. Ogawa, S. Imazeki, Н. Yamaguchi, Н. Matsuura, 1. Harada and Т. Shimanouchi, Ви/l.
C/lem. 50С. Jp".,. 51, 748 (1978).
15. а.А Crowdcr and M.R. Jalilian, Са1l. J. 5peclrosc., 22, 1 (1977).
16. а.А. Crowder and S. Ali, J. Mol. 5Irиcl., 25, 377 (1975).
17. Н. Murata, Н. Matsuura, К Ohno and Т. Sato, J. Mol. 5tтCI., 52, 1 and IЗ (1979).
18. а. Sbrana and У. Schettino, J. Мо/. 5pectrosc., 33, 100 (1970).
19. J. Som. О. Bhaumik, О.К MukhcIjee and G.S. Кastha, IlIdiall J. pиre Appl. Phys., 12,
149 (1974).
20. W.A Seth Paul and J. Meeuwesen, B/I/I. 50С. СЫт. Belg., 90,127 (1981).
21. W.А.L.к. A1 Rashid and M.F. EI Bcrmani, 5pectrocllim. ACla, Ратl А, 47А, 35 (1991).
22. S. Chattopadhyay, L. Chakravorti and G.S. Kastha, I"diall J. pиre Арр/. Phys., 25, 456
(1987).
23. а. Varsanyi, Assigllmellls[or Vibralio"a/ Speclra of5cvell HlllldredBellzeпe Derivatives,
J.Wiley & Sons, New York (1974).
24. а.А. Crowder and Н. Fick, J. Mol. 5Irиc/., 147, 17 (1986).
25. а.А Crowder, 5peclrocIlim. Асш, Parl А, 42А, 941 (1986).
26. а.А Crowder and Р. Blankenship,J. Мо/. 5Irllct., 196, 125 (1989).
27. S.W. Charles, F.C. Cullen and N.L. Owen, J. Mol. 5IтCI., 34, 219 (1976).
28. а.А. Crowder, J. Mol. 5Irllcl., 158, 229 (1987).
29. Т. Fujiyama, ВII/I. C/lem. 50С. Jp"" 44, 3317 (1971).
30. L.A.E. Batista de Carvalho, А.М. Amorim da Costa, M.L. Duartc and J.1.c. Tcixcira-
Dias, 5реСlюсЫт. ACla, Part А, 44А, 723 (1988).
31. N. Sato, У. Hamada and М. Tsuboi, 5pec/rocllilll. ACla, Parl А, 43А, 943 (1987).
32. J.R. Durig, W.B. Beshir, S.E. Godbey and T.J. Hizcr, J. Raтa" 5peclrosc., 20, 311
( 1989).
33. J. Jakes and S. Кrimm, 5pectrocIlim. Acta, Parl А, 27А, 35 (1971).
34. а. Geiseler and Н. Kessler, Ber. ВШlsе"gеs P/,ys. CI/em., 68, 571 (1964).
35. К. Fukushima and В.1. Zwolinski, J. Мо/. 5peclrosc., 26, 368 (1968).
36. Т. Torgrimsen and Р. К1аЬое, Acla С//ет. 5ca"d., 5er. А, 24, 1139 (1970).
37. D.W. Scott and M.Z. El-Sabban, J. Мо/. 5peclrosc., 30,317 (1969).
38. К.а. Allum, J.A Creighton, J.H.S. Green, а.1. Minkoff and L.1.S. Рrinсе, 5pecrrocIIiт
ACla, Parl А, 24А, 928 (1968).
39. М. Hayashi, У. Shiro and Н. Murata, ВII/I. CI/em. 50С. Jp"" 39, 112 (1966).
40. М. Otha, У. Ogawa, Н. Matsuura, 1. Harada and Т. Shimanouchi, 8/1/1. Cllem. 50С. Jp""
50, 380 (1977).
41. R.P. Нirschmann, R.N. Кniseley and У.А Fassel, 5pectrocIIim. ACla, 20, 809 (1964).
42. а.А. Crowder and Н.К Мао, J. Мо/. 5IrIlCI., 18,33 (1973).
43. J.K Brown and N. Sheppard, Tra"s. Faraday 50С., 50, 1164 (1954).
104 Norllla/ Vibт/io/ls a/ld Absolp/io/l Regio/ls о/ CH2X
44. С. Kombaki, 1. Ichishima. К. Kutanal1i, Т. Miyaza\va, Т. Slliпшпоuсhi al1d S. МiZl1shiпщ
ВIIII. CI/cIII. 50С. JplI., 28, 330 (1955).
45. К. Таl1аЬе al1d S. Sаёki, J. Mol. 5Ir11CI., 27, 79 (1975).
46. N.T. McDevitt, AL. Rozck, F.F. BCI1t1ey al1d АО. Davidson,J. C/rcl1l. P/,YS., 42, 1173
(1965).
47. К. Radcliffe al1d J.L. Wood, Tra/ls. Fara,/a)' 50С., 62, 1678 (1966).
48. R.G. Sl1yder al1d J.H. Sсlшсhtsсhl1еidеr, J. Мо/. 5pcclrosc., 30, 290 (1969).
49. М. Hayaslli. К. ОI1ПО al1d Н. Murata, ВIIII. CI/С/II. 50С. JP/I., 46, 2332 (1973).
50. У.А. Pozdyshev. Yu.A Pel1til1 al1d У.М. Tatevskii, Ор'. 5peclrosc., 3, 211 (1957).
51. F. Ciampclli al1d С. Tosi, 5pec/rocIliIII. ACla, Part Л, 24А, 2158 (1968).
52. J.R. Durig. А Wal1g, W. Bcshir al1d T.S. Little, J. Ral1lall 5peclrosc., 22,683 (1991).
53. Р. Derreumaux, М. Dauchcz апd G. VеrgОlСП, J. Мо/. 5t/"l/ct., 295, 203 (1993).
3.5.6 РroрупуI
lПе XCHzC=CH compounds (Х = F, Cl, Br, 1) belong 10 the point group С . and
the 3N 6 = 15 поrrnаl vibrations are dividcd into 10а' and 5а" types of vibration.
Substitution of IICX Ьу а torsion leads (о the 15 normal vibrations (9а' + 6а") of
CHzC=CH:
а': усн, vsCH z , уС=С, БСНz, wCHz, yC C, БСН, Б С С, БС С=С;
а": vaCH z , TCH z , pCHz, ')'СН, ')'C C=C and torsion.
lПе СН stretching vibration
lПе =сн stretch, ап excelIent group vibration, is characterized Ьу the very sharp
and strong absorption in the range 3315::1: 25 cт 1; this is the highest СН stretching
vibration, since the sрЗ and spZ hybridized СН bonds show the СН stretching аl
Iower frequencies. lПе band of the NH strctching vibration in secondary amides
(Section 7.3) and amines (Section 9.2), also occurring in this region, is broader and
по! so strong. Nyquist found values of 3332 ::1: 8 cт l for а series of 1-alkynes
with the basic structure Me(CHz)"C=CH (11 = 1 14) [32].
Methylene stretching vibrations
The methylene antisymmetric stretch appears weak1y 10 moderately а! 2970
::1: 40 Cm l. High values are found in the spectra of CIC(==O)OCH z C=CH
(3010), 1CHzC=CH (3008) and BrCHzC=CH (3006 Cm l) and 10w values in
Ihose of HzNCHzC=CH (2930), HC=CCHzCHzC=CH (2938 and 2945) and
MeCHzC=CH (2939 cm l). There is а great change (о find the vaCHz in the
region 2970 ::1: 30 cm l.
lПе methylene symmetric stretch is assigпеd in the range 2935 ::1: 40 Cm l. If the
contribution of the absorption а! :::::2875 cm l (о this vsCH z is laken into accounl,
the region increases (о 2915 :i: 60 cm l. BrCHzC=CH (2975) and CICHzC=CH
(2968 cm l) give high values. In the spectra of MeOCHzCHzC=CH (у . 2935
3.5 Carboп-boпded Me/hy/eпe
105
and 2855) and HOCHzCHzC=CH (1/" 2928 and 2890 cm l) the lowcr value
mау Ьс assigncd (о v.,CHzO and the higher (о I/"CHzC, but HzNCHzC=CH and
HOCHzC=CH cxhibit а medium band а! 2855 and 2873 cm 1 respectively which
is assigncd to thc v.,CHz.
Although thc rcgions of vaCH z and v.,CH z overlap each other, the two vibrations
appear а! different wavenumbcrs.
The С=С strctching vibration
With а range of 2125 ::1: 25 cт l and а wcak to moderate band intensity,
the С=С stretching vibration takes а unique place as а good group vibration.
Because of the influence of the halogen, FCHzC=CH (2150) and CICHzC=CH
(2147) absorb at high values. This band shifts (о lower wavenumbers in the
spectra of MeOCHzC=CH and EtOCHzC=CH (2115) and HzNCHzC=CH,
MeHNCHzC=CH and MezNCHzC=CH (2100 cm I). Тhe С=С stretching
frequencies of (еп l alkynes in the gas phase are reported as being in the range
2147::1: 15 cт l [32].
Methylene deformations
The methylene scissoring vibration is moderately active in the region 1440 :i: 25
cm l, in which other CH z scissors also absorb.
lПе methylene wag is assigned in а range (1305 :i: 75 cm l) in which
also overtones of Б ""СН and I ""СН give rise (о а weak but broad
typicaI band. The HW side of this region is limited Ьу FCHzC=CH (1375),
ClzP(==S)OCHzC=CH (1367) and CIC(==O)OCHzC=CH (1366 cm l) and the
LW side Ьу NCSCHzC=CH with 1235 for the anti conforrner and 1247 cm l for
the gallc/le. The 10w values observed in the spectra of ICHzC=CH (1160) (Section
3.1.4) and BrCHzC=CH (1218) (Section 3.1.3) are outside the above mentioned
region.
lПе twist is assigned а! 1255 ::1: 80 cm J, with the highest va1ues for
HzNCHzC=CH (1335), MeOCHzC=CH (1284) and CIC(==O)OCHzC=CH
(1270 Cm l) and the lowest for NCSCHzC=CH (1179) and CICHzC=CH (1179
Cm l). lПе lower wavenumbers from ICHzC=CH (1116) and BrCHzC=CH
(1152 cm l) are not taken into account.
lПе C C stretch and methylene rock
Based оп spectra of analogous compounds, it appears that the methylene rock
absorbs а! Iower wavenumbers than the C C stretching vibration. Nevertheless
some spectroscopists assign higher wavenumbers (о the rock. ТаЫе 3.26 shows
that the spectroscopists are по! always unanimous in assigning the C C stretch
and the methylene rock.
106 Noтza/ VilJт/io"s a"d AlJsorp/io" Regiol1s о/ CI-l2X
ТаЫе 3.26
R CH2C=CH уСС pCHz rcf.
HC=CCHz 1021 950 [7]
HOCHz 1020 950 [8]
Me 1008 782 [2]
H2C==C==CH 1005 890 [10]
CIC(==O)O 992 937 [21]
Br 961 866 [24,25]
CI 960 908 [25,26]
MeO 938 899 [16]
Me 840 782 [1]
F 938 1018 [15, 23, 24]
ЕtO 920 1016 [19]
MeO 893 1007 [17, 18]
HO 917 980 [15]
OO 907 971 [15]
In this (ех! the pCH z is assigned а! а lower wavenumber (865 ::1: 85) than that
of the C C stretching vibration (930 ::1: 90). Nyquist and Potts assign the yC C
in а few RCHzC=CH compounds а! 930::1: 30 cт 1 [31].
сн deformalions
lПе in plane and out of plane =сн deformations are nlOderately (о strongly active
in the regions 660::1: 30 and 635 ::1: 15 cm l. In addition 10 the усн and уС=С,
these deformalions take а special place as group vibrations of CHzC=CH. Often
Ihe two deformations coincide and give rise (о опе broad band because Ihere is
only а sIight difference in energy between in plane and out of plane deformations
in molecules with а straight chain. In the spectra of FCHzC=CH (675 and 635) and
CIC(==O)OCHzC=CH (689 and 645 cm l) the Б =СН and 'у =СН are clearly
separated, Ьи! in those of MeCHzC=CH (634 and 630) and EtCHzC=CH (634
and 629 cт l) both deformations absorb closely together because of the smalI
difference in electronegativity. Higher l alkynes exhibit опе broad band which for
Me(CH z )IIC=CH (11 = 1 14) is situated at 631::1: 3 cт l [32]. Overtones of these
deformations give а weak Ьи! broad absorption in the region of the CH z wag and
t\vist. Such а typical band is usualIy seen in the spectra of 1 alkynes а! 1250 ::1: 10
cm l [31].
Skeletal deformations
lПе vibrational analysis reveals that the external skeletal R C C deformation
is in the range 505 ::1: 70 cт l, in which the low values for BrCHzC=CH (399)
and ICHzC=CH (364 Cm l) are по! included. lПе utility of the out of plane and
3.5 Carboп boпded Me/hy/eпe
107
in-plane C C=C skelctal dcformations, which are weakly active in the respective
ranges 330 ::1: 35 and 195 ::1: 45 ст 1, is very limited for identification purposes.
ТаЫе 3.27 Absorption regions (cm J) of the normal viЬrаtiопs
of CHzC=CH
Vibration Region Vibration Region
уСН 3315::1: 25 pCHz 865 :!: 85
vaCHz 2970 ::1: 40 Бсн 660 :!: 30
v"CI-Iz 2915::1: 60 ,сн 635:!: 15
уС=С 2125::1: 25 C C ext. sk. def. 505 :!: 70
Бснz 1440 ::1: 25 ,C C=C 330 :i: 35
wCHz 1305 ::1: 75 БС С=С 195 :i: 45
TCHz 1255 ::1: 80 torsion
yC C 930 ::1: 90
lПе following R CHzC=CH molecules are taken into account:
R = D [зо], Me [1 3], СDз [1], Et [3 5], nPr [5, 6], nBu and
nPent [5], HC=CCHz [7], HOCHz [8], MeOCH2 , iPr [9],
HzC==C==CH [10], HzN [11, 12], OzN [11], MeНN , Me2N ,
Nз [13], HO [14, 15], DO [15], MeO [16---18], EtO [19],
HC(==O)O [20], CIC(==O)O [21], ClzP(==S)O [21,23], NCS [22],
F [15,23, 24], CI [24----27J, Br [24,25,28, 29], I [24].
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5Ir/lct.,41, 203 (1978).
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(1978).
11. У. Hamada, М. Tsuboi, М. Nakata and М. Tasumi,J. Mol. 5peclrosc., 107, 269 (1984).
12. N.V. Riggs, AlIst. J. CI,em., 40, 435 (1987).
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(1987).
14. J. Travert, J.c. Lavalley and О. Chenery, 5pectrocllim. Ас/а, Par/ А, 35А, 291 (1971).
15. R.A. Nyquist, 5peclrocllim. Acta, Part А, 27А, 2513 (1971).
108 Norllla/ VilJ/'{t/io"s ат! A/Jsorp/io" Regio"s о/ CH2X
16. А Bj0rseth and J. Guslavsen,J. Mol. 5Irllct., 23, 301 (1974).
17. W.A. Seth Paul. J.P. Tollel1aere, Н. Mceusen 311d F. HUller, 5pcct/'Ocllilll. ACla, Parl А,
30А, 193 (1974).
18. S.W. Charlcs, Ес. Cullen, G.I.L. Jones al1d N.L. O\ven, J. C/1CIII. 50С., F(//"Q{/ay т,'аIlS.
2,70,758 (1974).
19. S.\V. Cllarles, F.C. Cullen and N.L. O\vcn, J. C/1CIII. 50С. F(//"(/(/ay TтllS. 2, 72, 351
(1976).
20. G.I.L. Jones, О.а. Lister al1d N.L. O\ven, J. C/Ielll. 50С. Fara,lay TrallS. 2, 71, 1330
(1975).
21. R.A. Nyquist, 5peclrocl!illl. Ас/а, Рт'l А, 28А, 285 (1972).
22. Т. Midtgaard, а. Gundersen and С.1. Niclsen, J. Mol. 5/rllct., 176, J 59 (1988).
23. R.A. Nyquist and W.W. Muelder, J. Мо/. SI/"/,ct., 2, 465 (1968).
24. J.c. Evans and R.A Nyquist, 5peclrocl!illl. ACla, 19, 1153 (1963).
25. R.A Nyquist, AL. Johnson and Y.S. Lo, 5pectrocl!illl. Acta, 21, 77 (1965).
26. КА Nyquist, T.L. Reder, G.R. Ward and а.1. Kallos, 5pectrocllim. Acta, Parl А, 27А,
541 (1971).
27. Е. Hirota and У. Morino, BIIII. Cllem. 50С. JplI., 34, 341 (1961).
28. Е. Кikuchi, Е. Hirota and У. Morino, BIIII. C/lem. 50С. Jpll.,. 34, 348 (1961).
29. R.A. Nyquist, T.L. Reder, F.E Stec and а.1. Kallos, 5pecl/'Ocllim. ACla, Part А, 27А,
897 (1971).
30. Н. Priebe, С.1. Nielsen and Р. К1аЬое, 5pec/roc//illl. ACla, Part А, 36А, 1017 (1980).
31. R.A. Nyquist and W.1. Potts, 5peclrocl!illl. Acta, 16,419 (1960).
32. R.A. Nyquist, Арр/. Spectrosc., 39,1088 (1985).
3.5.7 CyanomethyI
lПе simplest compounds that contain the CHzC=N structure unit are
XCHzC=N (Х = F, CI, Br, 1). lПе 12 normal vibrations arc composed of 8а'
and 4а" species of vibration. Substitution of уСХ (а') Ьу а torsion (а") gives the
12 vibrations of CH2C=N:
а': vsCH z , vC=N, БСН z , wCHz, yC C, Б С С, БС С=N;
а": vaCHz, TCHz, pCHz, "')'C C=N and torsion.
Mcthylene stretching vibrations
lПе vaCHz is found in the range 2980 ::1: 50 cт ]. The highest wavenumbers (3020
::1: 10 cт l) are due (о XCHzC=N (Х = F, CI, Br, 1) (see Section 3.1), followed
Ьу /ralls N=CCHzCHzC=N (2998) and NзСНzС=N (2996 Cm I). The lowest
wavenumbers have Ьееп traced in the spectra of HzC==CHCHzC=N (2936) and
HzC==C(Me)CHzC=N (2947 cт ]). Most of the investigated molecules were
found 'о give this antisymmetric stretching in the region 2970 ::1: 30 Cm l. lЛе
symmetric counterpart appears in the range 2915 ::1: 65 cm l with compounds such
as XCHzC=N (Х = F, CI, Br) (2973:!: 4 cm l) а! the HW side and MeSCHzC=N
(2857), BrCHzCHzC=N (2857), nPrCHzC=N (2875) and EtCHzC=N (2885
cт l) а! the LW sidc. lПе remaining molecules show the vsCHz а! 2930 :f: 40
cm l.
3.5 Carboп-bollded Me//ly/eпe
109
Тhe C=N strctching vibration
Тhe CHzC=N group is bcst recognized Ьу the C=N strеtсhiпg vibration
in the narrow rcgion 2260 ::1: 15 Cm l. lПе intcnsity of the sharp peak is
modcrate (о strong with the exccption of the vC=N iп XCHzC=N, for which
Х prcsents а strongly ncgative group (c.g. FCHzC=N). Тhe С=С stretching
vibration absorbs upwards of 100 Cm l lower with а much weaker iпtепsitу
(Section 3.5.6). Thc highcst valucs for thc C=N strеtсhiпg vibration have Ьееп
attributed in the spectra of N=COlzC=N (2275), HzNC(==O)CH2C=N (2271)
and HO(O==)CCHzC=N (2271 cm l), thc lowest in those of СDзСНzС=N,
cPrCHzC=N, MeSCHzC=N and ICHzC=N in the neighbourhood of 2245
cm t. lПе vC=N in HzC==C(Me)CHzC=N and HzC==CHCHzC=N is situated
а! 2247 Cm l. The lower absorption band (2220 cm l) iп the spectrum of
HzC==C(Me)CHzC=N [30] comes probabIy from the conjugated C=N of
the isomers [29]. Conjugated organonitriles, however, exhibit vC=N а! lower
frequencies (2225 ::1: 10) than non conjugated aliphatic nitriles (2245 :I: 15 cm l)
[42,43].
Methylene deformations
lПе methylene scissors absorbs in the range 1425 :I: 30 cm l with а moderate
(о strong intensity. This range is limited Ьу /ra1lS N=CCHzCHzC=N (1455 and
1445) and FCHzC=N (1453 Cm l) а! the HW side and Ьу N=CCHzC=N (1395),
MeSCHzC=N (1400), ICHzC=N (1408) and BrCHzC=N (1410 cm l) а! the
LW side. The methylene scissors is usual1y observed а! 1430 :I: 20 cm l.
lПе methyIene wag is weakly (о moderately active in the region 1295 :I: 65
cm l, in which the extreme values from FCHzC=N (1381), ICHzC=N (1155)
and BrCHzC=N (1220 Cm l) are по! included (Section 3.1). Disregarding aIso
the values 1359, 1353 and 1237 Cm l in the spectra of N=CCHzCHzC=N,
MeOCHzC=N and MeSCHzC=N, most of the R CHzC=N compounds absorb
in the region 1295 ::1: 45 cm t.
Disregarding the low values of BrCHzC=N (1155) and 1CHzC=N (1100
cm 1), the methylene twist is assigned in the region 1230 :I: 55 cm l. Нigh
values originate from the spectra of MeOCHzC=N (1285) and MeCHzC=N
(1272 Cm l) and low values from those of N=CCHzCHzC=N (1178 and 1232),
MeSCHzC=N (1184) and CICHzC=N (1185 cт I). Usual1y the twist is assigпеd
а! 1230::1: 40 Cm l, wel1 separated from the wag.
C C stretching and methylene rocking vibration
It is по easy matter (о estabIish the absorption regions of the C C stretch and the
CH z rock from pubIished data, probably because of their соuрliпg опе to the other.
With reservations, it is assumed that the C C stretch absorbs in the region 955 :I:
110 Nomт/ VilJтliolls arld AbsOlplioll Regiolls о/ CH2X
65 cm 1 and the CH z rock а! 840 ::1: 80 cm l. In thc cxamplcs in ТаЫс 3.28 tl1c
maximum and minin1Um values arc includcd.
ТаЫе 3.28
Compound
FCHzC=N
tra/ls N=CCHzCHzC= N
gallclle N =CCHzCHzC=N
McCHzC=N
MeSCHzC=N
cPrCHzC=N
H2C==CHC H zC=N
N=CCHzC=N
CICH2CHzC=N
BrCHzCHzC=N
yC C
1019
1005,951
975, 963
1004
965
960
936
936
919
896
pCHz
911
917,762
818,816
784
844
830
865
893
885
800
Skeletal deformations
Setting aside the Iow values from halogen bonded CHzC=N (Section 3.1),
the external C C skeletal deformation, strongly coupled with БС С=N,
is assigned in the range 535 ::1: 70 cm l. In the spectrum of gallclle
N=CCHzCH2C=N the absorptions а! 604 and 480 cт ! are attributcd (о this
skeletal deformation. lПе out of plane C C=N skeletal deformation is weakly
active а! 365 :!: 25 cт l and the in plane C C=N deformation а! 225 ::1: 65
cm l.
ТаЫе 3.29 Absorption regions (cm I) of the normal vibrations
of CHzC=N
Vibration Region Vibration Region
vaCHz 2980 ::1: 50 yC C 955 ::1: 65
vsCHz 2915::1: 65 pCHz 840 ::1: 80
vC=N 2260 ::1: 15 C C ext. sk. def. 535 ::1: 70
Бснz 1425 ::1: 30 'YC C=N 365 ::1: 25
wCHz 1295 ::1: 65 БС С=N 225 ::1: 65
TCHz 1230::1: 55 torsion
R CHzC=N molecules
R = Me [1 7, 41], СDз [3], Et [7 10], nPr [7, 11], cPr [12],
N=CCHzCHz [6], N=CCHz [6, 13, 14], CNCHz [15], CICHz [4,
9, 16---18], BrCHz [4, 9], HO(O==)C [19], NaO(O==)C [19, 20],
3.5 Carboп bollded Me//ly/elle
111
H2N(O==)C [21J, iВuO(O==)C , EtO(O==)CHN(O==)C ,
H2N(S==)C [22J, H2C==CH [23 26], H2C==C(Me) [26---30],
N=C [6, 31, 321, Ph [44], 4-ClРh [33], 4-МеОРh , 2-Тh ,
Nз [34J, MeO [35, 36], MeS [10], F , CI and I [37 39],
Br [37----40].
References
1. а.А. Crowder, 5peclrosc. Le/l., 20, 343 (1987).
2. а.А. Crowdcr, 5peclrocllim. ЛСIa, Parl А, 42А, J229 (1986).
3. Н.Н. Heise, F. Winther and Н. Lutz, J. Mol. 5pec/rosc., 90, 531 (1981).
4. Р. К1аЬое and J. Grundnes, 5peclroclliт. Ас/а, Par/A, 24А, 1905 (1968).
5. N.E. Ouncan and G.J. Janz,J. С//ет. PII)'S., 23, 434 (1955).
6. R. Yamadera and s.кrimm, 5pec/rochiт. ACla, Par/ А, 24А, J677 (J968).
7. J.1. Lucier, Е.с. Tuazon and F.F. Bentley, 5peclroclliт. ACla, Parl А, 24А, 771 (1968).
8. а.А. Crowder, J. Mol. 5Ir/lc/., 158,229 (1987).
9. Т. Fujiyama, B/lII. Clleт. 50С. JplI., 44, 33J7 (1971).
10. S.W. Charles, F.c. CuHen and N.L. Owen, J. Mol. 5/r/lc/., 34, 2J9 (1976).
11. а.А. Crowder, J. Мо/. 5/rtICI., 200, 235 (1989).
J2. С.1. Wurrey, У.У. Yeh, М.О. Weakly and Y.F. Kalasinsky,J. Ramall 5peclrosc., 15, 179
(1984).
13. W.E. Fitzgerald and а.1. Janz, J. Mol. 5pectrosc., 1, 49 (1957).
J4. Т. Fujiyama, К Tokumaru and Т. Shimanouchi, 5peclroclliт. Ас/а, 20, 415 (1964).
15. а. Schrumpf and S. Martin, J. Mol. 5Ir/lc/., 101,57 (1983).
16. Е. Wyn Jones and W.J. Orville Thomas, J. CI,еlll. 50С., 101 (1966).
17. M.F. EI-Berrnani and N. Jonathan,J. Cllem. 50С., 1712 (1968).
18. К. ТапаЬе, J. Mol. 5/rllc/., 25, 259 (1975).
19. О. Sinha and J.E. Katon, Appl. 5peclrosc., 26, 599 (1972).
20. Е. Spinner, J. C/lem. 50С., 4217 (1964).
21. L. Уап Haverbeke and М.А Неrrnап, 5peclrocllim. ACla, Par/ А, 31А, 959 (1975).
22. А Ray and O.N. Sathyanarayana, B/lII. Clleт. 50С. Jpll., 46, 1969 (1973).
23. О.Ас. Compton and W.F. Murphy, 5pec/rocIli1ll. Ас/а, Part А, 41А, 1141 (1985).
24. A.L. Уеrrnа, J. Мо/. 5pec/rosc., 39,247 (1971).
25. а.Н. Griffith, L.A Harrah, J.W. Clark and J.R. Ourig, J. Mol. 5tr/lct., 4, 255 (1969).
26. О.А.с. Compton, S.C. Hsi and Н.Н. Mantsch, J. P/1YS. CI,em., 85, 3721 (1981).
27. О.А.С. Compton, S.c. Hsi, Н.Н. Mantsch and W.F. Murphy, J. Raтall Spectrosc., 13,
30 (1982).
28. S.H. Schei, 5pec/rocllim. Acta, Part А, 39А, 327 (1983).
29. О.Ас. Compton, W.F. Murphy and Н.Н. Mantsch, 5pec/rocIli1ll. ACla, Part А, 37А, 453
(1981).
30. АД OiaHo, 5pec/rocllim. Ас/а, Par/ А, 35А, 1189 (1979).
31. Т. Fujiyama and Т. Shimanouchi, 5pectroclli1ll. Acta, 20, 829 (1964).
32. В.1. Уап der Veken and Н.О. Oesseyn,J. Mol. 5Ir/lct., 23, 427 (1974).
33. S. Chakravorti, АК Sarkar, Р.К Mallick and S.B. BaneIjee, /lIdiall J. PI/ys., 56В, 96
(1982).
34. Р. К1аЬое, К Kosa, C.J. Nielsen, Н. Priebe and S.H. Schei, J. Мо/. Slrиct., 160, 245
(1987).
35. S.W. Charles, Ес. CuHen, G.I.L. Jones and N.L. Owen, J. CI/em. 50С. Faraday Tralls.
2,70,758 1974)
36. R.G. Jones and W.J. Orville Thomas, J. Chem. 50С., 692 (1964).
112 Norl1la/ Vibra/iolls alld Absorp/ioll Regiolls о/
CH2X
37. R.G. Jones and W.J. Orvillc-Тhоmаs,J. CI1Cт. Soc., 4623 (1965).
38. J.R. Durig and D.W. Wertz, Spcc/roclliт. Лс/а, Par/ Л, 24А, 21 (1968).
39. а.А. Cro\vdcr, Mol. PII)'S., 23, 707 (] 972).
40. F. Watari and К. Aida, Spcc/rocllim. Лс/а, Par/ Л. 23А, 2951 (1967).
41. C.J. Wurrey. W.E. Bucy and J.R. Durig, J. PI/)'s. CI/cm., 80, ]]29 (1976).
42. R.A. Nyquist, Appl. Spcc/rosc.. 41, 904 (] 987).
43. R.E. Кitson and N.E. Griffith, Лllаl)'/. CI,cm., 24, 334 (1952).
44. а. Varsanyi, ЛssigllmСlllS [о, Vibra/iollal Spec/ra O[SCVCII H/llldrcd BCIlZCIIC Deriva/ivcs,
J.Wilcy & Sons, Ne\v York (1974).
4
Normal Vibrations and
Absorption Regions of СНХ 2
4.1 DIНALОGЕNОМЕТНУL
lПе
CHXz group (Х = F, CI, Br, 1), just like the СХ з group, has nine normal
vibrations:
уСН, БСН, wCH, vaCXz, vsCXz, wCXz, TCXZ, БСХ z and torsion.
(! is quite possibIe that rotational isomers give rise (о more than опе band for
the same vibration. Molecules such as MeCHCl z , traпs
FzCHCHClz and Iraпs
CICHzCHClz show а plane of symmetry and belong (о the point group C s , (п
this case eleven (а') of the eighteen vibrations cause а change in dipole mоmеп!
in this plane and seven (а") cause а dipole change in а direction perpendicular
to the plane of symmetry. 111е 5а' and 4а" vibrations of the
CHClz group in
l,1
dichloroethane are Iisted in ТаЫе 4.1.
ТаЫе 4.1 Vibrations of MeCHC1z
а' а"
усн 3008 wCH 1230
Бсн 1280 vaCClz 691
vsCClz 647 TCC1z 318
wCC1z 405 torsion 293
БСС1z 274
114 Norlllal Vibтliol1s al1d Absol]Jliol1 Regiol1s о/ сих]
Gallclle
F2CHCHCI2 and gallc//e
CICH2CHCI2 Iшvе по plal1e of symmetry and
bclol1g to the point group С 1 . TI1C diffcrcnce betwcel1 а' al1d а" disappcars and
the litcrature docs по! agree in assignil1g the
CHX2 deformations in terms of
in
planc bCl1ding, \vag, twist or rock.
4.1.1 Difluoromethyl
Thc СН vibrations
Thc vibratiol1al analysis of difIuoromethyl compoul1ds rcvcals the СН stretching
vibration а! 2990 :!: 15 СП1
I, or mostly суеп а! 2995 :!: 10 cm
1 if the value 2995
cm
1 [2] is prcfcrrcd to 2975 cm
1 [1] in thc spcctrum of 1,1
difluorocthane.
Thc two СН dcformations are modcratcly (о strongly activc, опе а! 1395 :!:
50 and thc other а! 1275 :!: 70 cm
1. Thcy are sensitive to conformation but the
wavcnumbcrs of thc Iral1s al1d thc gallc//e conformcr rarely diffcr Ьу more than 40
cm
l. Ву analogy with С . molcculcs, thc first is considercd as the ЬСН (а') and
occurs normally а! 1370 :!: 25 cm
1, ncglccting thc wavcnumbcr 144З cm
1 in
thc Raman spcctrum of traI1S
F2CHCHF2. Thc sccond deformation is then the СН
wagging vibration (а") occurring in thc rangc 1295 :!: 50 cm
l, ехсср! for the low
valuc (1212 cm
1) in the spcctrum of CICF2CHF2.
The CF 2 strctching vibrations
Thc CF2 antisymmctric strctch givcs risc to а strong band in thc rangc 1155
:!: 50 cm
1, which diminishcs (о 1140 :!: 30 cm
! if thc valucs 1205, 1203
and 1104, in thc spcctra of respectivcly gallc//e-F2CHCHF2, BrCF2CHF2 and
CI2C==C(Cl)CHF2, arc ignored Ьи! without rcjection.
Thc CF2 symmctric strctch appcars strongly а! 1090 :!: 35, or а! 1080:!: 25 cm
1
without thc highcst valucs of 1125 cm
1 in thc spcctrum of Ira//s-F2CHCHF2 and
1118 cm
1 in that of McCHF2.
Thc CF2 strctching vibrations, although scnsitivc to thc conformational statc of
the molcculc, mcrit thc titlc 'group vibration' оп account of thcir intcnsity.
ТЬс CF2 skclctal deformations
Thc CF 2 wag is scnsitivc to rotational isomcrism, yiclding band scparations of up
to 100 wavcnumbcrs and morc. Thc highcst wags havc Ьссп assigncd in thc spectra
of galldle
F2CHCHF2 (780 and 59В), gallc//e
CI2CHCHF2 (765) and HOCH2CHF2
(749 cm
1), thc lowcst in thosc of McCHF2 (568), Ira//s
F2CHCHF2 (625 alld 542)
апd HO(O==)CCHF2 (574 cm
1). In mапу cases thc CF2 wag is obscrvcd а! 630
:!: 30 cm
1 as а modcrate to strong band.
4.1 DiI/alogellomelhyl
115
Thc СР2 in pIanc dcformation absorbs mostly а! 525 ::1: 50 cm 1, with а modcratc
to strong intcnsity, if thc low valucs for tralls F2CHCHF2 (479 and 417) and
HOCH2CHF2 (429 cm 1) arc ignorcd.
Thc third skclctal dcformation, thc СР2 1wisting vibration, absorbs wcakly to
modcratcly in the range 260 ::1: БО cm 1 if thc high value 383 cm 1 from the
spcctrum of McCHF2 is по! takcn into account. Тhc bCF2 and TCF2 absorptions
are virlualJy insensitivc to conformation.
Torsion
With the exccption of the mcthyl torsion in McCHF2 (220 cm t), mапу CНF2
torsions arc assigned а! 105 ::1: 35 cm 1.
ТаЫс 4.2 Absorption rcgion (cm l) of 'he поrrnа1 vibrations of CHF2
Vibration С . Rcgion Vibration С . Rcgion
I/СН а' 2990::1: 15 ""C F 2 а' 660 ::1: 120
ЬСН а' 1395 ::1: 50 bCF2 а' 495 ::1: 80
wCH а" 1275 ::1: 70 TCF2 а" 290 ::1: 95
l/ a CF 2 а" 1155::1: 50 'orsion а" 145::1: 75
I/ s CF 2 а' 1090::1: 35
R CHF2 moleculcs
R = Me [1, 2], HOCH2 [З], FCH2 [4], F2CH [4, 5], CI2CH [б],
FзС [7], CICF2 and BrCF2 [8], CI2C==CCI [9], HOC(==O) [10],
H2NC(==O) [11].
4.1.2 Dichloromethyl
The СН vibrations
With the cxccption of thc low valucs for gaиche HC(==O)CHCI2 (2970) and
Cl2CHCHCl2 (3012 and 2980 cm 1), thc СН strctching vibration is obscrvcd а!
3000 ::1: 15 cm 1,
Тhc two СН dcformations are scnsitive to thc conformational statc of thc
molccule. The band with thc highcst wavcnumbcr is oftcn assigncd to the ЬСН
in the rcgion 1255 ::1: 55 сm 1 , with gaиcJ/e McOC( ==O)CHCI2 (131 О) and trallS
HC(==O)CHCI2 (1200 cm ') as cxtrcmitics. Тhe absorption rcgion of thc СН wag
(1215 ::1: 35 cm l) is limitcd Ьу FC(==O)CHCI2 (1248) and CI2CHCHCICHCl2
(1229 and 1184 cm 1).
11б Norlllal Vibraliolls alld Absorplioll Regiolls о/ СНХ2
CC12 strctching vibrations
The CCl 2 stretching vibrations provide two moderate (о strong, Ьи! cOl1formation
scnsitivc, absorptiol1s. Thc l/aCCl2 is observcd in thc rcgion 750 :1: 90 cm l with
а! thc HW side, HOC(==O)CHCI 2 (840 [30, 35] or 817 [З2]) and а! thc LW side,
McCHCl2 (б91 [12,13] or 707 [14]) and СDзСНСI2 (660 cm I). For most of thc
R CHCI2 moleculcs tl1is absorption lics in tl1e narrowcr region 765 :1: 65 сm I ,
Thc CCl 2 symmctric strctching vibration absorbs in thc cxtensive rcgion 680 :1:
100 cm 1, which diminishcs (о 705 :1: б5 cm 1 if somc 11igl1 valucs in the spcctra
of MC2NC(==O)CHCI2 (780), FC(==O)CHCI 2 (778) and NaOC(==O)CHCI 2 (777)
and lo\v valucs in thosc of aromatic bondcd dichloromcthyl (605 :1: 25 cm 1),
McCHCl 2 (б04) and HC(==O)CHCI 2 (tralls: 610; gallcJ/e: 630 cm 1) are 110t taken
into account.
CCl2 skclctal dcformations
Thc thrcc skclctal dcformations in 1,1-dichlorocthanc, which bclongs (о the point
group C s , arc arrangcd in ordcr of dccrcasing wavcnumber as follows: wCCI 2 (a')
> TCCI 2 (a") > bCC1 2 (a'). In morc complex molcculcs such as R C(==O)CHCI2
thc dcformation with thc lowcst wavcnumbcr is dcscribed as thc CCl2 rock or twist
(а").
High valucs for wCCI 2 havc Ьссп assigncd in thc spcctra of Cl2CHCHCI2 (54б
and 353) and CICH2CHCI2 (525 cm 1) and low valucs in those of CIC(==O)CHCI 2
(262) and McOC(==O)CHCI2 (262 cm 1), in which thc dichloromethyl group is
attachcd (о а carbonyl group.
For the sccond skclctal deformation, Cl2CHCHCl2 and CICH2CHCI2 also score
а! thc HW sidc with 333 cm 1 and CIC(==O)CHCI2 а! the LW side with 176
cm '.
For thc third skclctal dcformation, thc lowcst wavcnumbers havc Ьссп observcd
in thc spcctra of BrC(==O)CHCI 2 (151) and CIC(==O)CHCI2 (lбб cm 1) and are
assigncd to thc CCI2 rock (а").
The CCI 2 skclctal deformations are scnsitivc (о rotational isomerism. For the
wag, thc band scparations bctwccn tralls and gaucJle conformcr сап reach 100
wavcnumbcrs, and those for thc in planc dcformation and rock rarcly аЬоуе 50
wavcnumbcrs.
Torsion
Thc absorption rcgion of the torsion (lб5 :1: 130) narrows to 110 :1: 75 cm 1 if the
valucs 293 for McCHCl 2 and 274 cm 1 for СDзСНС12 are по! takcn into account.
4.1 DillOlogellometlzyl 117
ТаЫе 4.3 Absorption regions (cm J) of 'hc поrrnа] vibra'ions of CHCI2
С., Q satura'cd kc'o bondcd aromatic
I/СН а' 2995 ::1: 20 2990 ::1: 25 3005
ЬСН а' 1255 ::1: 55 1255::1: 55 1275::1: 25
wCH а" ]215::1: 35 1220::1: 30 1210::1: 10
l/ a CCI 2 а" 745 ::1: 85 775 ::1: 65 725 ::1: 45
I/ s CCI 2 а' 685 ::1: 85 695 ::1: 85 605 ::1: 25
w or bCCI2 а' 435::1: 115 340 ::1: 80 385 ::1: 25
15 or WCCl2 а' 285 ::1: 50 225 ::1: 50 зоо
Р or TCC I 2 а" 225 ::1: 60 190::1: 40 280
'orsion а" 170::1: 125 105::1: 70 115
R CHCI2 moleculcs
R = Mc [12 14], СDз [14], HOCH2 [3], CI2CHCH2 [15, lб],
CICH2 [13, 17 19], F2CH [б], CI2CH [13,20, 21], CICH2CHCl ,
CI2CHCHCl and CICH2CCI2 [15], СlЗССН2 , McCHCI ,
СlзССНСl , MeCCI2 and СlзСССI2 [22], FзС [23], СlзС [13],
McOCF2 [24], Ph [25, 2б], 2 , 3- and 4 FPh [27], HC(==O) [28],
FC(==O) [31, 4б], CIC(==O) [29 33], BrC(==O) [З1],
McC(==O) [З4], McOC(==O) [30, 32, 3б], HOC(==O) [зо, З2,
35], NaOC(==O) [32, 38], HSC(==O) [37], H2NC(==O) [11],
McHNC(==O) and MC2NC(==O) [32], SiХз (Х = Н, О, F, CI) [З9].
4.1.3 Dibromomethyl
The СН vibrations
The absorption rcgion of I/СН (3005 ::1: 20 cm 1) is boundcd Ьу McCHBr2 (3023)
and Br2CHCHBr2 (2985 cm 1).
Disrcgarding the low ЬСН (1143 cm l) for Iral/s Br2CHCHBr2 and thc high
СН waggings (1183 and 1172 cm 1) in thc spcctra of МсСНВr2 and trallS
BrCH2CHBr2, thc two absorption rcgions do по! overlap опс anothcr: БСН: 1235
::1: 45; wCH: 1135 ::1: 20 cm '.
CBr stretching vibrations
Disrcgarding the low valuc (620 cm l) in thc spcctrum of McCHBr2, thc l/aCBr2
occurs а! б85 ::1: 45 cm 1. Thc I/sCBr2 usually absorbs а! 575 ::1: 50 cm 1 with
thc cxception of опе of thc symmctric strctchings of tra//S-Вr2СНСНВr2 (б37 and
5В6 cm 1). Both stretching vibrations cxhibit strong bands but thcy arc sensitivc
to conformation.
118 Norтal Vibralio//s a//d Absorplio// Regio//s о/ СНХ2
CBr2 skelclal dсfоrшаtiопs
Тhc first CBr2 dcformalion or WCBr2 is oflen localcd in Ihe region 305 :!: 95 cm 1
with thc cxccplion of gallcl/e-Вr2СНСНВr2 (450 and 217 cm I).
Тhc sccond deformalion, absorbing in the range 205 :!: 45 сш 1, is oflen
dcscribed as bCBr2. TIIC value 275 сш 1 in the spcclrum of MeCHBr2, however,
is assigncd to thc CBr2 twiSI (а") and is oulsidc thc abovc-mcnlioned rcgion.
Thc third dcformation, wilh tlle lowcst wavenumbcr (155 :!: 45 cm I), is assigned
10 TCBr2, Ьи! in Ihc spcctrum of McCHBr2 (172 cm l) 10 bCBr2.
ТаЫе 4.4 Absorption regions (cm l) of thc поrrnаl vibrations of CHBr2
Vibration С . Rcgion Vibralion С . Rcgion
I/СН а' 3005 :!: 20 wCBr2 а' 330 :!: 120
ЬСН а' 1210:!: 70 b CBr 2 а' 220 :!: 55
,,-,СН а" 1150 :!: 35 TCBr2 а" 155 :!: 45
l/ a CBr 2 а" 675 :!: 55 'orsion а" 100:!: 65
I/ s CBr 2 а' 585 :!: 60
R CHBr2 molcculcs
R = Me [40], BrCH2 [41, 42], Br2CH [20, 43], N=C [44],
CIC(==O) and HSC(==O) [45], NaOC(==O) [З8].
References
1. G.A. Guirgis and G.A. Crowder, J. Flllorille С//ет., 25, 405 (1984).
2. О.С. Smith, R.A. Saundcrs, J.R. Niclsen and Е.Е. Fcrguson, J. C/lem. P//ys., 20, 847
(1952).
3. М. Рсrt'Шi, Spec/roclJim. Ас/а, Par/ А, 35А, 37 (1979).
4. У.Е Kalasinsky, Н.У. Anjaria and T.S. Litt1c, J. P/JYs. CI/eт., 86,1351 (1982).
5. Р. Кlaboe and J.R. Niclscn, J. С//ет. P//ys., 32, 899 (1960).
6. У.В. Kartha, S.B. Kartha and N.A. NаrаsirnhаП1, Proc.llldiтl Acad. Sci., 65А, 1 (1967).
7. J.R. Niclscn, Н.Н. Claassen and N.B. Moran, J. Cllem. P/,yS., 23, 329 (1955).
8. Р. Кlaboc and J.R. Niclscn,J. С//ет. P/,yS., 34,1819 (1961).
9. Р. Кlaboc, G. Ncerland and S.H. Schci. Speclroc//iт. Ас/а, Part А, 38А, 1025 (1982).
10. J.R. Barce10 and С. Otcro, Spec/rocl/im. Ас/а, 18, 1231 (1962).
11. О. Troitino, Е. Sanchcz de la Blanca and М.У. Garcia, Spec/rocIJim. Acta, Par/ А, 46А,
1281 (1990).
12. L.W. Oaasch, С.У. Liang and J.R. Niclscn,J. Clleт. P//ys., 22, 1293 (1954).
13. S. Suzuki and А.В. Ocmpsler, J. Мо/. S/rllc/., 32, 339 (J 976).
14. О.С. МсКеап, J.c. Lavallcy, О. Sau, H.G.M. Edwards and У. FawCC\l, Spec/roc//im.
Ас/а, Par/ А, 33А, 913 (1977).
15. А.В. Dcmps'cr, К. Price and N. Shcppard,Spectroc//im. Acta, Par/A, 27А, 1579 (1971).
16. М. Braalhcn, О.Н. Chris'cnscn, Р. Кlaboc, R. Scip and R. St01cvik, Ас/а C/lem. Scalld.,
Ser. А, 33А, 437 (1979).
17. S.O. Chrislian, J. Grundncs, Р. Кlaboe, C.J. Nic1sen and Т. Woldbaek, J. Mol. Strllc/.,
34,33 (1976).
4.2 /sopropyl
119
18. К. Kuratani and S.-I. Mizushima,J. Chem. PI/ys., 22,1403 (1954).
19. R.H. Harrison and К.А. Kobe,J. С//ет. P//ys., 26,1411 (1957).
20. G.W. Chantry, Н.А. Gcbbic, P.R. Griffi'hs and R.F. Flakc, Spec/roc/lim. Acta, 22, 125
(1966).
21. К. Nai'o, 1. Nakagawa, К. Kura'ani, 1. IchishiП1а and S.-I. Mizushima,J. Chem. P//ys.,
23, 1907 (1955).
22. А.В. Ocmpstcr, К. Pricc and N. Sheppard, Spec/roc/lim. Ас/а, Par/ А, 27 А, 1563 (1971).
23. J.R. Nielscn, с.У. Liang and О.с. Smilh, J. Chem. P//ys., 21, 1060 (1953).
24. Y.S. Li and J.R. Ourig, J. Мо/. S/rиc/., 81,181 (1982).
25. P.J.A. Ribciro-Claro and J.J.c. Tcixeira-Dias, J. Ramall Spec/rosc., 15, 224 (1984).
26. P.J.A. Ribciro-Claro, А.М. О'А Rocha Gonsalvcs and J.J.c. Tcixeira-Oias, Spec/rochim.
Ас/а, Par/ А, 41А, 1055 (1985).
27. S. Tariq and Р.к. Vcrma, Spec/rochim. ACla, Par/ А, 39А, 1027 (1983).
28. G. Lucazcau and А. Novak, J. Мо/. S/ruc/., 5, 85 (1970).
29. А. Miyaka, 1. Nakagawa, Т. Miyazawa, 1. Ichishima, Т. Shimanouchi and S. Mizushima,
Spec/roc//illl. Ас/а, 13, 161 (1958).
30. R. Faus'o and J.J.c. Tcixcira-Oias, J. Мо/. S/ruc/., 144,241 (1986).
31. A.J. Woodward and N. Jona'han,J. PI/ys. C/lem., 74, 798 (1970).
32. J.E. Ка'оп, Т.Н. S'out and G.G. Hcss, Appl. Spec/rosc., 40, 1 (1986).
33. J.R. Ourig, М.М. Bcrgana and Н.У. Phan,J. Мо/. S/rиc/., 242,179 (1991).
34. J.R. Ourig, J.A. Hardin and C.L. Тоl1еу, J. Mol. S/rиct., 224, 323 (1990).
35. L.M. Babkow, У.У. Vashchinskaya, М.А. Kovncr, G.A. Puchkovskaya and YU.Ya.
Fialkov, Speclroc/lim. Ас/а, Par/ А, 32А, 1379 (1976).
36. У. Mido and Н. Hashimoto, J. Мо/. S/ruc/., 131,71 (1985).
37. H.S. Randhawa and W. Walter, J. Мо/. S/rиc/., 38, 89 (1977).
39. 1.У. Kochikov, G.M. КurаП1shiпа, S.V. Syn'ko and Yu.A. PCnlin, J. Mol. S/rиc/., 172,
299 (1988).
40. J.R. Ourig, А.Е. Sloan, J.W. Тhompson and J.O. Witl, J. С//ет. PI/ys., 60, 2260 (1974).
41. S. Suzuki and G. Vergotcn, Spec/roc//im. Ас/а, Par/ А, 37А, 37 (1981).
42. Т. Torgrimsen and Р. Кlaboc, Асш C/le/1/. SC01ld., 24, 1145 (1970).
43. G.L. Carlson, W.G. Fatc'ey and J. Hiraishi, J. MoL Struct., 6, 101 (1970).
44. F. Wa'ari and К. Aida, Spec//'Oc/lim. Ас/а, Par/ А, 23А, 2951 (1967).
45. H.S. Randhawa, IlIdiШI J. C/lem., 19А, 152 (1980).
46. J.R. Ourig, М.М. Bcrgana and Н.У. Phan, J. RаlllШI Spec/rosc., 22,141 (1991).
4.2 ISOPROPYL
Molecules of typc МС2СНХ (Х = F, Cl, Br, 1) havc а plane of symmctry, \vhich
encloses the halogen, thc ccntral carbon and the sccondary hydrogcn. Тhcy bclong
to the point group C s . The 27 normal vibrations are distributcd among 15а' and
12а" spccies of vibration. Substitution of thc I/СХ (а') Ьу а torsion (а") rcsults in
27 normal vibrations for thc isopropyl group, which in thc casc of C S symmetry
are divided in 14а' and 13а" typcs of vibration:
а': l/аМс(2), I/sMe, I/СН, Ь а Мс(2), bsMc, ЬСН, рМс(2), I/sCC2, ЬСС 2 , skelctaI
dcformation and torsion Мс;
а": l/ а Мс(2), I/sMc, Ь а Мс(2), bsMc, ."СН, l/аСС2, рМс(2), skclctal dcformation,
torsion Ме and torsion СС 2 .
120 No/'//ral Vibтliolls alld AbsOl'plioll Regiolls о/ СНХ 2
The methyl stretching vibrations, as well as tllc П1еtllуl dеfоrшаtiопs and rocks,
сап Ьс in-phase or out of pIJasc movcmcnts, leading (о а' or а" vibrations.
Thc СН strctching vibrations
Thc scvcn СН strctc!Jillg vibrations absorb witll modcratc (о strong intensity,
but sсldош givc scparatc bands. The in phasc alld out of phase vibrations often
coincidc. Thc four mctllyl antisymmetric strctchings arc found bctween 3005 and
2935 cm l, but usually lowcr than зооо cm l схсер! for iPrF (3005), iPrCl
(3005), iPrBr (3003)) alld iPrN02 (ЗО03 cm 1). Both mcthyl symmetric stretching
vibratiolls absorb bcJwccn 2940 and 28БО cm l, or сусп betwecn 2920 and 28БО
cm 1 with thc exccption of iPrBr (2931), iPrNCO (2929), iPrCI (2927), iPrC(==O)F
(2927) and iPrNCS (2924 cm l). Thc СН strctching vibration рroЬаЫу occurs а!
2930 :!: 25 СП1 l.
Thc СН dcformations
The four mcthyl antisymmctric dcformations are active betwcen 1485 and 14ЗО
cm 1 with modcratc intcnsity. Thc а' and а" vibrations often coincidc, principally
thosc with thc highcst wavcnumbcr. Thc нw sidc is limitcd Ьу iPrC(==O)OMc
(148З), iРrС(==О)ОСDз (1482), iPr S iPr (1483) and iPrC(==O)Me (1482
cm l) and thc LW sidc Ьу iPrl (1430 cm 1). Thc rcmaining methyl antisymmetric
dcformations have Ьесп obscrved а! 14БО :!: 20 сm 1.
Sctting asidc thc high values for thc highest Ь"Ме in the spectra of iPrN02
(1400), iPrC(==O)F (1399), iPrC(==O)H (1395), iРrSiСlз (1393), iPrOC(==O)F
(1392) and iPrC=N (1391 cm 1) and the low valucs for the lowcst bsMe in thc
spcctra of iPrF (1354) and iРrСН(Мс)iРr (1351 and 1366 cm 1), most of the methyl
symmctric strctching vibrations have Ьссп observed bctwcen 1390 and 1360 сm 1 ,
Thc isopropyl group is bcst recognizcd Ьу thc two moderate to strong absorptions
with about cqua1 intensity of bsMc, oftcn named as а 'symmetrical doublet'.
With the cxccption of Si and P isopropyl (1290 :!: 15 cm 1) the а" СН
dcformation (mcntioned as /,СН but also as ЬСН) is assigncd а! 1320 :!: 30 cm 1.
The а' ЬСН appcars usually in thc region 12б5 :!: З5 cm t, but in the spcctrum of
iPrl а! 1210 cm 1.
Skelctal stretching vibrations and mcthyl rocking vibrations
In the rangc 119 7б5 cm ' four mcthyl rocks and two СС2 skelcta1 stretchings
arc obscrvcd, wcll scparatcd from cach othcr and mostly with а weak to modcrate
intcnsity.
Thc highcst in-phasc mcthyl rock а! 1170 :!: 20 cm 1 is а good group vibration.
lп the spectra of iPrNH2 (1177), iPrPF 2 (11б8) and iPrPC12 (1165) and iPrSH
(1162 cm I), howcvcr, this absorption is assigned (о the l/аСС2.
4.2 /sopropyl
121
Tlle СС2 antisymmetric strctching vibration is usually sccn а! 1115 :1: 45 cm 1 ,
а wavcnumbcr that in the abovc mcntioncd cascs is assigncd to а mcthyl rocking
vibration. Disregarding the valucs 1159 and /123 in thc spcctrum of iPrCH(Mc)iPr,
1080 in that of 2 HO Ph iPr and 1085 :1: 15 cm 1 in thosc of Si and P-bondcd
iPr, this region is reduced to 1125 :1: 25 cm l.
The second in phasc mcthyl rock is usually located in thc rcgion 1080 :1: 40
cm l, with the exception of iPrSCN (1130), iPrCH(Mc)iPr (1038 and 1076) and
iPrNH2 (103б cm I). In the spcctra of iPrC(==O)X (Х = Н, Cl, F, ОМс) this
absorption is strongly influenccd Ьу the l/ а СС2.
The highcst out of phase methyl rock mау Ьс assigncd а! 970 :1: 30 cm '. А
shift to higher frcqucncies occurs whcn thc mcthyl group is attachcd to Si or Р
(1010 :1: 15 cm l) and а small shift to lowcr frcqucncics in the spcctra of iPrl
(937), iPrOMe (938) and iPrSCN (938 cm 1).
The sccond out of phasc mcthyl rock сап Ьс found in thc rangc 930 :1: 20 cm 1
if some higher values in the spcctra of Si and P bondcd isopropyl (945 :1: 30
cm 1) and in that of iPrC(==O)Me (952 cm l) arc по! takcn into accaunt.
The СС2 symmetric strctching vibration is rcportcd in thc extensivc region 835
:1: 70 cm ', which is reduced to 855 :1: 40 cm l Ьу ncglccting thc cxtrcmc valucs
in the spcctra of iPrCH20C(==O)CH2C=N (905), iPrNCO (903), iPrC=N (7б9),
iPrC(==O)F (780) and iPrOMc (800 cm 1).
Skcletal dcformations
The СС2 in planc deformation providcs а wcak band in thc rangc 450 :1: б5
cm 1 but most of these skclctal bendings havc Ьссп obscrvcd а! 440:1: 40 cJп '.
The following compounds are rcsponsibIc for thc widc sprcad: iPrC=N (510),
iPrC(==O)F (486), iPr CH==N iPr (483 and 40В), iPrl (398), iPrSH (39б),
iPrN02 (387) and iPrC(==O)D (385 cm 1).
The vibrational analysis of isopropyl compounds revcals anothcr two skclctal
dcformations: а C C R in planc dcformation or СС 2 wag (а') and а C C R
out of planc deformation or СС2 twist (rock). Thesc morc cxtcrnal dcforrnations
are often wcakly active а! 3БО :1: 50 and 320 :1: 45 cm l with thc cxccption of
iPrBr (290 and 282) and iPrl (270 and 250 cm I), which arc influcnccd Ьу the
heavy halogen.
The following R iPr compounds havc Ьссп takcn into account:
R = CIMe2CCH2 and CIMc2CH2CH2 [1], McCHCICH2 and
McCHBrCH2 [2], PhCH2 [58], HC=CCH2 [3],
McNHC(==O)NНCH2 , EtNHC(==O)NНCH2 , nPrNHC(==0)NНCH2 ,
nBuNHC(==O)NHCH2 and iBuNHC(==O)NHCH2 [4],
cHexNHC(==O)NHCH2 [5], N=CCH2C(==O)OCH2 , McSCH2 [6],
CICH2 [7 10], BrCH2 [9 11], iРrСН(Мс) and EtCHMcCHMc
[12], cPr [13], CIMc2C [1], Ph [58], 2 , з and 4-МсРh [58],
2 , з and 4 iPrPh [58], 2 , з and 4 HOPh [58], HC(==O) [14,
1п
O OO OO O OO OO OOOO
OO OOO OO OOOO M . OM
OO . MM O OO MMM
MMMMMMM
z
OO O OO O O OO OOOOO
]
8 И
OO...VMMMN O OO.MMNN
MMMMMMM
О
OOOOOO OO OOO O O
MMMM.
п
OOOO OO O O O
OO V OO VOONV N
= SS OO.MMN
]
] й
.;
OOOO OOOO O OO OOOOOOO
NNNN N NV M MVNNM
Z п
g
MMMMMMM
о
SS
R
OO O OO O O OO OO
OOOO M OO OO NOO NOO M M IV
OOOOVVVVMMMN O OO MMN
MMMMMMM
и
I ]
К
и
с
О
. О
. 11
t u
<
F
ooaooooooo oo cocoo o
NN NN N N N N
п
oo ooooo ooo ooo
g
MMMMMMM
u coooo ooooo 00
Е c N V N
OOOO OOO S *
O OO
oo v =
NNNNNNN
u
и
OOOO OOOOO OOOOO O
NNNN N N NN N NNv
oooooooo oo oo o c o
ooOO OO OO NOO N v N
ooOO V V MN O OO M NN
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..... ........... ... ..... .. ........
g . . g
. : ИИ
: UVVU UVUUVVU а arl g .
U OO U U :
4.2 /sopropyl
123
15], OC(==O) [14], McC(==O) [16], 2 HOPhC(==O) [17],
FC(==O) [18], CIC(==O) (19], McOC(==O) and СDзОС(==О)
[20], HO [21, 53], McO [22, 23], ЕtO [22], iPrO [22, 23],
FC(==O)O [24], O==N O [25, БО], 02NO [БО], HS [26---
28], DS [28], McS [26, 29, 30], EtS [2б, 31, 32], nPrS and
nBuS [31], iPrS [2б, 31), iPrSS [2б], NCS [33, 34],
H2N [35, З6], D2N [35], McNHC(==O)NH , EtNHC(==O)NH ,
nPrNHC(==O)NH , nBuNHC(==O)NH and iPrNHC(==O)NH [4],
cHcxNHC(==O)NH [5], R S02NH [З7], iPr CH==N and
iPr CD==N [36], OCN [З8, 39], SCN [40--42], 02N [4З],
МсзSi , CIMe2Si , CI2McSi and СlзSi [4б], H2P and 02P [59],
F2P [44], CI2P [45], F [47 50], CI [51 5З, 61], Br [52 54],
I [52, 53], N=C [52, 53, 55 57].
References
1. G.A. Crowder and М.Т. Richardson, Spectroc/lim. Ас/а, Par/ А, 38А, 1123 (1982).
2. G.A Crowdcr and R.M.P. Jaiswa1, J. Mol. S/rllc/., 99,93 (1983).
3. G.A. Crowder, J. Мо/. S/rllc/., 193,307 (1989).
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5. У. Mido. Spec/roc/lim. Acta. Part А, 32А, 1105 (1976).
6. N. Nogami, Н. Suge'a and Т. Miyzawa, 8,,11. CI/eт. Soc. Jpп., 48, 2417 (1975).
7. G.A Crowder and W.-L. Lin, J. Мо/. Str"c/., 64, 193 (1980).
8. А J.Bamcs, M.L. Evans and Н.Е. Наl1аm, J. Мо/. Strllct., 99, 235 (1983).
9. J.R. Ourig, J.F. Sullivan and S.E. Godbcy, J. Мо/. S/rllc/., 146,213 (1986).
10. N.т. Oevitt, A.L. Rozek, ЕЕ Bentlcy and А.О. Oavidson, J. C/lem. P/,yS., 42, 1173
(1965).
11. G.A. Crowder and M.-R. Jalilian. Spec/roc/liт. Ас/а, Рат/ А, 34А, 707 (1978).
12. G.A. Crowder and L. Gross,J. Мо/. S/rиc/., 118, 135 (1984).
13. АВ. Neasc and C.J. Wurrcy, J. Raтaп Spec/rosc., 9, 107 (1980).
14. А Piart-Goypiron, М.Н. Baron, J. Вс110С, M.J. Coulangc and Н. Zinc, Spec/roc//i/1/.
Асщ Par/ А, 47А, 363 (1991).
15. J.R. Ourig, G.A. Guirgis, W.E. Brcwer and т.s. Lillle, J. Мо/. S/rиc/., 248, 49 (1991).
16. Т. Sakurai, М. Ishiyama, Н. Takcuchi, К. Takeshita, К. Fukushi and S. Konaka, J. MoL
S/rllc/., 213, 245 (1989).
17. W.А.L.к. AI-Rashid and М.Е EI-Berrnani, Spec/rocllim. Acta, Par/ А, 47А, 35 (1991).
18. J.R. Ourig, G.A Guirgis, W.E. Brcwer and G. Baranovic, J. PI/ys. C/lem., 96, 7547
( 1992).
19. G.A. Guirgis, Н.У. Phan and J.R. Ourig, J. Мо/. S/r"c/., 266, 265 (1992).
20. R.M. Moravie and J. Corsel,J. Мо/. S/r"ct., 24, 91 (1975).
21. L.I. Lafcr, V.I. Yakcrson and G.A. Kogan, 8,,11. Sci. Acad. U.S.S.R. (Div. Chem Sci.),
8, 1717 (1969).
22. R.G. Snyder and G. Zcrbi, Spectroc/rim. Ас/а, Par/ А, 23А, 391 (1967).
23. АО.Н. Clague and А Oanli, Spcc/roc/lim. Ас/а, Par/ А, 24А, 439 (1968).
24. B.J. Уап dcr Veken and Н.Н. Licfooghc,J. Мо/. S/r"ct., 247, 257 (1991).
25. B.J. Уап der Vckcn and R. Maas, J. Мо/. S/rllc/., 200. 413 (1989).
26. O.W. Scott and J.P. McCullough, J. А/1/. C/lem. Soc., 80. 3554 (1958).
27. О. Smith and J.P. Oev1in, J. Мо/. SpeCIrOsc., 25, 174 (1968).
124 Normul Vibтlio//s атl AbsOIplio// Regio//s о/ СНХ 2
28. J.R. Ourig, G.A. Guirgis and О.А.С. СОП1рtоп, J. P/,yS. С//ет., 84,3547 (1980).
29. М. Oshak\l, У. Shiro and Н. M\lfata, B//II. С//ет. Soc. JplI., 45,3480 (]972).
30. J.P. McC\lllough, H.L. Fil1kc, J.F. Mcsserly, R.E. PCllllington, I.A. Hossenlopp and G.
Waddington, J. Ат. C/lem. Soc., 77, 6119 (1955).
31. М. Ollsak\l, Н. M\lfala and У. Shiro, SpeclroclJim. Ас/а, Part А, 33А, 467 (1977).
32. М. Sakakibara, 1. Harada, Н. Matsuura and Т. SlliП1аПО\lсhi, J. Мо/. Slrllct.,49, 29
(1978).
33. R.P. Hirschmann, R.N. Knisclcy and У.А. Fasse1, Spectroc//im. Ас/а, 20, 816 (1964).
34. G.A. Cro\vder, J. Мо/. S/r//c/., 7, 147 (1971).
35. J.R. O\lfig, G.A. Guirgis and О.А.с. СОП1рIОП, J. PI,ys. С//ет., 83, 1313 (1979).
36. А. Piart-Goypiron, М.Н. Baron, Н. Zine, J. Всllос alld M.J. Coulangc, Spec/roc//im.
ACla, Par/ А, 49А, 103 (1993).
37. М. Goldstcin, М.А. Russe1 and Н.А. WiIlis, Speclroc//illl. Ас/а, Par/ А, 25А, 1275
(1969).
38. J.R. O\lfig, K.J. Kancs and J.F. Sullivan, J. Мо/. S/rиc/., 99,61 (1983).
39. R.P. Hirschmann, R.N, Кnisclcy and У.А. Fasse1, Spec/roc/lilll. Acla, 21, 2125 (1965).
40. R.N. Кnisclcy, R.P. Hirschmann and У.А Fasse1, Spec/rocllilll. ACla, Part А, 23А, 109
(1967).
41. J.R. Ourig, J.F. S\llIivan, T.S. Litt1e and S. Cradock,J. Мо/. S/r//ct., 118, 103 (1984).
42. J.R. O\lrig, J.F. Sullivan, О.Т. O\lfig and S. Cradock, Call. J. С//е1ll., 63, 2000 (1985).
43. J.R. O\lrig, J.A. SП100tеr SП1i'h, Y.S. Li and ЕМ. Wasacz,J. Мо/. S/ruc/., 99, 45 (1983).
44. J.R. Ourig, M.-S. Cheng, Y.s. Li, Р. Grower and АЕ. Slanley, J. P/,yS. C/lem., 93, 3492
(1989).
45. J.R. Ourig, M.-S. Chcng, М.Е. Harris and T.J. Hizer,J. Mol. Strllct., 192,47 (1989).
46. К. Ohno, К. Taga, 1. Yoshida and Н. Murala, Spec/roc/lim. ACla, Par/ А, 35А, 883
(1979).
47. J.H. Griffilhs, N.L. Owen and J. Shcridan, J. С//е1ll. Soc. Faraday Tra//s. 2, 9, 1359
(1973).
48. G.A. Crowdcr and Т. Koger, J. Мо/. S/rllc/., 23, 311 (1974).
49. G.A. Cro\vdcr and Т. Koger,J. Мо/. S/rllc/., 29, 233 (1975).
50. J. Gustavsen and Р. КJaboe, Spec/roc//illl. АС/а, Part А, 32А, 755 (1976).
51. C.G. Opaskar and S. Кrimm, Spectroc//illl. Ас/а, Part А, 23А, 2261 (1967).
52. Р. Кlaboe, Spec/rocllim. Acta, Part А, 26А, 87 (1970).
53. J.R. Ourig, с.М. Playcr Jr., Y.S. Li, J. Bragin and C.W. Hawley, J. C/lelll. P/,yS., 57,
4544 (1972).
54. Р. Кlaboe, А. Linde and B.N. Cyvin, Spec/rocIIilll. Acta, Part А, 30А, 1513 (1974).
55. R. Yamadara and S. К:rimm, Spec/roc//illl. Acta, Part А, 24А, 1677 (1968).
56. B.N. Cyvin and S.J. Cyvin, Acla С//е/1/. Scalld., 26, 3943 (1972).
57. 0.А.с. Compton and W.F. Murphy, Speclroc//illl. ACla, Part А, 41А, 1141 (1985).
58. G. Varsanyi, Assigllllle1lts /or Vib,'a/iolla/ Speclra о/ Sevell HIII/(/red Bellzelle Deriva/ives,
J.Wiley & Sons, Ncw York (1974).
59. J.R. Ourig and A.W. Сох Jr., J. P//ys. С//ет., 80, 2493 (1976).
60. R. Maas, Thesis, ША, Antwcrp, 1992.
61. J.F. Sullivan, А Wang, M.-S. Chcng and J.R. Ourig, Call. J. С/,е1ll., 69, 1845 (1991).
5
Normal Vibrations and
Absorption Regions of СНХ
5.1 НALOGENOMETHYLENE
Тhe 27 normal vibrations of Mc CHX Mc arc divided, according to С .
symmetry, into 15а' vibrations, of which ninc arc for thc mcthyl group, опс СС2
symmetric stretch and опс СС 2 deformation, and 12а/I vibrations: ninc mcthyl
vibrations and опе СС 2 antisymmctric strctch. Six fundamcntal vibrations (4а' +
2all) bclong to the CHX group:
а': I/СН, I/СХ, ЬСН, ЬСХ;
all: wCH and wCX.
although the СХ vibrations arc influenced Ьу thc skclcton of thc compound. In less
symmctrical molecules thc differcntiation bctwccn а' and а/I disappcars.
5.1.1 Fluoromethylene
Тhe absorption regions of CHF are dcduccd from 2 fluoropropanc do, dз and -d 6
and 2 fluorobutane and thcrefore по! cntircly rcprcscntativc Ьи! only indicativc.
The СН vibrations are active in the regions of thosc of thc СНСl group Ьи! thc CF
vibrations absorb а! considerabIy highcr frequencics.
R CHF R' molccules
R R'
Mc Me (1--4], E! [З], СDз [49];
СDз СDз [4].
] 2б NO/'/lIal Vibraliolls alld AbsOl'plioll RegiollS о/ сих
5.1.2 Сhlоroщеthуlепе
Tlle СН vibrations
Other mctllyl and/or methylcne vibrations somctimcs cover tlle СН stretching
vibration in the rangc 2940 :1: 40 cm '. Tlle weak to moderate Ьапd in tlle region
1330 :1: 50 cт t is due to the СН out-of plane deformation. Tlle limits arc found
in thc spcctra of Me(CHCl)2Me (11': 1З57 and 1289; g: 1З79 and ВОЗ) and in
that of McCHCICH2CHCIMc (1379 and 1325 cm 1). This deformation is often
obscrved а! 1340 :1: 25 cm '. Thc СН in planc deformation cxhibits а moderate
to strong band in the range 1245 :1: 45 cm 1.
ССl vibrations
Thc most charactcristic absorption is thc moderate to strong band а! 650 :1: БО
cm 1, duc to thc C Cl strctch. Thc conformcrs of 2,3 dichlorobutane provide thc
limits: 70б and 597 cm 1. Thc first ССl dcformation, attributed to the bCCI, is
wcakly to modcratcly activc а! 345 :1: 55 cm l. The second is assigned to wCCl
or 'УСС1 and absorbs wcakly to moderatcly а! 280 :1: 50 cm 1.
СDз
Et
CICH2
CI2CH
R CHCl R' molcculcs
R R'
Me Mc [5 ], E! [8 11], iВи [12], CH2CI [13 15], СН2ССlз
[1б], CH2CHCIMc [10], CHCI2 [13], CHClMe [17, 18],
CHCICHCIMe [18], CCI2Me [19], C(==O)CI, C(==O)OMc
[20], C(==O)OE! [21], CH==CH2 [22,48];
СDз [7];
E! [10], CH2Cl [15], СН2ССlз [lб];
CH2Cl [23, 24], CHCI2 [23], ССlз [13], CHCICH2CI [25];
CHCI2 [23], ССlз [13].
5.1.3 Bromomethylene
Thc СН vibrations
Thc СН strctching vibration providcs а wcak to modcratc band in thc rangc 2940
:1: 40 cm l, in which also mcthyl and mcthylene are active. Thc СН out of plane
dcformation gives risc to а wcak to modcratc band а! 1340:1: З5 cm 1 and the СН
in-planc dcformation absorbs modcrately to strongly а! 1240:1: 40 cm l.
Thc CBr vibrations
Thc CBr stretching vibration occurring in the rcgion 545 :1: 75 cm 1 provides thc
most charactcristic absorption. Thc intensity varics from modcrate to strong and the
5.2 Cyallomethyle"e
127
band is generally sensitive to conformation. N=CCHBrC(==O)NH 2 (б20) absorbs
а! the HW sidc and McCHBrC(==O)OEt (475 cm l) а! thc LW sidc. Most of thc
compounds SllOW this I/CBr а1 550 :!:: 50 cm 1. Тhc in-planc and OU1-of-planc CBr
dcformations are observcd rcspcctivcly in thc rcgions 300 :!:: БО and 230 :!:: б5
cm 1.
R CHBr R' molccules
R R'
Me Me [б 8, 26], E! [8, 9], iВи [12], CH2CI [14], CH2Br [14,
15, 27], СН2ССlз [1б], CHBrMe [28], C(==O)CI, C(==O)Br,
C(==O)OMe [20], C(==O)OE! [21];
СDз [7, 2б];
CH2Br [15];
СН2ССlз [16];
CH2Br [24];
C(==O)NH2 [29].
СDз
Et
tBu
BrCH2
N=C
5.2 СУАNОМЕТНУLЕNЕ
Thc 30 normal vibrations of а simplc compound such as McCH(CN)Me arc dividcd
over 17а' and 13а" typcs of vibration. Aftcr dcducting 11а' and 10ЗIl vibrations,
ninc vibrations for the CH(CN) fragmcnt rcmain:
а': I/СН, vC=N, БСН, I/C CN, b C CN, bC C=N;
all: wCH, 'Y C CN and 'YC C=N.
Тhe СН vibrations
The СН vibrations cover almost the samc rcgions as thosc of the R CНX R'
(Х = F, Cl, Br) compounds: I/СН 2940 :!:: 40, ""СН 1345 :!:: 30 and ЬСН 1250 :!::
50 cm 1.
Тhc C=N stretching vibration
Тhc C=N stretch (2250 :!:: 15 cm 1) is thc most characteristic band and а good
group vibration, but the intensity lcavcs much to Ьс desircd.
Skcletal vibrations
Тhc skclctal vibrations are couplcd with othcr vibrations, and the numbcr of
invcstigated molecules is too small to dcducc uscful absorption rcgions. Тhc
following regions are only indicativc:
128 Noттl Vib/'Qlio"s a"d Absorplio" Regio"s о/ СНХ
I/C CN bC C CN "YC C CN
810 :1: 80 495:1: 45 380 :1: З5
"YC C=N
325 :1: 45
bC C=N
175:1:45
R СН(СN) R' molcculcs
R R'
Me Mc [6, 7, 3()"",32], CH==CH2 [32];
Cl(CH2)3 Ph 4 Br;
Ph СН(СN)Рll [33];
Br C(==O)NH2 [29].
5.3 HYDROXYMETHYLENE
МеСН(ОН)Ме cxhibits in the sterically favourcd C s structure 17а' and 13а1'
vibrations. Тhc mcthyl groups are responsiblc for 9з' and 9а" vibrations and the
СС2 skelcton takes 2а' and 1а" vibrations for itself. The following vibrations belong
to the CH(OН) unit:
а': 1/0Н, I/СН, ЬОН, ЬСН, I/СО, ЬСО;
а": wCH, "УОН and "УСО,
Тhe ОН vibr3tions
Тhc ОН stretching vibr3tions in associated molecules show а broad, strong band in
thc rcgion ЗЗ70:l: 30 cm '. In dilute solutions the free ОН absorbs sharply in the
neighbourhood of 3БОО cm ', Тhe associated ОН in planc dcformation gives risc
to а weak Ьи! broad 3bsorption in thc rangc 1400 :1: 30 cm 1 зпd is coupled to
wCH. In dilutc solutions this band shifts to 1280 :1: 30 cт ' [44--47]. The out of
planc dcformation is assigncd in thc rcgion б30 :1: 30 cm 1 зs 3 broad band with
modcratc intcnsity. In thc unbonded statc this Ьroзd band disappcars and returns
as а frcc torsion а! 280 :1: 50 cm ' [41].
Тhe СН vibrations
Тhe weak bands of thc СН vibrations occur in nearly the sзmе regions as the СН
vibrations of methyl and methylene: I/СН 2940 :1: 40, wCH 13б5 :!: 35 зпd ЬСН
1320:1: 30 cm 1.
Тhc СО vibrations
Aftcr the ОН strctching vibration, thc СО stretch is the most charactcristic
absorption of the CH(OH) fragment. Тhis vibration absorbs in secondary
5.3 Hydroxyтe/hyleпe
129
alcohols in the region 1110:1:: 30 cm ' with а modcratc (о slrong intcnsity, that
is, higller than in primary alcohols (1045 :1:: 45) [43]. Тhis band oftcn shows
multiple minima because of the coupling with 1hc СС2 strctching vibration and
the methyl rock. Оп dilution, the association with thc ОН dcformation is rcmovcd
and this band shifts 10 lower wavcnumbcrs. In unsaturatcd sccondary alcohols of
(уре R СН(ОН) СН==, the I/СО absorbs а! 1050:1:: 30 cm l, in thc middlc
of the region of primary alcohols. Тhc СО in-plane dcformation appcars wcakly а!
аЬои! 470 :1:: 30 cm l and the out of planc counterpart is а littlc strongcr in the
rcgion 360 :1:: 30 cm l.
R СН(ОН) R' molecules
R R'
Me Me [34), Et, tBu, СFз [35, 3б), cPr [37], CH2C02 [38);
Et C02 [38];
FзС СFз [39--41], ССlз [42);
Ph СН(Ме)NН2 [50).
ТаЫе 5.1 Absorplion regions (cm l) оС Ihc поrrnаl vibrations оС R CHX R' (Х = F, Cl, Br,
CN, ОН)
Vibration С . CHF CHCI CHBr CH(CN) CН(OН)
1/0Н а' 3370:1: 30
I/СН а' 2930 :1:: 10 2940 :1:: 40 2940 :!: 40 2940 :!: 40 2940 :1: 40
I/C=N а' 2250 :!: 15
ЬОН а' 1400 :!: 30
""СН а" 1340 :1:: 15 1330 :1:: 50 1340 :!: 35 1345 :!: 30 1365 :!: 35
ЬСН а' 1260:1:: 20 1245 :1:: 45 1240 :!: 40 1250 :!: 50 1320 :1: 30
I/СО а' 1110:!:30
I/CF а' 955 :1:: 15
vC CN а' 810 :!: 80
I/ССI а' 650 :1:: 60
,ОН а" 630 :!: 30
I/CBr а' 545 :!: 75
bC C CN а' 495 :!: 45
ЬСО а' 470:!: 30
bCF а' 420 :1:: 20
,C C CN а" 380 :!: 35
,СО а" 360 :1: 30
6ССl а' 345 :1:: 55
,C C=N а" 325 :!: 45
6CBr а' 300 :1:: 60
""CF а" 370 :1:: 20
""СС! а" 280 :1:: 50
""CBr а" 230 :1:: 65
bC C=N а' 175 :!: 45
130 Normal Vibтlio//s a//d AbsOIplio// Regio//s о/ С/-/Х
References
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20. R. Oas and SK Nandy, IlIdiall J. P/,yS., 52В, 85 (1977).
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30. R. Yamadcra and S. Кrimm, SpectrocIIim. Ас/а, Part А, 24А, 1677 (1968).
31. B.N. Cyvin and S.J. Cyvin, Acla С//еl1l. Scalld., 26, 3943 (1972).
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5.3 Hydroxyтelllyleпe
131
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6
Normal Vibrations and
Absorption Regions of СХ 2
Just like СН 2 , the СХ2 fragment displays six fundamental vibrations. R CX2 R'
compounds in \vhich R is identical to R' сап bclong to the point group С2У' In this
case the six normal vibrations arc divided into 2аl + а2 + 2ы1 + Ь2 species in which
Ь 1 and Ь 2 сап Ье exchanged according to the choice of the symmetry plane. For
compounds in which R differs from R' the а, and Ь 2 vibrations cl1ange into а' and
the а2 and Ь 1 vibrations changc into а" if the moleculc belongs to the point group
C s . Thc following vibrations are considcred as inherent in the CX2 struc1ure
unit:
l/аСХ2 (Ь 1 )(а"), I/sCX2 (al)(a'), БСХ 2 (а1)(а'), wCX 2 (Ь 2 )(а'), РСХ2 (Ь))(а"), ТСХ2
(а2)( а").
6.1 DIFLUOROMETHYLENE
The CF 2 strctching vibrations
The CF2 fragment gives rise to two strong bands: l/ a CF 2 (1195 :1:: 85) and
v s CF 2 (1130 :1:: 70 cm 1). The broad region of the antisymmetric slretch is due
to thc low values in thc spec1ra of CF2I2 (1110), CF2Br2 (115З), CF2Cl2 (1167)
and FзССF2I (1161 cm 1). Thc molccules CF2I2 (1067) and CICF2CFCl2 (1087
cm l) arc rcsponsibIc for thc lowcst va1ues of the symmetric stretch. For most of
the diftuoromcthylene compounds the regions are more attractive: l/aCF2 а! 1225
:1:: 50 and I/ s CF 2 а! 1150:1:: 50 cm '.
Thc CF 2 dcformations
The CF2 scissoring vibration is situated in thc broad rcgion 520 :1:: 155 cт 1
as а moderate to strong band. The moleculcs N=C(CF2)C=N (tralls: 650; galtc/le:
Norтal Vibralioпs aпd Absorplioп RegiollS О[СХ 2 13З
671 cm l) and C1CF2NO (644 cm )) take carc ofthc uppcr limit, апdFзССF2Х (Х
= Br and 1) and CF2Br2 wi1h 367 cm 1 kecp thc lowcr limit. Тhcrc is а considcrabIc
chance of finding these CF 2 scissors in thc rangc 510 :f: 70 cm 1. Тhc couplcd
vibrations CF2 wag, CF 2 rock and CF 2 1wist arc classificd in thrcc largc rcgions
which are reduced (о:
""'СР2: 415 :f: 85; pCF2: 375 :f: 65 and TCF 2 : 295 :f: б5 cm 1
if thc extreme values in the spectra of thc compounds in ТаЫс б.l arc по! takcn
into account.
ТаЫе 6.1 CF2 dcformalions
"", CF 2
tralls-МеСF2СН2Сl
ga/lclle MeCF2CH2Cl
McOCF2CHCI2
ga/lclle N ==CCF2CF2 C==N
СFзСF2СI
СFзСF2Вr
СFзСF21
515
508
526
523 and 484
362
332
300
pCF2
428
428
375
469 and 364
316
298
262
358
325
313
280 and 238
183
154
133
TCF2
R CF2 R' molecules
R R'
Mc Me [1, 2], CH2CI [3], Cl and Br [4];
(CF2CH2)".-iСН2СF2)" [5];
FзС СFз [б, 7], Cl, Br and I [8], C(==O)OH [9J, C(==O)OR
[10] (R = Ме, Et, nPr, iPr, пВи, iВи and nPcnt);
N==C C==N [12], CF2C==N [13];
McO CHCI2 [11];
CI CFCI2 [14], N==O [15], Cl [16---18];
Br Br [17];
I I [19],
6.2 DICHLOROMETHYLENE
Тhc CCl2 stretching vibrations
AJthough thc absorption rcgions ovcrlap cach othcr, the CCI2 stretching
vibrations are obscrved as moderate to strong scparatc bands. Thc largc rcgion of thc
antisymmetric stretching vibration is produced Ьу compounds such as FCCI2F (920)
and FзСССl2СFз (912 cт ) оп the опе sidc and McCCl2CHCl2 (б40 or б9б),
Iraпs McCC12Et (б45) and DзСССl2СDз (БОО cт l) оп thc othcr sidc. Extrcmc
valucs for thc symmetric stretch arc found in thc spcctra of 02NCCI2N02 (7б2),
134
6.3 Dibrol1lol1lell/ylelle
gallclle McCCl2CCl2Me (722 and 565), Iralls-МеССl2Еt (545) and DзССI2СDз
(52б cm I). Most of the R CCI2 R' compounds display these stretcl1il1g
vibrations in tlle rcgions l/aCCI2: 755:1: ]00 and //sCCI 2 : 620:1: 70 cm l.
Tlle CCI2 dcformations
Тhc CCl 2 dсfоrП1аtiопs arc obscrvcd in four regions whicll overlap eacll other.
Disregarding the high valucs in the spectra of CCI2F2 (wag: 465 and rock:
435), N=CCCI2C(==O)NH2 (\vag: 494 and twist: 37б), FCCl 2 CF 2 CI (wag: 440)
and N=CCCI 2 C=N (wag: 440 cm 1) and the values assigned for gallclle
McCCI 2 CCI 2 Mc (wag: 428 and 365; rock: 288 and 249 and twist: 245 and 238
cm 1), thc rcgions Ьссоmе much morc attractivc:
wCCI 2
380 :1: 40
p CCI 2
340 :1: 40
bCCI 2
250 :1: 40
TCC I 2
300 :1: 40
R CCI2 R' molcculcs
R R'
Mc Mc [20---25], E! [22, 25 28], CHCI2 [29], CCI2Me [30], F
[З1];
СDз [21];
CH2CI [32, 33], CHCI2 [32];
ССlз [29];
СFз [б];
C=N [34, 35], C(==O)NH2 [3б];
N02 [37];
CF2Cl [14], N==O [15], F [11).-..18];
N==O [15].
DзС
C]CH2
CI2CH
FзС
N=C
02N
F
Br
6.3 DIВROMOMETHYLENE
Thc CBr2 strctching vibrations
The CBr2 strctching vibrations appcar modcrately to strongly in thc rcgions:
l/aCBr2 б50 :1: 70 and I/sCBr2 530 :1: 50 cm l. Тhc high values assigned in the
spcctra of CF2Br2 (I/ а : 8З1 and I/s: б23) and СFзСВr2СFз (I/ а : 850 cm 1) are
outsidc thc abovc mcntioncd rcgions.
Тhe CBr2 dcformations
19noring, without rcjecting, thc high valucs for WCBr2 in the spcctrum of
N=CCBr2C(==O)NH2 (447) and for bCBr2 in that of McCBr2Et (258 cm 1),
thc CBr2 deformations arc expcctcd in thc regions:
Normal Vibratiolls QlId Absorplioll Regiofls о/ СХ2 135
ЗБО :J: 40
pC Br 2
320 :J: 30
TCBr2
250 :J: 40
bCBr2
180 :J: 30
WC Br 2
R CBr2 R' moleculcs
R R'
Mc Mc [20, 24], Et[39], CBr2Mc [38];
FзС СFз [6];
N=C C=N [34, 35], C(==O)NH2 [3б];
F F [17];
Cl NO [15].
ТаЫе 6.2 Absorption rcgions (cm 1) of 'hc поrrnаl
vibrations of CX2 (Х = F, СI and Br)
Vibration CF2 CCI2 CBr2
l/ a CF 2 1195 :J: 85
I/ s C F 2 1130 :J: 70
l/ a CCI 2 760 :J: 160
l/ a CBr 2 650 :J: 70
I/ s CC1 2 645 :J: 120
I/ s CBr 2 530 :J: 50
bCF2 520 :J: 155
WCF2 415 :J: 115
WC Cl 2 418 :J: 80
wCBr2 385 :J: 65
p CF 2 365 :J: 105
p CCI 2 340 :J: 95
p CBr 2 320 :J: 30
TCC l 2 305 :J: 75
БССl2 250 :J: 40
TCBr2 250 :J: 40
TCF, 245 :J: 115
ЬСВ;2 205 :J: 55
References
1. G.A. Crowdcr and О. Jackson, Spec/roc//im. Acla, Par/ А, 27А, 2505 (1971).
2. J.R. Ourig, G.A. Guirgis and Y.S. Li, J. Cllem. P/,YS., 74, 5946 (1981).
3. G.A. Crowdcr, J. Мо/. S/rtlc/., 15,356 (1973).
4. J.R. Ourig, S.M. Craven, C.W. Hawlcy and J. Bragin, J. CI/eпr. PI,yS., 57, 131 (1972).
5. G. Corti1i and G. Zcrbi, Spec/roc//i/1/. Асш, Par/ А, 23А, 285 (1967).
6. Н. BUrger and G. Pawclke, Spec/roc//im. Ас/а, Par/ А, 35А, 525 (1979).
7. E.L. Расе, А.С. Plaush and Н.У. Samuclson, Spec/rocIIiпr. Ас/а, 22, 993 (1966).
8. О. Risgin and R.C. Taylor, Spec/roc/lim. Ас/а, 15, 1036 (1959).
9. G.A. Cro\vdcr, J. F/I/ori//e Cllem., 1,385 (1971П2).
13б
6.3 Dib/'O/l/o/l/ell/ylelle
10. G.A. Cro\vder, J. F/rlOri"e CIICIII., 2,217 (1972173).
11. Y.S. Li and J.R. DlIrig, J. Мо/. S/rllc/., 81, 181 (1982).
12. Н.О. DcsseYl1, B.J. Уаl1 der Vekcl1, L. Уаl1 Haverbcke and М.А. НсrП1ап,J. Мо/. S/rllc/.,
13, 227 (1972).
13. J.E. Guslavsen, Р. Кlaboc, C.J. Nielscn and D.L. Ро\ус 11 , Spec//'Ocl1im. Ас/а, Par/ А,
35А, 109 (1979).
14. Р. Кlaboc and J.R. Niclsen,J. Мо/. Spectrosc., 6,379 (1961).
15. N.P. Emsling al1d J. pfab, Spec/rocllim. Ас/а, Рап А, 36А, 75 (1980).
16. S. Giorgianni, А. GnП1\)i, L. Fral1co and S. Ghersctti, J. Mol. S/rиct., 75, 389 (1979).
17. L.H. Ngai and R.H. Мапп, J. Мо/. Spec/rosc., 38, 322 (1971).
18. Н.Н. Claasscn,J. С//ет. P/,yS., 22,50 (1954).
19. 1. McAlpine and Н. Sutcliffe, Spec/roc/lim. Ас/а, Par/ А, 25А, 1723 (1969).
20. М.с. Tobin, J. Ат. С//{!т. Soc., 75, 1788 (1953).
21. G.A. Cro\vdcr, Spec/rocl1im. Асш, Part А, 42А, 1079 (1986).
22. M.S. Wu, Р.с. Painter and М.М. СоIСП1ап, Spec/roc//i/1/. Ас/а, Part А, 35А, 823 (1979).
23. J.H.S. Grccn and D.J. Harrison, Spec/roc/li/1/. Ас/а, Par/ А, 27А, 1217 (1971).
24. Р. Кlaboc, Spec/roc//im. Acta, Par/ А, 26А, 977 (1970).
25. S.H. Chough and S. Кrimm, Spec/roc//i/1/. Ас/а, Par/ А, 46А, ]419 (1990).
26. К Ohno, У. Shiro and Н. Murata, Bll/l. CI/e/1/. Soc. Jp"" 47, 2962 (1974).
27. G.A. Cro\vdcr and W. Y. Lin,J. Мо/. S/rllc/., 62,1 (1980).
28. К. Ohno, К. Taga, ]. Yoshida and Н. Murala, Spec/roc/lim. Ас/а, Par/ А, 36А, 721
(1980).
29. А.В. Dempstcr, К Pricc and N. Sllcppard,Spec/roc/lim.Acta, Par/A, 27А, 1563 (1971).
30. А.О. Diallo, Spec/roc/lim. Ас/а, Par/ А, 35А, 597 (1979).
31. J.R. Durig, C.J. Wurrcy, W.E. Bucy and А.Е. Sloan, Spec/roc//im. Ас/а, Par/ А, 32А,
175 (1976).
32. А.В. DСП1рs'сr, К. Pricc and N. Shcppard, Spec//'Oc//im. Acta, Par/ А, 27А, 1579 (I971).
33. D.L. Powcll, Р. Кlaboc, К. Sacb0 and G.A. Crowder,J. Mol. S/rllct., 98, 55 (1983).
34. L. Уап Havcrbckc, Н.О. Dcsseyn, B.J. Уап der Vekcn, Bll/l. Soc. C/lim. Ве/., 82, 133
(1973).
35. S.Bj0rklund and Е. Augdahl, Spec/rocl1im. Ас/а, Par/ А, 32А, 1021 (1976).
36. L. Уап Havcrbcke and М.А. Нсrrnап, Spec/roc//im. Ас/а, РQI'/ А, 31А, 959 (1975).
37, А.О. Diallo, Spec/rocl/i/1/. Acta, Par/ А, 27А, 239 (1971).
38. А.О. Diallo, Spec/rocl/im. Ас/а, Par/ А, 32А, 295 (1976).
39. А.О. Diallo, Spec/roc!Jim. Acta, Par/ А, 38А, 687 (1982).
7
Normal Vibrations and
Absorption Regions of С(==Х)У
7.1 CARВONYL COMPOUNDS
7.1.1 Formyl
Thc C(==O)H group posscsscs six normal vibrations which arc dcscribcd as
follows:
I/СН, I/С==О, ЬСН, I'СН/С==О, ЬС==О and torsion.
Thc СН stretching vibration
The highcst СН stretching vibrations are found in thc spcctra of formatcs (29З5 :f:
45 cm 1). Formyl f1uoride scores highest with 2980 cm 1. For CICH20C(==O)H
in thc crystaIline state the value is 2980 cm ' Ьи! in thc liquid statc 29б8 cт 1
[109,111, 112]; formic acid as а dimcr givcs 2957 [93, 95, 9б] and 2949 [9б] and
as а monomer 2942 cm 1 [9З, 94, 9б]. Aldchydes, thioformates and formamidcs
absorb in thc rcgion 2850 :1:: 45 cm 1 with high valucs for 2 FзСРhС(==О)Н
(2895) and H2NC(==O)H (2882) and low valucs for МсСН==СНС(==О)Н (2805)
and 2 McPhC(==O)H (2808 cm 1). Thc unambiguous assignmcnt of this wcak
to modcratc band in aldchydes is oftcn disturbcd Ьу thc ovcrtonc of thc СН
in planc dcformation (2745 :f: 45 cm I), which incrcases in intensity Ьу Fcrmi
rcsonance. In a halogen substituted aldchydcs, in which thc halogen slightly lowers
thc absorption frequency of ЬСН, thc ovcrtonc does по! causc Fcrmi rcsonancc, for
cxamplc Сl з СС(==О)Н and ВrзСС(==О)Н. Тhis typical Fcrmi doublct, in which
both absorptions arc in esscnce implicatcd in thc СН strctching vibration, is vcry
uscful in idcntifying aldchydcs [138, 139].
138 Normal Vibralio//s а//{! AbsOl]Jlio// Regio//s о/ С(==Х) У
saturatcd aldcl1yde unsaturatcd aldcl1yde аrОП1аtiс aldcl1ydc
I/СН
2 х БСН
2840 :!: 30
2720 :!: 20
2830 :!: 30
2720 :!: 20
2850 :!: 45
2755 :!: 35
Тhc с==о strctcl1ing vibration
Logically thc с==о strctching vibration provides thc most charactcristic band of
thc С(==О)Н group, whicl1 absorbs vcry strongly in thc rcgion 1745 :!: 95 cm 1. ln
formatcs thc largc rcgion (1765 :!: 75) is produced Ьу F C(==O)H, which displays
thc I/С==О а! 1837 cm l (Scction 7.1.2). FоrП1iс acid and its estcrs (Section 7.1.7)
absorb 1730:!: 40 cm 1. Saturated aldehydcs absorb strongly in tl1c region 1755:!:
35 cm 1 with а! thc HW sidc the o: halogenatcd aldehydcs such as F з СС(==О)Н
(1788) and С1зСС(==0)Н (1758) and а! the LW sidc Ira//s cPrC(==O)H (1700
cm 1). For МС(СН2)"С(==0)Н (// = 12) the rcgion narrows to 1730 :!: 5 cm 1
[141]. Most of thc investigators [38, 41--46,49, 50] find 1745 and 1732 cm 1
bands in thc vapour state spcctrum of Н(О==)СС(==О)Н while Durig et al. [З9]
find 1729 and 1707 cm 1 in thc spcctrum of the crystals. Aromatic aldehydes,
formamidcs (Scction 7.2) and thioformatcs show thc I/С==О in the range lб90
:!: 30 сm 1. Most of thc benzaldchydcs absorb in the neighbourhood of 1700
cm 1. High values arc found in thc spectrum of 4 HO(0==)CPhC(==0)H (1719
with 1б88 for thc acid) and in thc spcctra of pyridinccarboxaldchydcs (:::::1712
cm 1), and lo\v valucs in thosc of 4-Мс2NРhС(==0)Н (lб61) and 2 , з and 4
HOPhC(==O)H (:::::16б5 cm l). McHNC(==O)H absorbs а! 1720 cm 1 as а gas
[125] or in а N2 matrix [124] Ьи! а! 1бб6 cm l as а liquid. Unsaturated aldchydes
cxhibit thc с==о band in thc rcgion 1б85:!: 35 cm 1. The highcst valucs (:::::1720
cт 1) arc found in thc vapour phasc spcctra of the compounds Н2С==СНС(==0)Н,
МсСН==СНС(==О)Н and Н2С==С(МС)С(==0)Н, which absorb in the vicinity of
1б95 cm 1 as а liquid. For most of thc unsaturated aldchydes the с==о strelching
vibration occurs а! 1б75 :!: 25 cm 1. Тhc low values (:::::lб05) in thc spectra of
sa1ts of ,В-kеtоаldсhуdсswith thc formula R C(==0)CH2C(==0)H (R = Мс, Et,
iPr, 'Ви), in which thc с==о bond is weakcncd Ьу the contribution of the епоl
tautomcr [12], are по! lakcn into account.
Тhe СН in-planc dcformation
Тhc СН in-planc dcforma1ion or СН rocking vibration mostly appears in the rcgion
13БО:!: 55 cm 1 as а wcak 10 modcrate band. Оп the HW side of this region опе
finds thc absorptions of а fcw benzaldchydes such as 2 FзСРI1С(==0)Н (1415),
З МеРhС(==О)Н (1408) and 3 FPhC(==0)H (140б cm 1). In thc spcctra of 4
Х substituted bcnzaldchydcs Nyquist et al. [140] assign thc ЬСН а! 1387 :!: 7
cm 1, with ovcrtones ncar 2775 cm 1. Тhc lowcst values appcar in the spectra of
Н(О==)СС(==О)Н (1312 and 1338), D(O==)CC(==O)H (1335) and HSC(==O)H
7.1 Carbollyl Coтpoullds
139
(1339 сm 1). The уаl ие 1504 сm 1 in thc уарош phasc spcclrum of formaldehyde
falls outside the abovc mentioncd region. Most of the aldchydcs show this ЬСН а!
1370:1: 25 cm 1. The overtones should Ьс cxpcctcd ncar 2745 :!: 45 cm 1.
The сн/с==о wagging vibration
The СН/С==О wag is assigncd in 1he largc rcgion 885 :!: 185 cm 1 with а wcak
to modcrate intensity. The broadness of the rcgion stcms from thc fact that thc
absorption а! high {low} frequcncies has mostly thc charactcr of а СН {С==О}
wag. Thc 1/6 (wCH 2 : Ь,) а! 11б7 cm 1 in thc spcctrum of formaldchydc is по!
takcn into account. (п МсС(==О)Н thc СН wag (7б4 cm t) is couplcd 10 thc
mcthyl rock (1102 cm 1). (п the spectrum of EtC(==O)H thc СН wag is assigncd
а! 89б cm '. А compound such as Н(О==)СС(==О)Н displays the СН wagging
vibrations а! 1048 and 801 cm 1. High wags arc found in thc formatcs with 1050
cm ) for НС(==О)ОН and valucs in thc ncighbourhood of 1040 cт 1 for thc
estcrs of formic acid. In the spcctrum of cthyl formatc Dahlqvist and Euranto
[109] assign the shoulder (1015 cm ') псх! to thc I/ s COC to thc ""СН, whcrcas
Charlcs et al. [110] prcfer the wcak band а! 920 cm '. Aromatic aldchydes show
thc сн/с==о wag рroЬаЫу in thc rcgion 775 :1: 55 cm 1, although in thc spcctra
of some benzaldchydcs this vibration is assigncd in thc ncighbourhood of 1000
cm ) [б9, 70].
с==о in-plane deformation
Тhc с==о in plane deformation сап Ье found in thc cxtcnsivc rcgion 550 :1: 220
cm 1 as а weak to modcrate absorption. Mostly thc ЬС==О appcars а! б15 :!:
155 cm ' if the low valuc of а ЬС==О in the spcctrum of Н(О==)СС(==О)Н
(55] and 339 as а gas and 55] and 388 cm 1 in the solid phase) is по! takcn
into account. Saturated aldehydcs [135] show thc ЬС==О in the region 5б5 :!: 100
cm 1 \vith EtC(==O)H (6БО), nPrC(==O)H (6б1) and CICH2C(==0)H (4б3 cm t)
as cxamplcs. The rangc of unsaturatcd aldchydcs (б40 :1: 100 cm l) is in good
agrccmcnt with that of aromatic aldchydcs (б45 :1: 55 cm 1). In thc spcctra of
XC:SCC(==O)H (Х == CI, Br, 1, Н, О) thc ЬС==О is assigncd rcspcctivcly а!
738, б91, б70, б15 and б09 cm 1 and in the spcctrum of МсСН==СНС(==О)Н а!
542 cm l. Thc highcst valucs arc found in thc spcctra of formatcs and formarnidcs:
МсОС(==О)Н (767), HC:sCCH 2 0C(==0)H (765) and McHNC(==O)H (770
cm 1).
Torsion
Тhe weak absorption in the rcgion 125 :1: б5 cm 1 is assigncd to thc C(==O)H
torsion.
140
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7.1 Carboпy! Coтpoltllds
141
R C(==O)H moleculcs
R = H [1, 2], Me [1, 3 5, 13б], СОз [1, 5], CH20 [5],
Et [6---9], McC02 [8], nPr [7], PhCH2 , HOCH2 [10, 11],
R'C(==O)CH2 (R'== Ме, Et, iPr, tBu) [12], FCH2 [13], CICH2 [14,
15], CI2CH [16], cPr [17], iPr [18, 19], tBu [20, 21],
СFз [22 28], ССlз [29 31], СВrз [29,30, 32], H(O==)C [33---51],
O(O==)C [38,41,44,45, 47], HO(O==)C [52, 53], H2C==CH [4:Ц8,
54], MeCH==CH [54---56], H2C==C(Me) [5б, 57], Mc (CH==CH)2 ,
Ме (СН==СН)з and Mc(CH==CH)2C(Me)==CH [58],
HOCH==CH [4б, 60], H2NCH==CH and D2NCH==CH [59],
HOCH==C(Br) [60, 61], HC=C [б2--65], OC=C [б2--64],
McC=C [б6], N=C [65], XC=C (Х = CI, Br, 1) [б4, б7], Ph [бg.....
72], 2 , 3 and 4 McPh [70], 4-ЕtРh , 2-, з- and 4-FзСРh [73], 4-
tBuPh , 4 N=CPh [74], 4 HO(O==)CPh [74], 2 HOPh [75, 7б],
3 HOPh [92], 4 HOPh [77, 92], 2 , з and 4-МсОРh [78, 79], 2 and
4 EtOPh [74], 2 , 3 and 4 02NPh [77,80, 92], 4 Mc2NPh [77,81 J, 4
McSPh , 2 , 3 and 4 FPh [70,71], 2 , 3 and 4 CIPh [70,71, 82], 2 , 3-
and 4 BrPh [70], 2,4 Mc2Ph and 2,5 Mc2Ph [83], 2,3 (HO)2Ph and
3,4 (HO)2Ph [84], 2 НО З МсОРh , з-НО 4 МсОРh and 4-
HO 3 McOPh [85], 2,3 (McO)2Ph , 2,4-(МсО)2Рh and 3,4
(MeO)2Ph [8б], 2,4 CI2Ph , 3,4 CI2Ph and 2,б СI2Рh [87],
2,4,б (МсО)зРh , 2,4,5 (МсО)зРh and 2,3,4-(МсО)зРh [88], 2-, 3-
and 4 Py [89], 2 Fu [90, 91], 2-Th , HO [93 98], oo [93,
97 99], MeO [100 109], СDзО [105 107, 109], ЕtO [109, 110],
CICH20 [109, 111 113], CICD20 [109, 111], H2C==CHO [114],
HC=CCH20 [109, 115], HS [11б, 137], McS [117], H2N [11g.....
123], D2N [118, 120, 123], McNH [123---125], McND [123, 12б],
H2NHNC(==S)NH [127], MC2N [125, 12g.....1З2], F [133, 134],
CI [134].
References
1. Р. Cossce and J.H. Schach'schncidcr,l. C/leт. P//ys., 44, 97 (1966).
2. J.W.c. Johns and W.B. Olscn, J. Мо/. Spec/rosc., 39, 479 (1971).
3. KS. Pitzer and W. Weltner, J. А/1/. С//ет. Soc., 71, 2842 (1949).
4. J.C. Evans and H.J. Bcmstein, Call. J. С//ет., 34, 1083 (1956).
5. Н. Hollenstcin and Н.Н. GUnlhard, Spec/roclJim. Ас/а, Par/ А, 27А, 2027 (1971).
6. Е.Е Worden Jr., Spec/roc/liт. Ас/а, 18, 1121 (1962).
7. G. Sbrana and У. SchCtlino, J. Мо/. Spectrosc., 33, 100 (1970).
8. S.G. Frankiss and W. Kynaslon, Spec/roc/liт. Ас/а, Par/ А, 28А, 2149 (1972).
9. Р. Уап Nuffe1, L. Уап dcn Endcn, С. Van Alscnoy and H.J. Gcisc,J. Мо/. Strllc/., 116,
99 (1984).
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7.1 CarbollY! Compouпds
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144 No/тal Vibralio//s a//d Absorplio// Regio//s о/ с(==х) у
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7.1 Carboпy! Compounds
145
7.1.2 Fluoroformyl (fluorocarbonyl)
Thc C(==O)P group provides six normal vibrations of which опlу thc с==о
strctching vibration Icads to а good group vibration:
I/С==О, 1/СР, ЬС==О/СР, ,(w)C==O/F, Ь(р)СР/С==О and torsion.
Thc с==о strctching vibration
РС(==О)Р shows thc с==о strctch а! 1928 cm I (gas) or 1909 cm 1 (liquid) and
F(O==)COOC(==O)F shows l/ а С==О а! 1927 and I/ s C==O а1 1902 cm 1, Ьи! thc
othcr R C(==O)F compounds absorb strongly in thc rcgion 1845 :i: 55 cm l.
Thcsc high valucs arc influcnccd Ьу thc clcctroncgativity of thc ftuorinc atom,
which confcrs а largely doubIc bondcd charactcr to thc с==о bond and causcs thc
frcqucncy to deviatc significantly from thc mсап с==о frcqucncy (::::::1700 cm t).
For СF з С(==О)F and СF з ОС(==О)F this valuc rcachcs 1900 cm l. А! thc lowcr
side thcre is absorption Ьу McSSC(==O)F а! 1793 cm 1 as а liquid and 1829
cm 1 as а gas and also Ьу thc Q unsaturatcd acid fluoridcs with, as examples,
Н 2 С==С(Ме)С(==0)Р (solid: 1790; liquid: 1804; gas: 182б), H2C==CHC(==0)F
(S-trans: 1803; S cis: 1813 cm 1) and PhC(==O)F (1810 cm l).
Thc C F strctching vibration
Тhe C F stretching vibration appcars modcratcly to strongly in thc cxtcnsivc
rcgion 1150:1: 140 cm l. As thc CF stretch couples rcadily to thc R C strctching
vibration, thc formcr is somctimcs dcscribcd as ап R C F [7] out-of-phasc
strctch, absorbing in thc above mcntioncd rcgion, and thc lattcr as an in phasc
R C F strctcl1 absorbing а! lowcr frcqucncics. Тhe origin of thc lattcr absorption
сап Ьс for instancc а C C stretching vibration which occurs псзr 830 cm 1
or ап O C strctch near 900 cm l. In F2C==0 thc tcrms out of-phasc I/CF
(1249) and in phasc I/CF (9б5 cm l) arc clcarly relcvant. In acid ftuorides this
I/CF occurs а! higl1cr wavenumbcrs (1175 :1: 115 cm 1) than in ftuoroformatcs
(1075 :1: б5 cm 1) and in sulfur bondcd R C(==O)F compounds (1070 :1: 30
cm 1). F(O==)CC(==O)F givcs rise to а I/CF а! 1290 and а! 1122 cm 1 but for
most of the acid fluorides thc rangc is rcduccd to 1150 :1: 85 cm l. Low C F
strctching vibrations are assigned in thc spectra of Мс(СDз)НСОС(==О)F (1010),
iPrOC(==O)F (1015) and McOC(==O)F (1054 cm I).
Тhc C==O/CF deformations
Тhc C==O/CF dcformations give risc to thrcc absorption regions usuaIly assigncd to
the in plane deformation or bC==O/CF (680 :1: 110), thc out of-planc deformation
or ,'(w)C==O/CF (545 :1: 125) and thc rocking vibration or P(b)CF/C==O (415 :1:
146 Normal ViЬПlliо"s ат! AbsOIplio" Regio"s о/ С(==Х) У
155 cm 1). TllC iшрrас!icаЫу wide rangcs arc causcd Ьу thc Пuоrоfоrmа!сs, wl1ich
absorb а! :::::100 сш 1 I1igllcr wavcnumbcrs than o!ller R C(==O)F compounds.
Thc thrcc dсfоrшаtiопs of МсОС(==О)Р, CICH 2 COC(==O)F a"d iPrOC(==O)F in
thc gas phasc arc rcpor!cd in the vicinity of 790 (уС==О/СР), б70 (ЬС==О/СР)
and 550 сш 1 (рСР/С==О). 1" fluoroformatcs Ihc highcr wavcnumbcr (775 :1:
15 cm 1) is assigned 10 111C ou!-of-plane dcforma!ion Ьи!, as Ihcsc vibralions arc
mixcd, it is по! а! аll obvious if а dcformation occurs in planc or out of planc or
if а dсfоrшаliоп posscsses morc thc characlcr of а с==о or а СР dcformation.
ТаЫе 7.2 Absorplion rcgions (cm ') of !he поrrnаl vibralions of C(==O)F
Vibration a:-saturated с==о bondcd a:-unsaturatcd fluoroformates sulrur-bonded
I/С==О 1845 :1: 55 1870 :1: 30 1825 :1: 35 1855 :1: 45 1820 :1: 30
I/CF 1150 :1: 85 1195 :1: 95 1155 :1: 70 1075 :1: 65 1070 :1: 30
bC==O/CF 670 :1: 100 625 :1: 55 655 :1: 75 770 :1: 20 650 :1: 20
1'C==O/CF 510:1: 90 485 :1: 35 545 :1: 65 650 :1: 20 535 :1: 45
pCF/C==O 420 :1: 80 345 :1: 85 470 :1: 80 540 :1: 30 420 :1: 80
'orsion 110 :1: 65 70 :1: 35 85 :1: 35 105 :1: 20
R C(==O)F moleculcs
R== H and o [1 3, 53], Mc [ 8], СDз [4, 5, 7], EI [9, 10, 541,
FH2C [11 13], CIН2C [14, 15], BrH2C [1б], CI2HC [17, 58],
cPr [18], cBи [55], iPr [19], СFз [20---25], F(O==)C [2 28],
CI(O==)C [2б, 29], H2C==CH [30, 5б], H2C==C(Me) [31, 32],
H2C==CF [33], F2C==CF [34], HC=C [35 37], OC=C [35, 3б],
MeC=C [38], N=C [37], Ph [39, 40], 4 MePh [40], MeO [41,
42], СDзО [42], ЕtO [43], CIН2CO and CID2CO [44], iPrO [45],
MC20CO and Мс(СDз)НСО [45], СFзО [4б], CH2==CHO [57],
F(O==)COO [59], McS [47], McSS [48], Cl(O==)CSS [49],
F(O==)CSS [501, F [51], Cl [51,52].
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23. R.L. Rcding\on, Spec/rocllim. Ас/а, Par/ А, 3JA, 1699 (1975).
24. Е. Oltavianclli, Е.А. Castro and А.Н. Jubcrt, J. Мо/. S/rllc/., 254, 279 (1992).
25. J.S. Francisco and l.н. Williams, Spec/roc//im. АС/а, Par/ А, 48А, 1115 (]992).
26. J. Goubeau and М. Adc'helm, Spec/roc/lim. Ас/а, Par/ А, 28А, 2471 (1972).
27. J.R. Durig, S.c. Brown and S.E. Hannum, J. C/lem. P//ys., 54, 4428 (1971).
28. J.G. Contraras and J.O. Machuca,A/I. Qlli/1/., 77, 370 (1981).
29. J.R. Durig and М.Е. Harris, J. Mol. S/rиct., 81, ]95 (1982).
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31. J .R. Durig, Р.А. Brlctic and J.s. Church,J. С//ет. Phys., 76, 1723 (1982).
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33. J.R. Durig, А.-У. Wang, T.S. Littlc, Р.А. Brlctic and J.R. Buccncll,J. Chem. P/,yS., 91,
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36. W.J. Balfour and М.К. Phibbs, Spec/rocl/im. Асщ рат/ А, 35А. 385 (1979).
37. W.J. Balfour, S.G. Fougcrc and О. Кlapstcin, Spec/roc//i/1/. Ас/а, Par/ А, 47А, 1127
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38. W.J. Balfour, К, Bcveridgc and J.C.M. Zwinkcls, Spec/rocllim. Ас/а, Par/ А, 35А, 163
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40. G. Varsanyi, Assig/lme/l/sfor Vib,'a/io/lal Spectra ofSeve/l HUI/dred Be/lze/leDerivatives,
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41. G. Williams and N.L. Owcn, Tra/ls. Faraday Soc., 67, 950 (1971).
42. J.R. Durig, T.S. Litt1c and C.L. То1lсу, Spec/rocl/im. Ас/а, Рат/А, 45А, 567 (1989).
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45. B.J. Уап dcr Vckcn al1d Н.Н. Licfooghc,J. Мо/. SIrIlC/., 247, 257 (1991).
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51. А.Н. Niclscn, T.G. Burkc, P.J.H. Woltz and Е.А. Joncs,J. CI/em. PI/ys., 20, 596 (1952).
52. R.A. Nyquist, Spec/roc//im. Ас/а, Par/ А, 28А, 285 (1972).
148 Noтral Vibтliol/s al/d AlJso/'pliol/ Regiolls о/ с(==х) у
53. G. Yarwood, Н. Niki and Р.О. Makcr, J. P/,ys. CJ/e11l., 95, 4773 (1991).
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59, с.о. Оеllа Vedova and H.G. Mack, J. Мо/. Strиc/., 274, 25 (1992).
7.1.3 Ch\oroformy\ (chlorocarbony\)
Тhc six C(==O)Cl normal vibrations are usually assigncd as follows:
I/С==О, I/C Cl, I'C==O/CCl, bC==O/CCl, bCCl/C==O and torsion.
The с==о strctching vibration
Thc с==о strctch absorbs strongly in the region 1790 :1: 55 cm 1, with the
cxccption of FC(==O)Cl (18б8 cm l). More than опе conformation leads to scveral
bands in thc abovc-mcntioncd absorption rcgion. Thc highest с==о strctching
vibrations сап Ье found in the spcctra of CI(O==)CC(==O)Cl (1845 and 1774),
CIC(==O)Cl (1827) and (ВиС(==О)Сl (1825 and 1778 cm 1) and the lowcst in
thc spectra of carbamoyl chlorides R'R"NC(==O)Cl (R', R" = Н, Ме, Et) (::::::1740),
PhCH==CHC(==O)Cl (1753), 2 ТhC(==O)Cl (1753), 3 02NPhC(==O)CI (1755),
3 ClPhC(==O)Cl (1758) and Mc C=CC(==O)Cl (1758 cm l). The majority of
the invcstigated n101cculcs wcrc found to givc this I/ O in thc rcgion 1790 :1: 30
cm l, \vhich is reduced to 1800:1: 15 cm 1 for R'CH 2 C(==O)C\ compounds and
еуеп to 1802 :1: 2 cm l for МС(СН2)"С(==О)СI (1/ = 2 lб). \п the spectra of
aromatic acid chloridcs the I/С==О (1775 :1: 20 cm 1) is often accompanied Ьу а
smaller band (1740 :1: 10 cm t). Thc highcr frcquency band has the larger intensity
and is called thc carbonyl stretching absorption band, and the lower frequcncy band
is callcd the first overtonc of а complex planar modc involving stretching of thc
phcnyl C(==O) CI bonds in thc ncighbourhood of 865 cm l [84].
Тhc C Cl stretching vibration
Тhe C Cl strctch 'wandcrs' in the cxtcnsivc rcgion 745 :1: 185 cm 1. Although
the intcnsity of thc band is modcrate to strong, it is по! а good group vibration,
In addition, this I/C CI is sensitive to conformation [83] and the assignments in
literaturc are oftcn controvcrsial. The highest valucs arc obscrved in thc spectra
of aromatic acid chloridcs (8б5 :1: б5 cm 1) with 3 02NPhC(==O)Cl (930) and
3 CIPhC(==O)Cl (909 cm 1) as maxima, Ьи! most of the bcnzoyl chlorides show
а strong band in the region 855 :1: 45 cm 1. Тhis complex vibration is due to
the coupling between thc C CI strctching vibration and thc phcnyl C stretch in
7.1 CarbollY! Compou//ds
149
which tl1c I/C Cl furnishcs thc highcst contribution [57, б3, б5, 84]. For benzoyl
chloridc this vibration is assigncd а! 875 cт 1 although Condit et al. [БО] prcfcr
б7З cm 1 and assign the strong band а! 875 cm 1 to ап in-planc substitucnt
scnsitivc ring dcformation. То аll probability thc chloroformatcs also absorb а! high
wavcnumbcrs (790 :!: 60), whilc valucs in thc vicini1y of б90 cm 1 arc assigncd
to tl1c ,с==о [48---51]. Hory [85] оп thc othcr hand puts this I/C CI а! б91
:!: З cm I in а scrics of chloroformatcs. Тhc lowcst C CI stretching vibrations
arc rcportcd in thc spcctra of СDзС(==О)СI (5б3), Iralls-CH20C(==O)CI (5б5),
galtc//e-CI2CHC(==O)CI (578) and МсС(==О)СI (595 cm J). For most of thc acid
chlorides thc C CI strctching vibration is situatcd а! 750 :!: 150 cm l. Ncglccting
thc abovc mentioncd values and thc high valuc for CBrF 2 C(==O)Cl (8ЗО), thc
rcgion for thc a-saturated compounds narrows to 70S:!: 75 cm 1. EtC(==O)CI
absorbs а! б93 cm ' and thc rcmaining МС(СН2)пС(==О)СI compounds (// = 2
1б) а! б80 cm 1. In the spcctrum of CIC(==O)CII/J and 1/4 occur rcspcctivcly
а! 575 and 849 cm l.
Thc с==о deformations
Thc C==O/C CI deformations, absorbing wcakly to modcratcly in thc rcgions
575 :!: 115 and 4б5 :!: 75 сm, arc mainly с==о dcformations. Thc highcst wavc-
numbcr is often assigned to thc out-of-planc dcformation but, for lack of а planc
of symmctry, it is по! aIways clear if а vibration occurs in-planc or out-of-plane.
Тhc chloroformatcs alkyl OC(==O)Cl (alkyl = Мс, Et, nPr, iPr, пВи and iBu)
( б90), НС=ССН20С(==О)Сl (б89) and PhOC(==O)CI (б84 cm 1) show а
sharp absorption in thc ncighbourhood of б90 cm 1, assigncd to thc ,с==о [48---
51] or to thc I/C CI [85]. Low values for the ,с==о arc found in thc spcctra of
CI(O==)CCH==CHC(==O)Cl (497 and 4БО) and Н2С==СНС(==0)Сl (495 cт 1).
The very low valuc of 440 cm 1 for CIC(==O)CI is outsidc this rcgion.
The domain of thc ЬС==О (4б5 :!: 75 cm J) is dclimitcd Ьу 4-
BrPI1C(==O)Cl (536), 2,4-СI 2 РhС(==О)СI (535) and 3,4-СI2РhС(==0)Сl (532
cm 1) оп the опс sidc and Ьу Cl(O==)CCH==CHC(==O)Cl (393 and 430),
МсО(О==)ССН==СНС(==О)Сl (410) and cis-сРrС(==О)СI (415 cm t) оп thc
othcr sidc. Thc low value for CIC(==O)CI (297 cm t) is по! takcn into account.
The C CI deformation
The C CI/C==O in-planc dcformation is gcncrally assigncd in thc rangc 325
:!: 90 cm 1 with compounds such as FC(==O)CI (415), НС=СС(==О)Сl (414),
МсОС(==О)Сl (413) and trallS-СI2СНС(==О)СI (410 cm l) at thc HW sidc and
Cl(O==)CC(==O)CI (290 and 225), CI(O==)CCH2CH2C(==0)Cl (2БО and 230),
Irаns,llш/s-Сl(О==)ССН==СНС(==О)СI (232 and 241), CIC(==O)CI (240) and
СН2==С(Мс)С(==О)СI (249 cm l) а! the LW sidc. Espccially in thc casc of lo\v
wavcnumbers the C Cl group makcs thc highcst contribution to this deformation.
150 Noтtal Vibralio"s a"d AbsOIplio" Regio"s о/ с(==х) у
ТаЫе 7.3 Absorp'ion rcgion (cm 1) оС tlte поrшаl vibratiol1s оС C(==O)Cl
Vibration Q-saluratcd с==о bonded сltlоroСоrшаtеs aromatic uпsаtша'сd carbarnoyl
chloridcs
I/С==О 1800 :!: 30 1810 :!: 35 1780:!: 20 1775 :!: 20 J 760 :!: 25 1740:!: 05
, - 1:!: 110 690 :!: 70 790 :!: 60 865 :!: 65 700 :!: 100 640 :!: 40
I :!: 95 630 :!: 50 675 :!: 15 620 :!: 50 560 :!: 100 615 :!: 45
:!:: 55 440 :!: 50 500 :!: 40 480 :!: 60 440 :!: 50 460 :!: 20
f: 90 315 :!: 90 365 :!: 50 330 :!: 50 320 :!: 95 390 :!: 20
:!: 60
R C(==O)CI molcculcs
R== H [1, 2], Me [3---6], СDз [3, 5], CH20 [3], E! [7, 8], nPr [9],
PhCH2CH2 , CICH2CH2 [9], Cl(O==)CCH2CH2 [10], PhCH2 ,
FCH2 [11 15], CICH2 [16---20, 89], BrCH2 [1б, 21], C]2CH [22
25], Br2CH [2б], iPr [27], cPr [28 30], cBu [31], tBu ,
СFз [З2 37], ССlз [24], СВrз [38], CBrF2 [86], F(O==)C [39,
40], Cl(O==)C [41 3], Me(O==)C [44], MeO(O==)C [45, 46],
McO [4, 48, 49], СDзО [48], ЕtO [47], nPrO , пВиО ,
iPrO , iBuO , CICH20 and CICD20 [50, 51], H2C==CHCH20 ,
HC=CCH20 [49], PhCH20 , PhO , MeS [4, 52, 53],
F(O==)CSS [54], CI(O==)CSS [88], Ph [55---62, 90], C605 [БО],
2 , 3 and 4 XPh (Х = F, Cl, Br, 1, Мс, ОМс and N02 [б3], FзС
[87]), 4 XPh (Х = CI, Br, ОМе, NMc2 and N02 [64, б5], N=C,
nPr, nBu, !Bu), 2,4 CI2Ph , 3,4 CI2Ph and З,5 СI2РI1 [6б, б7], 2
Fu [б8], 2 Тh , H2C==CH [б9 72], MeCH==CH and Me2C==CH
[73], C](O==)CCH==CH [74], McO(O==)CCH==CH [4б, 75],
XCH==CH (Х = Cl, Br, 1) [7б], H2C==C(Me) [77], PhCH==CH ,
HC=C [78---80], OC=C [80], McC=C [78], McHN and
MeDN [81], Me2N , E!2N , F [49, 82], Cl [82].
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74. J.M. Landry and J.E. Katon, Spectrocl1im. Ас/а, Par/ А, 40А, 871 (1984).
75. J.E. Kalon and Р.-Н. Chu, J. Мо/. S/rllc/., 82, 61 (1982).
76. К. Kamiciiska-Trcla, Н. Baraiiska and А. Labudziiiska,J. Mol. S/rиct., 54, 59 (1979).
77. J.R. Durig, Р.А. Brlctic, Y.S. Li, А.-У. Wang and T.S. Lit,lc, J. Mol. S/rиc/., 223, 291
( 1990).
78. Е. Augdahl, Е. Кlosler Jensen and А. Rogslad, Spectrocl1im. Ас/а, Part А, 30А, 399
(1974).
79. W.J. Balfour, R.H. Mitchell and S. Visaisouk, Spec/rocl1im. Ас/а, Par/ А, 31А, 967
(1975).
80. W.J. Balfour and М.К Phibbs, Spec/roc//im. Ас/а, Par/ А, 35А, 385 (1979).
81. W. Buder and А. Schmid', Spec/roc//im. Ас/а, Part А, 29А, 1419 (1973).
82. А.Н. Niclscn, т.G. Burkc, P.J.H. Wo'lz and Е.А. Jones,J. CJ/em. P//ys., 20, 596 (1952).
83. J.E. Ка'оп and W.R. Feairhcllcr Jr., J. C/lem. P//ys., 44, 144 (1966).
84. R.A. Nyquis', Арр/. Spectrosc., 40, 79 (1986).
85. Н.А. Ory. Spectrocl,im. Ас/а, 16, 1488 (1960).
86. т.А. МоhаП1еd, Н.О. S'idham, G.A. Guirgis, Н.У. Phan and J.R. Durig, J. Ramall
Spec/rosc., 24, 1 (1993).
87. R. Shanker, R.A. Yadav,I.S. Singh and O.N. Singh,J. Ramall Spec/rosc., 23,141 (1992).
88. S.E. Ulic, P.J. Aymonino and с.о. Ое1lа Vedova,J. Ramall Spec/rosc., 22,675 (1991).
89. А.А. E1-Bindary, Р. Кlaboc and C.J. Niclscn, Ас/а С/,ет. Scaтl., 45, 877 (1991).
90, G. Varsiinyi and S. Szokc, Vibra/iollal Spectra о! Bellze"e Deriva/ives, Academic Press,
New York (1969), рр. 361, 370.
7.1.4 Bromoformy\ (bromocarbony\)
Just likc C(==O)Cl, thc C(==O)Br furnishcs six normal vibrations:
I/С==О, I/CBr, ,C==O/CBr, bC==O/CBr, bCBr/C==O and torsion. Only the
I/С==О is а good group vibration.
7.1 Carbo"yl Coтpoullds
153
Thc с==о strctching vibration
The с==о strctching vibration providcs а strong band in thc rcgion 1780 :f:
50 cm 1. The Q saturatcd C(==O)Br compounds absorb а! highcr wavc-
numbcrs (18UO :f: 30) than thc Q unsaturatcd oncs (1765 :f: 30 cm I). Thc
higllcst valucs are obscrved in thc spcctra of F з СС(==О)Вr (1826), СО з С(==О)Вr
(1825) and EtC(==O)Br (1824 cm t) and the lowcst in thosc of McNHC(==O)Br
(1738), H2C==C(Mc)C(==0)Br (175U), Br(O==)CC(==O)Br (1792 and 1752) and
PllC(==O)Br (1765 cm I). The rcgion 1790:!: 3О cm 1 is appropriatc to locatc а
C(==O)Br group.
The C Br strctching vibration
Thc C Br stretching vibration is obscrvcd in thc cxtcnsive rcgion б85 :f: 1б5
cm l, which is made so extensivc Ьу thc strong and broad absorption а! 851 cm 1
in thc spectrum of benzoyl bromide; this band is assigncd to thc I/C Br Ьу Grecn
and Harrison [29]. Condit et al. [3О], howcvcr, altributc thc absorption а! б57
cm 1 to the I/C Br and that а! 851 cm 1 to ап in-planc ring modc. Low I/C Br
frequcncics are found in thc spcctra of СD з С(==О)Вr (525) and McNHC(==O)Br
(545 cm 1) but generally thc C Br strctching vibration is activc in thc rcgion б55
:f: 90 cm l. For McC(==O)Br this strctching modc is assigncd а! 570 cm l.
Thc с==о dcformations
Thc C==O/CBr deformation with the highcst wavcnumbcr (520 :f: 1БО cm l)
is usually assigned to the out of planc dcformation so far as thcrc is а planc of
symmctry. The HW side of this region is limitcd Ьу б78 cт 1 from FзСС(==О)Вr
and 629 cm 1 from PhC(==O)Br. The lowest valucs are from Br(O==)CC(==O)Br
(405 and 3б2) and trallS CICH2C(==0)Br (398 cm I). А narrowcr rcgion such as
500 :f: БО cm l must Ьс acccptabIe for this out-of.planc deformation.
The rcgion 400 :f: 90 cm 1 is oftcn assigncd to thc C==O/CBr in-planc
dcformation with 486 cm l for PhC(==O)Br and 47б cm 1 for EtC(==O)Br. Thc
lowcst values arc from BrCH2C(==0)Br with ЗlO cm l for thc gaucl/e conformcr
and 359 cm 1 for the tralls conformcr.
Thc C Br dcformation
The CBr/C==O in.plane dcformation or CBr/C==O rock is activc in thc
rcgion 2БО :f: 85 cm 1. Thc cxtrcmc valucs arc found in thc spcctra of
H 2 C==CHC(==0)Br (S tl'Q11S: З45; s cis: 327 cm 1), H2C==C(Mc)C(==O)Br
(332) and Br(O==)CC(==O)Br (190 and 17б cm I). Thc rcgion 2БО:f: БО cm 1
is а good approximation for this CBr dcformation.
154 No,."tal Vib/'Qlio"s а//(! AbsOI'plio" Regio"s о/ с(==х) у
ТаЫе 7.4 Absorpliol1 rcgions (сП1 ]) of 'hc поrП1аl vibrations of
C(==O)Br
Vibration Rcgion Vibration Rcgion
/IC==O 1780 ::1: 50 bC==O/CBr 400 ::1: 90
/ICBr 685 ::1: 165 bCBr/C==O 260 ::1: 85
С==ОIСВr 520 ::1: ]60 'orsion 90::1: 60
R C(==O)Br molccules
R = H [1], Me [2 ], СDз [5], Et [7], FCH2 [8 10], CICH2 [11,
17], BrCH2 [12 14], CI2CH [15], MeCHBr , cPr [lб], cBu [26],
FзС [18, 19], Me2CBr , MeC(==O) [20], BrC(==O) [21 23],
H2C==CH [24], H2C==C(Me) [25], CICH==CH and BrCH==CH
[31], Ph [29, ЗО], 4 McPh [28], McNH [27].
References
1. G. Yarwood, Н. Niki and Р.О. Maker,J. P//ys. С//е11l., 95, 4773 (1991).
2. J.c. Evans and H.J. Bemstein, Call. J. С//е11l., 34, ]083 (1956).
3. J. Overcnd, R.A. Nyquist, J.c. Evans and W.J. Potts, Specl/'Oc/lim. Ас/а, 17, 1205 (1961).
4. J.C. Evans and J. Ovcrend, Spec/roc//i11l. Ас/а, 19, 701 (1963).
5. L.C. НаН and J. Overcnd, Spec/roclli11l. Лсta, Par/ А, 23А, 2535 (]967).
6. J.A. RаП1sау and J.A. Ladd,J. CI/e11l. Soc., В, 118 (1968).
7. S.G. Frankliss and W. Kynaston, Speclroc//i11l. Ас/а, Part А, 31А, 661 (1975).
8. J.E.F. Jenkins and J.A. Ladd,J. С//е11l. Soc., В. 1237 (1968).
9. А.У. Кhап and N. Jonathan, J. C/le11l. P/,yS., 52, 147 (1970).
10. А.А. EI-Bindary, А. Ноm, Р. ЮаЬое, c.J. Nie1sen and Е1.М. Таl1З,J. Мо/. Struc/., 273,
27 (1992).
11. А.У. Кhап and N. Jonalhan,J. С/,е11l. PIIYS., 50,1801 (1969).
12. К. ТапаЬс and S. Sаёki, Speclroclli11l. Ас/а, Part А, 28А, 1083 (]972).
13. J.R. Ourig, Н.У. Phan and T.S. Little, J. Мо/. S/rllc/., 212, 187 (] 989).
14. 1. Nakaga\va,l. lchishiП1а, К. Kuratani, Т. Miyazawa, Т. Shimanouchi and S. МizushiП1а,
J. CI,e11l. P/,yS., 20,1720 (1952).
15. A.J. Wood\vard and J. Jonathan,J. P//ys. C/lem., 74, 798 (1970).
16. J.E. Kalon, W.R. Feairhcller Jr. and J.T. MiI1er Jr., J. C/le11l. PI,yS., 49, 823 (1968).
17. А.А. EI-Bindary, Р. Кlaboc and C.J. Niclscn, Acla C/le11l. Scalld., 45, 877 (1991).
18. с.У. Встсу, Spec//'Oclli11l. Acta, 20, ]437 (1964).
19. с.У. Всmсу and А.О. Corrnicr, Spec/roclli11l. Acta, Par/ А, 33А, 929 (1977).
20. W.J. Ray and J.E. Katon, Spcc/roc//i11l. Асш, Par/ А, 36А, 793 (1980).
21. J.R. Ourig, S.C. Brown and S.E. Hannum,J. CJle11l. PI,yS., 54, 4428 (1971).
22. J.R. Ourig, S.E. НаппuП1 and F.G. Baglin,J. CI/e11l. P//ys., 54, 2367 (1971).
23. J.G. Con'rcras and J.O. Machuca,AlI. QlIi11l., 77, 370 (1981).
24. J.R. Ourig, R.J. Вспу and Р. Groncr, J. С//е11l. P/IYS., 87, 6303 (]987).
25. J.R. Ourig, W. Zhao, R.J. Bcrry and т.s. Liltle, J. Мо/. S/ruct., 212, 169 (1989).
26. К. Hanai and J.E. Kalon,J. Mol. S/rllcl., 70,127 (1981).
27. W. Budcr and А. Schmid', Spec/roc/li11l. Асщ Part А, 29А, ]419 (1973).
7.1 Carb01lY! CoтpoUl/ds
155
28. G. Varsanyi, Лssig//тс//ts [or Vibralio//a/ Spectra o[Seveп HUlldred Beпzelle Derivatives
John Wilcy & Sons, Ncw York (1974). '
29. J.H.S. Grccn and D.J. Harrison, Speclroc//i/1/. ACla, Parl А, 33А, 583 (]977).
30. О. Condil, S.M. Cravcn and J.E. Katon, Арр/. Spec/rosc., 28, 420 (1974).
31. К. КаП1iепskа-Тrсlа, Н. Baranska and А. Kabudzinska,J. Мо/. S/rиc/., 54, 59 (1979).
7.1.5 Acetyl
Тhc С(==О)СНз structure unit givcs rise to ЗN б = 15 normal vibrations of
which nine are inherent to the methyl group:
l/аМС, I/ Mc, I/ s Me, vC==O, ЬаМе, b Me, bsMc, рМс, р'Мс, I/СС, 6С==0, fC==O,
b C C and two torsions.
Mcthyl strctching vibrations
TypicaI for acctyl compounds is the weak intcnsity of thc methyl strctching
vibrations (Scction 2.1.б).
l/аМС I/ Mc I/sMe
3005 ::!: 40 2975 ::!: 45 2905 ::!: б5 cm 1
Thc с==о stretching vibration
Thc highest values for thc I/С==О arc furnishcd Ьу acctyl halidcs ХС(==О)Мс
(Х = F, CI, Br, 1) (1840 ::!: 30), acctic anhydridc МсС(==О)ОС(==О)Мс (1827
and 1755) and acctylhypochloritc СlOС(==О)Мс (1818 cm 1). Sctting asidc thcse
high valucs, the с==о strctching vibration cxhibits а strong band at 1710 ::!:
70 cm l. With the exception of FзСС(==О)Мс (1780 cm l]) thc Q-saturatcd
mcthyl ketones show the I/С==О in the rcgion 1720 ::!: 25 cт 1. At thc HW
sidc CI 2 CHC(==O)Me (1743) and FCH 2 C(==0)Mc (1740 cm 1) clcarly sho\v the
influcnce of the halogen. At the LW sidc cPrC(==O)Mc absorbs at 1б97 cm l. Most
of thc saturated kctones are active а! 1715 ::!: 15 cm 1 and сусп at 1715 ::!: 5 cm 1
for R C(==O)Me compounds if R contains only mcthyl or methylcnc, branchcd
or not. Thc thioanhydride McC(==O)SC(==O)Mc absorbs at 17б9 and 1712 cm 1
Ьи! the thiol acctates do so in the rcgion 1б95 ::!: 15 cm l [80]. А hydrogcn bridgc
in aromatic methyl kctones produces а supplcmcntary lo\vcring of thc absorption
frcqucncy of the с==о stretching vibration: 2-НОРhС(==0)Мс shows thc I/С==О
at lб43 and 4 HOPhC(==O)Me at 1б4б cm l. Тhc vcry low valucs for thc
споl form [13] of МеС(==О)СН2С(==О)Мс (lб20) and McC(==S)CH 2 C(==0)Mc
(1бl0 cm l) are outside the abovc mcntioncd absorption rcgion of thc с==о
strctching vibration.
156 Noттl Vib1'llliolls t/Iltl AlJSOl1Jlioll Uegiolls о/ С(==Х) У
Mcthyl dсfоrшаtiопs
As сопtrаstсd witl1 thc wcak absorptions of tl1c шсtl1уl strсtсl1iпg viЬrаliопs, thc
шсtl1уl sушmсtriс dсfоrпшtiоп absorbs ПlОdсrаtсlу (о strongly.
ЬаМс b Me bsMe
1445 :!: 35 1430 :!: 40 13б5 :!: 25 cm 1
Мсtl1уl rocking vibrations and C C strctch
In most of the сошроuпds the C C strеtсhiпg vibrations arc coupled to thc methyl
rock (Sесtiоп 2.1.б)
рМс р'Мс I/C C
1085 :!: 70 985 :!: 85 90S:!: 95
Тhc с==о in planc dcformation
With thc cxccption of ХС(==О)Мс (Х = Н, Cl, Br, 1), the с==о deformation
in thc rcgion 580 :!: 115 cm 1 is describcd as the in planc с==о deformation.
Thc СН/С==О dcformation in НС(==О)Мс а! 764 cm l falls outside this
region, Ьи! ОС(==О)Мс rcvcals this vibration а! б68 cm l, which dcmonstrates
the infIucnce of thc light hydrogcn atom. Thc highcst wаvепuшЬеrs are
thosc for CINHC(==O)Mc (б93), s cis Н 2 С==СНС(==О)Мс (690) апd
McC(==O)NHC(==O)Me (648 and 560 cm l) and thc lowest ешеrgе in thc spectra
of IC(==O)Mc (4б5), cPrC(==O)Me (487) and HSC(==O)Me (525 cm 1). The
rcmaining valucs arc situatcd in the rcgion 585 :!: 55 cm ! with 530 cm 1, for
2 propanonc.
The с==о out of planc dcformation
Тhe с==о out-of planc dcformation occurs variably in the rcgion 505 :!: 115 cm ' .
High valucs originatc from thc spcctra of EtNHC(==O)Me and nBuNHC(==O)Me
(б20), DзSiOС(==О)Мс (618 cm 1, coincidcnt with ЬС==О) and methyl апd ethyl
acetatc with б07 cm '. Тhe lowest values сошс from НОС(==О)С(==О)Ме (394),
МсОС(==О)С(==О)Мс (403), FCH 2 C(==O)Me (404) and 3 PyC(==O)Me (405
cm 1). Тhc remaining out-of planc dcformations are observed in the range 500 :!:
100 cm 1.
Skclctal deformation and torsions
Тhe C(==O) Mc skclctal dcformation is wcakly (о moderately active in thc
region 345 :!: 130 cm ]. Тhe highcst valucs havc Ьееп attributed in thc spectra
7.1 CarbollY! Coтpouпds
157
of FC(==O)Mc (473), MC2NC(==O)Mc (473), EtOC(==O)Mc, CICH 2 OC(==O)Mc
and Н2С==СНОС(==О)Ме with 462 cm 1 and nBuNHC(==O)Mc with 450 cm 1.
А! thc lower limi1 а few RC(==O)C(==O)Mc compounds absorbs, such as thosc
with R = МсО (121), СI (230) and НО (258 cm 1). Thc rcmaining skcletal
dcformations arc situatcd а! 355 :i: 95 cm 1.
Thc mcthyl torsion mау Ьс expcctcd а! 190 :!: 80 cm 1 and thc acctyl torsion
а! 100:i: БО cm l.
ТаЫе 7.5 Absorption regions (cm 1) of the normal vibralions of C(==O)Mc
Vibration Q-saturated Q-unsaturatcd aromatic с==о bondcd
voMc 3005 :i: 40 3000 :!: 30 3010 :!: 10 3020 :!: 15
I/ Me 2990 :i: 30 2960 :!: 30 2975 :!: 25 2990 :!: 10
I/sMc 2905 :i: 65 2900 :i: 50 2925:!:: 15 2930:!: 10
I/С==О 1735 :i: 45 1675 :i: 35 ]680:!: 30 1720:!: 20
ЬоМс 1440 :i: 25 1425 :i: 15 1445:!: 25 1425:!: 15
b Mc 1425 :i: 15 1415 :!: 25 1445 :!: 25 141О:!: 20
bsMe 1365 :i: 25 1355 :i: 1 О 1360:!: 15 1350:!: 10
рМс 1085 :i: 70 1060:!: 40 ]070:!: 25 1095 :I: 45
р'Ме 985 :i: 85 1000 :!: 25 1020:!: 20 1015:!: 10
vC C 895 :i: 80 895 :i: 85 955 :!: 25 900 :I: 80
Ьс==о 555 :i: 70 615 :!: 80 605 :!: 20 595 :I: 55
')'с==о 460 :i: 50 455 :!: 45 445 :I: 45 475 :I: 85
b-c c 375 :i: 50 4]0 :i: 25 375 :!: 45 310 :I: 95
'orsion Мс 200 :i: 70 205 :!: 20 175 :I: 45
torsion С(==О)Ме 100 :i: 60 :::::150 :::::130
Vibralion N-bonded O-bonded S-bondcd Halogcn-bonded
I/омс 2990 :i: 20 3010:!: 30 3000:!: 10 3030 :I: 15
I/ Me 2965 :i: 35 2970 :!: 30 2990 :!: 10 3010:!: 10
I/sMc 2900 :i: 45 2910 :!: 40 2920 :!: 10 2945 :I: 25
I/С==О 1690 :i: 45 1750:!: 20 1725 :!: 45 1840:!: 30
ЬоМс 1450 :i: 30 1445 :!: 20 1435:!: 15 1430:!: 05
6 Mc 1440 :!: 20 1435:!: 15 1420:!: 10 1425 :!: 10
Ь,Мс 1365 :i: 10 1370 :!: 20 1355:!: 10 1365 :I: 15
рМс 1080 :i: 50 1050 :i: 30 1120:!: 20 1080:!: 30
р'Мс 995 :i: 55 975 :i: 45 1000:!: 65 1035 :!: 35
I/C C 915:i: 85 860 :!: 50 960 :!: 30 895 :I: 65
Ьс==о 625 :i: 70 620 :i: 30 575 :!: 55 535 :I: 70
')'с==о 530 :i: 90 600 :i: 20 480 :!: 50 500 :I: 70
b-c c 420 :i: 55 415 :!: 50 390 :!: 50 375 :I: 100
torsion Мс 160 :!: 50 170 :!: 40
torsion С(==О)Ме
R C(==O)Mc compounds
R = H [1 5], D [1, 2, 4], Mc [3, 10], Et [82], nPr ,
nBu , nPcnt , HOCH2 , MC2C(OH)CH2 , McC(==O)CH2 [11 JЗ],
158 NОПl/аl VilJraliol/s а1/(! Absorpliol/ Rcgiol/s о/ С(==Х) у
McC(==S)CH2 [13], FCH2 [14---16], CICH2 [16 18], BrCH2 (16],
CI2CH [19], iPr [20], cPr [21, 221, FзС 123], 1I2C==CH [24---
27], McCH==CH [24], N==N==CH and N==N==CD [28],
N==N==C(Mc) [29], HS(Mc)C==CH [30], HC=C [31], Pll [32
35],2-,3- and 4-ХРll (Х = Мс [35], FзС, H2N \35], 02N [35], НО [35, З6],
МсО [35[, F, СI [35,37], Br [35]), 2- and з-МсС(==О)Рll , 3- and 4-ЕtРll ,
з- and 4-N=СРll [35], 3-FS(==0)2Рll , 2-, 3- and 4-Py [38], 2-Th ,
2-Fu [81], 2-Pyr [39], HOC(==O) [40--43], McOC(==O) [41,44],
NaOC(==O) [41, 45], CIC(==O) and BrC(==O) [41], H2N [46 8],
McND [49 5З], McC(==O)ND [54, 55], Me2N [56--61], CI2N [62],
N lm , R'NH (scc Scction 9.3), HO [48, б3 69], OO [б4, 65,
б7], R'O (scc Section 10.2.3), HS and DS [70], McS [71],
McC(==O)S [72], F [73 77], CI [б9, 73 75], Br [2, 73 75, 78],
I [75, 77, 79].
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25. H.J. Oclichmann, О. Bougcard and В. Schradcr,J. Мо/. S/I'//ct., 77, 179 (1981).
26. J .R. Durig and T.S. Liltle, J. CI/em. PI,yS., 75, 3660 (1981).
27. J. Ос SП1сdt, F. Уап Houtcgcm, С. Уап A1scnoy, H.J. Gcise, B.J. Уап der Vckcn and В.
Coppcns, J. Мо/. S/rllc/., 195,227 (1989).
7.1 CarbollY/ COтpOllllds
159
28. А. Po'ctti, G. Paliani, M.G. Giorgini and R. Calaliotli, Spec/rochim. Ас/а, Par/ А, 31A,
1869 (1975).
29. G. Davidovics, F. Dcbu, С. Marfisi, М. Monnicr, J.P. Aycard, J. Pourcin and Н. Bodol,
J. Мо/. Strtlct.. 147,29 (1986).
30. О. SiiП1ап. J. Frcsco and Н.В. Gray, J. Лт. C/lem. Soc., 96, 2347 (1974).
31. G.л. Crowdcr, Spec/rucIIim. ЛС/а, Par/ Л, 29А, 1885 (1973).
32. W.D. Mruss and G. Zundcl, SpectrocIJil//. Ас/а, Par/ А, 26А, 1097 (1970).
33. J.H.S. Grccn and D.J. Harrison, Spec/roc/lim. Ас/а, Par/ А, 33А, 583 (1977).
34. А. Gamhi, S. Giorgianni, А. Passcrini, R. Visinoni and S. Ghcrsetti, Spec/rochim. Ас/а,
Part А, 36Л, 87] (1980).
35. G. Varsзnyi, Лssigf/l//еll/sfоr Vibra/iolla/ Spec/ra ofSevef/ Hrтdred Beпzeпe Derivatives,
J.Wilcy & Sons, New York (1974).
36. W.A.L.K. AI-Rashid and М.Е EI-Bermani, Spec/rocIJim. Ас/а, Par/ А, 47А, 35 (1991).
37. Д, Gambi, S. Giorgiani, Д, Passcrini and R. Visinoni, Spectroc/lim. Acta, Рап А, 38А,
871 (1982).
38. KG. Mcdhi, /lIdiall J. P/,yS., 51A, 399 (1977).
39. J.c. Viljoen and А.М. Hcyns, Spectrosc. Le/l., 20, 765 (1987).
40. Н. Hollens'cin, F. Лkсrrnапп and Н.Н. GUnthard, Spec/roc/lim. Ас/а, Part А, 34А, 1041
(1978).
41. W.J. Ray and J.E. Ка'оп, Spec/roc/lil//. Ас/а, Par/ А, 36А, 793 (]980).
42. W.J. Ray, J.E. Katon and О.В. Phillips, J. Мо/. S/rtlc/., 74, 75 (1981).
43. J. Murto, Т. Raaska, Н. Kunttu and М. Riisancn,J. Мо/. S/rllc/., 200, 93 (1989).
44. J.K. Wi'П1shurst and J.F. Horwood, AlIs/. J. C/rem., 24, 1183 (1971).
45. J.E. Ка'оп and О.Т. Coving'on, Spec/rosc. Le/l., 12,761 (1979).
46. N. Jonathan, J. Мо/. Spec/rosc., 6, 205 (1961).
47. Т. Uno, К. Machida and У. Sai'o, BIIII. С//С/n. Soc. JPll., 42, 900 (1969).
48. S.T. King, Spec/rocIIim. Ас/а, Par/ А, 28А, 165 (1972).
49. В. Schneidcr, Д, Horeni, Н. Picova and J. Honzl, Collec/ Czecll. Cllem. Соттип., 30,
2196 (1965).
50. Н. Pivcova, В. Schncidcr and J. Stokr, Collec/ Czec/I. Cllem. COтmll1J., 30, 2215 (1965).
51. Д, Warshcl, М. Levitt and S. Lifson, J. Мо/. Spec/rosc., 33,84 (1970).
52. J. Jakes and S. КriП1П1, Spec/roc/lim. Acta, Part А, 27А, 19 (1971).
53. М. Ray-Lafon, М.Т. Forel and С. Garrigou-Lagrangc, Spec/rocllim. Асш, Part А, 29А,
471 (1973).
54. У. Kuroda, У. Sai'o, К. Machida and Т. Uno, Spec/rocllim. Ас/а, Par/ А, 27А, 1481
(1971).
55. У. Kuroda, У. Saito, К, Machida and Т. Uno, SpectrocIJim. Асщ Part А, 29А, 411
(1973 ).
56. R.L. Jones, J. Мо/. Spec/rosc., 11, 411 (1963).
57. С. Garrigou-Lagrangc, С. Ое Loze, Р. Васс10П, Р. Combclas and 1. Dagaul, J. СЫт.
P/,yS., 67, 1936 (1970).
58. G. Durgaprasad, D.N. Sathyanarayana, с.с. Patcl, H.S. Randhawa, А. Gocl and C.N.R.
Rao, Spectrochim. Ас/а, Part А, 28А, 2311 (1972).
59. Z. Mielkc and AJ. Bames, J. Cllem. Soc. Faraday Tralls. 2, 82, 437 (1986).
60. д'М. Dwivcdi, S. КriП1m and S. Mierson, Spec/roc/lim. Ас/а, Par/ А, 45А, 271 (1989).
61. У.У. Chalapa'hi and К.У. RаП1iаh, Proc. /lIdian Acad. Sci" 68А, 105 (1968).
62. J.E. Dcvia and J.c. Carter, Spectroc/liт. Ас/а, Par/ А, 29А, 613 (1973).
63. J.к. Wilmshurs', J. С//ет. P/,yS., 25, 478, 1171 (1956).
64. М. Haurie and Д, Novak, SpeclrocIIim. Acla, 21, 1217 (1965).
65. О. Clague and Д, Novak, J. Мо/. SIrIlC/., 5, 149 (1970).
66. J.L. Dcrissen,J. Мо/. Strllc/., 7, 67 (1971).
160 Noпllal VilJraliolls а//(! AlJSOlplioll Regiolls о/ с(==х) у
67. Р.Е Кrause, J.E. Kalol1, J.M. Rogcrs and О.В. Phillips, Арр/. Spec/rosc., 31, ] 10 (1977).
68. Н. HollcnslCil\ and Н.Н. GUl1tl\3ld, J. Mol. Spec/rosc., 84, 457 (1 '180).
69. R. Fausto and J.J.c. Teixcira-Dias, J. Мо/. S/1'IIc/., 144,2'5 (1'186).
70. H.S. Ral1dlta\va, W. Walter and С.О. Mcesc, J. Mol. S/1'IICI., 37, 187 (1977).
71. А. Sпюldсrs, G. Macs and Т. Zccgcrs-Huyskcns, J. Мо/. S/1'IICI., 172, 23 (1988).
72. В. Fortunato, M.G. Giorgini al1d Р. Mironc, J. Mol. St1'llct., 25, 237 (1975).
73. J. Ovcrcnd, R.A. Nyquist, J.c. Evans and W.J. POIIS, Speclroc//im. Ас/а, 17, 1205 (1961).
74. J.c. Evans and J.Overcl1d, Speclrocllim. АС/а, 19,701 (]963).
75. J.A. RаП\sау and J.A. Ladd, J. C/lem. Soc. В, 1]8 (1968).
76. с.у. Встеу and А.О. Com\icr, Spect/'Oc//im. Ас/а, Par/ А, 28А, 1813 (1972).
77. S. Tsuchiya,J. Мо/. S/rl/ct., 22, 77 (1974).
78. L.C. НаН and J. Ovcrcnd, Spectroc//im. Ас/а, Par/ А, 23А, 2535 (1967).
79. F.N. Nicolaiscn and J.S. Hansen, Ас/а C/lem. Scalld., Ser. А, 38А, 453 (1984),
80. R.A. Nyquist and W.J. POIIS, Spec/roc/lim. Acta, 15,514 (1959).
81. М. Senechal and Р. SаuП\аgпе,J. СЫт. P/,yS., 69, 1246 (1972).
82. J.R. Ourig, F.S. Feng, А. Wang and Н.У. Phan, Call. J. C/lem., 69, 1827 (1991).
7.1.6 Propionyl (propanoyl)
Thc С(==О)СН2СНЗ slructure unit possesses 24 normal vibrations, of which 18
arc dcrivcd frоП1 thc cthyl group. Thc rcmaining six are described as follows:
I/С==О, I/C(==O) C, ЬС==О, ')'с==о, Б-С(==О) С and torsion,
Evidcntly thc concepts in plane and out of plane lose their meaning if the moleculc
has по plane of symme1ry. In this case thc с==о in plane and out of plane
dcformations arc skclctal defonnations also, partly dcpcndcnt оп the Q atom.
Methyl and methylcnc slrctching vibrations
Thc fivc СН stretching vibrations are situated between 3000 and 2820
cm 1. Thc 1/0Ме in ХС(==О)Е! compounds (Х = F, Cl, Br) absorb in the
neighbourhood of 3000 cm 1 and the lowcst I!,CH 2 is assigncd in the spectrum of
EIC(==O)NHC(==O)Et (2820 cm l). Disregarding thcsc cxtremc values, the СН
stretching vibrations arc observcd bctwccn 2990 and 2870 сm 1 :
1/0Ме I/ Me l/оСН2 I/sMc I/sCH2
2980::1: 10 29б5::1: 25 2930::1: 25 2915::1: 25 2905::1: 35
Thc с==о strctching vibration
With the exception of FC(==O)Et, thc с==о stretching vibration provides а strong
absorplion in the rcgion 1740 ::1: 90 cm 1. Thc highest wavcnumbers are due to
ХС(==О)Е! (Х = F, CI, Br) with, respectivcly, 18б2, 1830 and 1815 cms l, wl1ich
clcarly dcmonstrates the influcnce of the halogen. Likcwise in the HW rcgion опе
7.1 Carbol/yl Compoullds
161
finds 1hc cstcrs of propanoic acid: EtC(==O)OMc (1744), EtC(==O)OEt (1740) and
EtC(==O)OiPr (1734 cm 1). AIiphatic kctoncs with thc formula R C(==O)Et in
which R = Et, nPr, iPr, пВи, iBu, nPcnt, BrCH 2 , CICH2CH2, МсС(==О) and
PllCH2 absorb in thc narrow rcgion 1715 :1: 2 cm l. Conjugation rcsults in а
considcrabIc lowcring of thc wavcnumbcr of I/С==О, as in СН 2 ==СНС(==О)Е!
(J685) and PhC(==0)E1 (1688 cm I), Ьи! halogcn subs1itutcd phcnyl cthanoncs
absorb somcwhat highcr: 4-СIРhС(==0)Е1 (1б91) and 3, 4-СI2РhС(==О)Еt (1б9б
cm 1). Jn dclimiting thc absorption rcgion of I/С==О, thc additionallowcring of
thc wavcnumbcr Ьу ап intramolccular hydrogcn bridgc is по! takcn into account,
for cxample: 2-НОРhС(==0)Е1 (1642 cm I). Тhc propionamidcs aIso absorb in
tllc LW region: EtC(==0)NH 2 (1660), E1C(==0)NHMc (1653), EtC(==O)NHEt
(1650), EtC(==O)NHPr (1б53) and EtC(==0)NMc2 (1б51 cm I).
Mcthyl and mcthylene dcformations
Thc methyl dcformations arc found in thc samc rcgions as thosc of Q-saturatcd
cthyl; the mcthyIcne scissors absorbs а! lower wavcnumbcrs. Тhc intcnsity of the
bands is moderatc (о strong.
ЬоМе b Mc ЬСН 2 bsMc
1470:1: 15 1455:1: 15 1425:1: 20 1380:1: 15 cm 1
Тhc mcthylene wag and twist givc rise to wcak or modcratc bands in thc rcgions
1340:1: 40 and 1265 :1: 25 cm 1.
Mcthyl rocks and C C stretching vibrations
In thc spcctra of R C(==O)Et compounds thc C C strctching vibrations and
thc mcthyI rocks are rcsponsibIe for four absorption rcgions. Thcsc vibrations arc
coupled in such а way to make it difficult to dctcrminc which vibration has thc
grcatcst con1ribution in а distinct absorption. Somctimcs thc vC(==O) C, with
the highcst wavenumber, is callcd thc antisymmctric strctch and thc I/C Mc, with
the lowest wavcnumber, the symmetric strctch [13, 1б].
рМе р'Ме I/C(==O) C I/C Mc
1130:1: БО 1050:1: 50 1015:1: БО 920:1: 80 cm 1
Mcthylcne rocking vibration
Тhc mcthylene rock providcs а weak to modcratc band а! 805 :1: 30 cm l, а rangc
comparabIe with that of the Q unsaturatcd cthyl compounds. X C(==O)E! (Х =
CI, Br) shows this РСН2 а! the LW sidc ( 784 cm 1) and ОС(==О)Е! а! thc HW
sidc а! 833 cm l,
lб2 Normal Vibтlio//s a//d AbsOlplio// Regio//s о/ с(==х) у
The с==о dеfоrпшtiопs
The absorption in tlle range 585 :1: 115 cm 1 is usually assigned 'о tlle с==о
in planc dcformation. Нigll valucs origiIlate from tlle spectra of nPrNHC(==O)Et
(700) and EtNHC(==O)Et (659 cm l) and lo\v valucs from tllOSC of BrC(==O)Et
(470) and CIC(==O)Et (505 сш I), in whicll tllc iпПuспсе of tllC halogcn catches
thc сус, Most ot' the с==о in-plane dcformations lшvе Ьееп observed а! 620 :1: 65
cm 1.
Thc с==о out of-planc dеfоrшаtiоп appcars in the rangc 520 :1: 90 cm 1.
Thc HW sidc of tl1is region is dеliшitеd Ьу 608 сш l from tlle spectrum of
EtC(==O)NDC(==O)Et (\vith the second ')'с==о а! 545) and Ьу 430 cm 1 in
that of 2 ThC(==O)Et. The remaining с==о out-of plane dcformations absorb in
the rcgion 520 :1: 70 cm 1.
Skelctal dcformations
Thc vibrational analysis of R C(==O)Et compounds rcveals two skeletal
dcformations: а dcformation with thc cthyl group and ап extcrnal dcformation.
Тhc lowcr limits arc dctcrmincd Ьу thc skelctal deformations of BrC(==O)Et а!
29б and 20б cm '.
bC(==O) C C
375 :1: 85
bR C(==O) C
2БО :1: 55
ТаЫс 7,6 Absorplion rcgions (СП1 l) of the попnаl vibralions of
C(==O)E!
Vibration Rcgion Vibration Rcgion
1/0Ме 2985 :1: 15 рМе 1130 :1: 60
I/;МС 2970 :1: 30 р'Ме 1050 :1: 50
l/ о СН 2 2930 :1: 25 I/C(==O) C 1015 :1: 60
I/.,Мс 2900 :1: 40 I/C Mc 920 :1: 80
I/ s CH 2 2880 :1: 60 Р СН 2 805 :1: 30
I/С==О 1740:1: 90 Ьс==о 585 :1: 115
ЬоМс 1470 :1: 15 ')'с==о 520 :1: 90
Ь;Мс 1455 :1: 15 bC(==O) E! 375 :1: 85
Ь СН 2 1425 :1: 20 b-C(==O) C 260 :1: 55
bsMe 1380 :1: 15 torsion Мс 220 :1: 30
WCH2 1340 :1: 40 'orsion Е! 130 :1: 70
ТСН2 1265 :1: 25 'orsion С(==О)Е'
Тhc following R C(==O)Et compounds arc taken into account:
R = H [1 3], D [2], Mc [19], Et [4], nPr , nBu , nPent ,
BrCH2 , CICH2CH2 , PhCH2 , iPr , McC(==O) , CH2==CH ,
7.1 Carboпy/ Coтpoltпds
1б3
Ph , 4 McPh , 2 and 4 HOPh [9, 20], 4-МеОРh , 4-РhСН20Рh ,
4 FPh [6], з and 4 CIPh [б], 4-ВrРh [б], 3, 4-СI2Рh , 2-
Тh [5], McNH , EtNH and nPrNH [7], EtC(==O)NH and
EtC(==O)ND [8], HO [10 12], DO [10, 12], McO [13, 14],
СDзО [13], ЕtO , NaO [18], F [15, 1б], CI [15, 17], Br [15].
References
1. G. Sbrana and У. Schcttino, J. Mol. Spec/rosc., 33, 100 (]970).
2. S.G. Frankiss and W. Kynaston, Spec/rocl/im. Acla, Рап А, 28А, 2]49 (1972).
3. Р. Уап Nuffcl, L. Уап den Enden, С. Уап Alscnoy and H.J. Gcisc, J. Мо/. S/rиc/., 116,
99 (1984).
4. Z. Buric and P.J. Krucgcr, Spec/roc//im. Ас/а, Par/ А, 30А, 2069 (1974).
5. J.J. Peron, Р. SаUП1апgс and J.M. Lebas, Spec/rocl1im. Ас/а, Par/ А, 26А, 1651 (1970).
6. W.A. Sclh Paul and J. Mccuwcsen, Bиll. Soc. C/lim. Be/g., 90, 127 (1981).
7. J. Jakcs and S. КriП1m, Speclrocllim. Ас/а, Par/ А, 27А, 35 (J971).
8. У. Kuroda, К. Machida and Т. Uno, Spec/rocl/im. Ас/а, Par/ А, 30А, 47 (]974).
9. W.A.L.K. AI Rashid and M.F. EI-Bcrrnani, Spec/rocl/im. Асla, Par/ А, 47А, 35 (1991).
10. У. Mikawa, J.W. Brasch and R.J. Jakobscn,J. Мо/. S/rиc/., 3, 103 (1969).
11. R.J. Jakobsen, У. Mikawa, J.R. Allkins and G.L. Carlson,J. Мо/. S/rиct., 10, 300 (1971).
12. J. Umemura, J. Мо/. S/rllcl., 36, 35 (1977).
13. R.M. Moravic and J. Corscl,J. Mol. Strиc/., 24, 91 (1975).
14. R.M. Moravic and J. Corsct,J. Мо/. S/rиcl., 30,113 (1976).
15. G. Frankiss and W. Kynaston, Spec/roc/lim. Acla, Parl А, 31А, 661 (1975).
16. J.R. Ourig, G.A. Guirgis and Н.У. Phan,i. Ramall Speclrosc., 21,359 (1990).
17. S. Oyngcseth, s.н. Schci and К. Hagcn,J. Мо/. S/rиc/., 116,257 (1984).
18. Е. Spinner, Р. Yang, Р.т.т. Wong and Н.Н. ManlSch, AlIs/. J. C/lem., 39, 475 (1986).
19. J.R. Ourig, F.S. Fcng, А. Wang and Н.У. Phan, Са//. J. Cllem., 69, 1827 (1991).
20. G. Varsanyi, AssigllIIIe/l/s for Vibra/iolla/ Spec/ra ofSevell HlIlldred Be//zelle Deriva/ives,
J.Wilcy & Sons, Ncw York (1974).
7.1.7 Carboxyl
Тhc nine normal vibrations of thc C(==O)OH group arc dcscribcd as foIlows:
1/0Н, I/С==О, ЬОН, //C O, 1 ОН, ЬС==О, 1 с==о, b-C O and torsion.
Carboxylic acids are best charactcrizcd Ьу thc ОН strctch, thc с==о stretch
and thc ОН out of plane dcformation and сусп Ьу thc c o strctch and the ОН
in-plane deformation.
Тhc ОН stretching vibration
Тhc vcry broad band with а maximum absorption а! З050 :1: 150 cm 1,
charactcristic of carboxylic acids, is duc to thc associated ОН ...0 strctching
vibration of mainly cyclic dimcrs. Тhc typical shoulders оп thc low frcqucncy
164 Norl1lal Vib/'Qlio//s ат! Absorplio// Rcgio//s о/ С(==Х)У
wiпg arc assigncd to ovcrtoncs апd сошЫпаtiопs of ЬОН al1d //c o, спlшпссd
Ьу Fcrmi rcsonancc. Iп saturatcd carboxylic acids tl1is //01-1. . .0 appcars iп thc
viсiпitу of З050 cm 1, ТllC ехас! wаvспumЬеr of 1his broad band is difficult to
dctcct becausc of thc СН strсtсhiпg bands supcrimposcd оп Н. F з СС(==О)ОН and
С1зСС(==0)ОН absorb а! 100 cm 1 higllcr апd bcnzoic acids а! approximatcly
100 cm l lowcr. Еуеп in dilutc solutions this band does по! disappcar complc1ely,
апd thc absorption in thc ncigllbourhood of 3500 cm ' is due to tllC frcc ОН
strсtсl1iпg vibration.
Thc с==о strсtсl1iпg vibration
ТllC с==о stretching vibration in the spectra of carboxylic acids givcs rise to а
strong band in thc region 1725 :1:: 65 cm 1. In tlle vapour state the monomcr
absorbs а! а wavcnumbcr 50 cm 1 highcr. The extcnsive rcgion of the saturatcd
carboxylic acids (17З5 :1:: 50 cm l) is attributable to thc higher values in the
spcctra of Q fluoro and Q chloro acids and to thc lowcr valucs, суеп to 1б85 cm 1,
in thc spcctra of dicarboxylic acids. Thc foHowing scrics iIIustrates the influcncc
ofthc halogcn: F з СС(==О)ОН (1785), F2CHC(==0)OH (17б6), FCH 2 C(==0)OH
(1730), Сl з СС(==О)ОН (1751), CI2CHC(==0)OH (1740) and CICH2C(==0)OH
(172З cm 1). In most of thc saturatcd carboxylic acids thc I/С==О is found
1! 1720:1:: 20 cm ', а rcgion that narrows to 1710 :1:: 5 cm ' for the serics
МС(СН2)IIС(==0)ОН (// = D---1б) [99]. Benzoic acids absorb а! 1б80 :1:: 20 cm ',
but the I/С==О of the thrcc isomcric pyridinecarboxylic acids faH outside this
rcgion ( 1715 cт 1) [97].
Thc ОН in planc dcformation
The ОН...О in planc dcformation, couplcd to thc c o strc1ching vibration, is
easy to obscrvc as а broad band with mcdium intcnsity, occurring in the region
1395:1:: 55 cm l. Thc sharp peaks of the СН deformations supcrimposcd оп it make
it some\vhat difficult to dctcct thc схас! wavenumbcr of this ОН deformation. Thc
highcst wa\'cnumbcrs havc Ьссп traccd in thc spectra of F з СС(==О)ОН (1450)
and F 2 CHC(==0)OH (1445) and thc lowcst in thosc of НС(==О)ОН (1340) and
НО(О==)СС(==О)ОН (1345 and 1395 cm t). Most of the carboxylic acids show
thc ЬОН...О а! 1415:1:: 25 cm 1. Thc frcc БОН of thc mопоmсr in thc vapour
statc occurs а! wavcnumbcrs approximatcly 50 cm l lower.
Thc c o strctching vibration
Thc c(==o) o stretching vibration, couplcd to the ОН in plane deformation,
cxhibits а modcrate to strong band in thc rcgion 1250 :1:: 80 cm l. Нigh valucs
appear in thc spectra of 2 PyrC(==0)OH (1329) and 4 BrPhC(==0)OH (132З) and
low valucs in thosc of N=:CCH 2 C(==0)OH (1173) and НО(О==)СС(==О)ОН
7.1 Carboпyl Coтpoullds
1б5
(1173 and 1230 cm I). Thc rcmaining carboxylic acids dispJay this vibration in
tllc rcgion 1260:1: 60 cm l. Hcxancdioic acid givcs both strctchings а! 1300 and
1280 cm 1. In thc scrics Мс(СН 2 )"С(==0)ОН (ll = ()"",lб) this rcgion is 1285 :t
10 cm 1. Monomcr acids in thc уарош slatc absorb :::::100 cm 1 lowcr.
Тhc ОН oU1 of pJanc dcformation
TllC 1 ОН. ..0 or out-of-planc ОН...О wag cxhibits а moderatc band in thc
shapc of а У in thc rcgion 9О5 :1: 65 cm ! [96]. Тhe highest valucs соmс from
H 2 NC(==0)C(==0)OH (970), НО(О==)ССНМсС(==О)ОН (970 and 930) and
НО(0==)СС(==0)СН 2 С(==0)ОН (9БО and 940 cm I). Q-Halogcn compounds
such as CICH2C(==0)OH (843) and Сl з СС(==О)ОН (849 cm l) arc rcsponsibIc
for thc lowcst wavcnumbcrs. UsuaIly 1hc 1 ОН. . .0 in carboxylic acids occurs а!
920 :1: ЗО cm l and in thc scries Ме(СН2)"С(==0)ОН (п = ()"",lб) а! 9З5 :t 5
cm l. In thc unbound state 1he 1 ОН disappcars to makc place for thc frcc torsion
а! lower wavcnumbers (:::::б50 cm I).
Тhe с==о in plane deformation
Тhc С==О in planc deformation is wcakly to modcrately activc in thc rcgion 725
:t 95 cm l. The highcst values arc obscrvcd in thc spcctra of 2-ХРhС(==0)ОН
(Х = F, Cl, Br) (:::::820 cm 1), 2 McPhC(==0)OH (809) and bcnzoic acid
(802 cm I). Acctic acid (б30), ICH 2 C(==0)OH (б35), EtC(==O)OH (640),
BrCH 2 CH 2 C(==0)OH (б40) and FCH2C(==0)OH (64б cm 1) scorc а! low wavc-
numbcrs, Ьи! formic acid and thc remaining n alkanoic acids display this 6С==0
in the vicinity of б70 сm t. Most carboxylic acids show thc с==о in-planc
dcformation а! 715 :1: б5 cm l with thc bcnzoic acids to thc HW side of this
rcgion. Тhcsc valucs arc in good agrcemcnt with thosc of mcthyl and cthyJ cstcrs
(715:1: 115 cm 1), but thcy arc significantly highcr than thc сопсsропdiпg valucs
in RC(==O)X (Х = Ме or Et) compounds (580 :t 115 cm t).
Тhc с==о out of planc deformation
Thc с==о out of-planc dcformation absorbs wcakly to modcratcly in thc cxtcnsive
rcgion 595 :1: 120 cm t. The highest wavcnumbcrs arc 715, 703, 702, б98 and
б93 cm 1 respectivcly from thc spcctra of 4-ХРhС(==0)ОН (Х = 02N, FзС,
Et, H 2 N and ОН) and the lowest соmс from H 2 NC(==0)C(==0)OH (480) and
ICH 2 C(==0)OH (485 cm 1). For acctic acid and propanoic acid thc \vavcnumber
is БОО cm 1 and for thc rcmaining n-alkanoic acids wavcnumbcrs are in thc
ncighbourhood of б30 cm l. Most carboxylic acids display thc "( с==о in а range
(595 :t 85) which is in the vicinity of that of mcthyl and cthy! cstcrs (б35 :t 130)
Ьи! higher than that of mcthyl and ethyl ketoncs (505 :t 115 cm 1).
166 Norтal Vib,'aliollS alld Absorplioll Regiolls о/ с(==х) у
ТllC c o dcformation
In thc C(==O)O dсfоrшаtiоп or C(==O)O rock, thc асссп! lics much
morc оп the c o dсfоrnшtiоп tlшп оп tllc с==о dcformation. This band
has а \vcak to шсdiuш intcnsity and makcs its appcarance in tllc cxtcnsive
rcgion 445 :!: 120 cm 1. ТllC highest wаvспuшЬсrs are assigncd in thc spcctra
of substitutcd bcnzoic acids (530 :!: 35 cm 1). Low valucs arc attributed in
thc spcctra of H2NC(==O)C(==O)OH (З26), НС(==О)С(==О)ОН (3б5) and
НО(О==)ССН2СН2С(==О)ОН (388 and 545 cm 1). Tl1is rcgion agrccs witll that
of the corrcspondil1g vibratiol1 in thc spcctra of mcthyl and ethyl csters (435 :!: 95
cm 1).
ТаЫе 7.7 Normal vibrations and absorp'ion rcgions (cm 1) of C(==O)OH
Vibration Q-sa'urated С==О bondcd Q-unsaturalcd aromalic
1/0Н. . .0 3050 :!: 50 3150:!: 50 3000 :!: 50 2950 :!: 50
I/С==О 1735 :!: 50 1730:!: 30 1690 :!: 20 1680 :!: 20
ЬОН.. .0 1395 :!: 55 1395 :!: 55 1400 :!: 40 1415 :!: 25
I/C O 1245 :!: 75 1220 :!: 50 1270 :!: 50 1300 :!: 30
/,ОН...О 905 :!: 65 905 :!: 65 900 :!: 50 900 :!: 50
Ьс==о 705 :!: 75 705 :!: 75 725 :!: 75 770 :!: 50
/,с==о 580 :!: 100 565 :!: 85 590 :!: 60 660 :!: 55
pc(==o) o 465 :!: 80 395 :!: 70 490 :!: 50 530 :!: 35
torsion
R C(==O)OH compounds
R = H [1 12], o [1 5], Mc [10, 11, 13 18], СDз [14, 17],
Et [19 21], McC02 [21[, СDзСD2 [19], Me(CH2)" (п== 2
1б), KO(O==)CC(MC)2CH2CH2 [22], HO(O==)CCH2CH2 [23, 24],
HO(O==)C(CH2)4 [25], HSCH2CH2 [26J, CICH2CH2 ,
BrCH2CH2 , iPrCH2 , HO(O==)CCH2 [27], KO(O==)CCH2 [28],
HO(O==)CC(==O)CH2 [31], PhCH2 , N=CCH2 [29], HOCH2 ,
HOC02 and HOCHO [3О], HSCH2 , HO(O==)CCH2SSCH2 ,
HO(O==)CCН(OH)CH2 and НО(О==)ССН(SН)СН2 [26J, FCH2
[З2], CICH2 [33 3б], BrCH2 [37], ICH2 [38], HO(O==)CCН(Mc)
[39], iPr , cPr [4Q.--42] , cBu [43, 44], CPCl1t [45], cHex ,
F2CH [32], CI2CH [4б, 47], FCICH and FCICD [48], (Bи [49],
HO(O==)CC(MC)2 OO(O==)CC(Me)2 and KO(O==)CC(Me)2 [50],
FзС [11, 32, 51 58], СlзС [4б, 59, БО], FзССF2 [61], Н(O==)C [б2,
б3], McC(==O) [б4--б7], CH20C(==O) , CH02C(==O) and
СDзС(==О) [64], HO(O==)C [б8, б9), H2NC(==O) [7 7З],
McO(O==)CCH2C(==O) [74], H2C==CH [75 77], H2C==C(Mc) ,
McCH==CH , HO(O==)CCH==CH and HO(O==)CCO==CO
7.1 Carbollyl Compounds
1б7
[78], KO(O==)CCH==CH [79], McO(O==)CCH==CH [80],
HO(O==)CCH==CH CH==CH [81], HC=C [82], Mc(CH2)4C=C ,
2 ThC=C , HO(O==)CC=C , Ph [834!5, 95], 2-ХРh (Х = Мс [85,
90], НО(О==)С [87, 88, 90, 95], H 2 N [90], McHN [8б], Mc 2 N [8б], 02N
[95], F [85], СI [85, 90], Br [85]), 3-ХРh (Х = Мс [85,91], НО(О==)С
[88,91], НО [91,95], МсО [91], H 2 N [91], +Н з N [89], 02N [95], F [85],
СI [85,91,95], Br [85], FS(==O)z), 4 XPh (Х = Мс [85, 92], Et, F з С,
НО(О==)С [88, 92, 93, 95], I-I(О==)С, H2N [92,95], MC2N [94], 02N [95],
НО [92, 95], МсО [92], ЕЮ, F [85, 95], СI [85, 92, 95], Br [85, 95], 1,
MCS(==0)2, FS(==0)2, H2NS(==0)2), 2 , 3 and 4-Py [97], 2-Fu [98],
2 Th, 2 Pyr ,
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1б9
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7.1.8 Methoxycarbonyl
Thc C(==O)OMc group is responsiblc for cightccn normal vibrations, of which
twclvc are due to the OMc and thc rcmaining six 10 thc C(==O)O structurc
unit:
I/омс (2), I/sMe, I/С==О, 8 0 Ме (2), bsMe, I/C(==O) O, рМе (2), vO C, ьс==о,
'УС==О, b C(===O) O, 8C 0 C and thrcc torsions.
Mcthyl stretching vibrations
In mcthyl estcrs the mcthyl antisymmctric strctching vibrations arc regularly
scen аЬоус 3000 cm l (Section 2.1.7). Halogcn-substitutcd acids scorc highest:
FC(==O)OMc (3047), CIC(==O)OMc (3044) and С1зСС(==О)ОМс (3040 cm 1).
Thc с==о strctching vibration
Thc most charactcristic band of csters ariscs from the с==о strctching
vibration occurring а! 1750 :!: 50 сm 1 with а strong to vcry strong
intensity. The exceptionally high wavcnumbcrs for FC(==O)OMc (1854) and
МсОС(==О)ОС(===О)ОМе (1830 and 1765 cm 1) and thc vcry low wavcnumbers
for КОС(==О)ОМе (lб80) and 2 HOPhC(==0)OMc (lб79 cm 1, intramolecular
H-bridgc) are outside this rcgion. Most mcthyl estcrs of a-saturatcd carboxylic acids
170 Noттl Vibтliolls alld Absorplioll ИеgiОIlS о/ с(==х) у
absorb а! 1745:1: 15 СП1 1 if tllc influcncc of thc IJalogcn is по! too substantial,
such as in FC(==O)OMc (1854), CIC(==O)OMc (1787), FзСС(==О)ОМс (1793)
and Сl з СС(==О)ОМс (1771 cm l). For МС(СН2)"С(==0)ОМС (11 = 1 20), this
rcgion narro\vs to 1743:1: 2 cm 1 [68]. Mcthyl cstcrs of n-unsaturatcd and aromatic
carboxylic acids SIIO\V tlle I/С==О а! 1725 :1: 20 cm 1. Seth Раиl and Уап Ouysc
[64] idcntificd thc rcgion 1730 :1: 15 СП1 1 for mопо and di substitutcd mc1hyl
bcnzoatcs and Nyquist [65] proposed 17З3 :1: 5 cm 1 for o plJtalic csters.
Mcthy\ dcformations
More often than по! both methy\ апtisуmП1еtriс deformations occur а! the same
\vаvеПUП1Ьсr (1460 :1: 25 cm 1). Thc high wavcnumber of the П1еthуl symmctric
dcformation (1435 :1: 15 cm I), displayed а! tlle LW sidc of the 1/ 0 Ме, is
remarkabIc. ТlIC \ow wаVСПUП1Ьсrs for bsMe in the spectra of H2NC(==0)OMc
(1369) and C12NC(==0)OMc (138б cm 1) are outside the above mentioned
region.
Thc C(==O) O strctching vibration
This vibration, oftcn considcrcd as the C O antisymmctric stretch, appcars
stronglyat 1255 :1: БО cm l, а region in good agrcemcnt with that of the I/C O
in carboxylic acids (1250 :1: 80 cm 1). Тhc highcst wavenumbcrs are furnishcd Ьу
such compounds as ХС(==О)СН==СНС(==О)ОМе (Х = С\, НО, 00 and NaO)
(:::::1315 cm 1) follo\vcd Ьу КОС(==О)ОМс (IЗI0), Н 2 С==С(Ме)С(==0)ОМс
(1307) and МсО(О==)СОС(==О)ОМс (1303 cm 1). Тhe lowest valucs соmс from
H2NC(==0)OMe (1195) and CI2CHC(==0)OMc (119б cm J). The remaining
compounds show thc I/C(==O) O а! 1245 :1: 45 cm l, with methyl formate
(1215) and mcthyl acctatc (124б cm l) as cxamplcs. lп addi1ion to the I/С==О,
this vibration is charactcristic for cstcrs.
Mcthyl rocks
With the cxccption of CI 2 NC(==0)OMc (1071 cm l), the рМе has Ьссп observed
а! 1185 :1: З5 cm 1, oftcn as а shouldcr оп thc \ow frequency wing of thc
I/C(==O) O absorption. In iPrC(==O)OMe this рМе (1194) is next to thc
I/C(==O) O (1202) Ьи! in tBuC(==O)OMe both vibrations coincide а! 1193 cm l.
Oisrcgarding the low values of 1075 and 1050 cm l respectivcly originating
from thc spcctra of H 2 NC(==0)OMc and CI 2 C(==0)OMe [55], the р'Ме absorbs
а! 1155 :1: З5 cm 1.
Тhe O C strctching vibration
Thc O Mc strctch, couplcd with thc methyl rock, appears in the widc
rcgion 975 :1: 125 cm 1 with ап intcnsity varying from wcak to strong. Тhis
vibration is oftcn called the symmetric СОС strctching vibration. Тhe high
7.] CarbollY/ Compoullds
171
values originated from cPrC(==O)OMe (1098), EtC(==O)OMc and iPrC(==O)OMc
(1091), КОС(==О)ОМе (1080) and PhNHC(==O)OMc (10б8 cm l) appcar
probabIy under the influence of thc mcthyl rock. Тhc lower wavcnumbcrs from
thc compounds Н 2 С==СНС(==О)ОМе (853), МсО(О==)СС(==О)ОМс (859),
DзСС(==О)ОМе (863), DС(==О)ОМе (878) and H2NC(==0)OMc (880 CJП 1)
соmе more in the neighbourhood of the frec I/ s COc. MOS1 Мс esters display thc
yO Mc at 980 :!: 80 cm 1 but it is not а good group vibration.
Тhe с==о deformations
Morc than опсс it happens that both dcformations arc assigncd а! thc samc wave
number,
Thc ЬС==О has Ьссп traced in the rcgion 715 :!: 115 cm I, limitcd Ьу 830
cm ' from CI2NC(==O)OMe followcd Ьу 82б cm 1 from КОС(==О)ОМс and
797 cm 1 from МеОС(==О)ОМе оп thc опе sidc and Ьу БОО cm 1 in thc
spcctrum of D з СС(==О)ОМе оп the other side. Gcncrally this vibration appcars
modcratcly а! 710 :!: 80 cm 1. Fluoro compounds such as FC(==O)OMe (789)
and F з СС(==О)ОМе (780) score higher than cstcrs of II-alkanoic acids such as
МсС(==О)ОМе (б40) and EtC(==O)OMe (б71 cm I). Thc absorption at б90сm ]
in thc spectrum of CIC(==O)OMc is assigncd to thc /,с==о (Scction 7.1.3).
Thc /' с==о absorption varies within the largc rcgion б35 :!: 130 cm 1 with а! thc
HW sidc DС(==О)ОМс (7б5), CI2NC(==O)OMc (735), МС2С==СНС(==0)ОМс
(735) and (СD3)2С==СНС(==О)ОМе (715 cm 1), and at thc LW sidc
Н 2 С==С(Мс)С(==О)ОМс (511), МсОС(==О)СН 2 С(==0)ОМс (534 and 517),
Н 2 С==СНС(==О)ОМс (530) and CIC(==O)OMc (540 CJП 1). Тhc rcmaining
RC(==O)OMc molecules display 1he /,с==о in thc morc convcnicnt rcgion б25
:!: 75 cm 1, just like the ethyl esters. Influenccd Ьу thc hydrogcn, thc 'УСН/С==О
in mcthyl formate absorbs а! а highcr wavcnumbcr (Scction 7.1.1).
Тhc c(==o) o deformation
Тhc c(==o) o deformation or c(==o) o rock absorbs wcakly to
modcratcly in the region 435 :!: 95 cm l. Thc compounds D з СС(==О)ОМс,
H 2 NC(==0)OMe, МеОС(==О)СН==СНС(==О)ОМс and МеОС(==О)ОМс
dcfinc thc uppcr limit with 521 :!: 3 cm l and RC:=CC(==O)OMc molccules
(R = МсС(==О), Мс and н) оссиру thc lowcr part of thc rcgion ( 340 cm I).
For most of the methyl estcrs thc rcgion 445 :!: БО cm ! givcs satisfaction. Mcthyl
acctatc absorbs а! 4З5 cm l and mcthyl propanoatc at 440 cm l. Saundcrs elal.
[бб] found 445 :!: 10 cm l for а scries of fourtccn aliphatic mcthyl cstcrs.
Skclctal C O C dcformation
Тhc skclctal C O C deformation appcars in thc region 320 :!: 70 cm t.
Тhc molcculcs МеСН==СНС(==О)ОМс (385) and Н2С==С(Мс)С(==0)ОМе
172 Noтral VilJтli01ls ат! AlJsorpli01l Regi01ls о/ С(==Х) у
(381) схЫЫ! tl1is band а\ I1igl1 \vavcnul11bcrs and МсС=СС(==О)ОМс (252),
DЗСС(==О)ОМС (28З) and CIC(==O)OMe (284 СП1 I) а\ low wаvспuшЬсrs.
МсОС(==О)ОМс givcs botl1 skclctal dcl'ormations а! 372 and 257 cm l.
Disrcgarding tl1cSC схtrсшс valucs, most of tllc П1сtl1уl cstcrs givc tl1is skclctal
dсfоrшаtiоп а! 325 :1: 40 CI11 t, схашрlсs bcing mctllyl formate (330) and mcthyl
acctatc (318 cm 1). Saundcrs е/ al. [66] foul1d ззо :1: 15 cm 1 for а scrics of
alipl1atic mctllyl estcrs.
ТаЫе 7.8 Absorption rcgions (cm 1) of tllC nomtal vibrations of
C(==O)OMe
Vibration Region Vibration Rcgion
1/0МС 3020 :!: 30 р'Мс 1155 :1: 35
'/ Mc 2990 :!: 40 1/0 C 975 :1: 125
I/sMc 2920 :1: 80 Ьс==о 715:1:115
I/С==О 1750 :!: 50 "'(с==о 635 :1: 130
ЬоМс 1460 :1: 25 Ь-С(==О)О 435 :1: 95
b Mc 1450:1: 15 Ьсос 320 :1: 70
bsMe 1435 :!: 15 torsion Мс 225 :1: 65
I/С(==О)О 1255 :1: 60 torsion ОМс
рМс 1185 :1: 35 torsion С(==О)ОМе
R C(==O)OMe molcculcs
R = H [1 1O], o [1 3], Mc [7 15], СDз [9 11, 15], Et [8, 25],
HOCH2 and OOCH2 [1б], N=CCH2 [17], PhCH2 , CICH2 [1
20], McOC(==O)C(==O)CH2 [21], cPr [22], iPr [8, 25], CI2CH [23,
24], tBu [8], FзС [8, 26---28], СlзС [24], McC(==O) [29, 30],
McOC(==O)CH2C(==O) [21], McNHC(==O) and McNDC(==O)
[31], McOC(==O) [7, 32, 33], CIC(==O) [34, 35], H2C==CH
[8, З6---40], McCH==CH [38, 40], MC2C==CH and (C03)2C==CH
[41], H2C==C(Mc) [42], MeOC(==O)CH==CH [35, 43, 44],
HOC(==O)CH==CH , OOC(==O)CH==CH and NaOC(==O)CH==CH
[45], CIC(==O)CH==CH [35, 45], PhCH==CH [4б], HC=C [47
49], MeC=C , MeOC(==O)C=C [48], N=C [49], Ph [5()"",5З],
з-МсРh [50], 4-МсО(О==)СРh [52], 2 H2NS(==O)2Ph , 2 , 3 and
4-НОРh [50, 54], З О2NРh [50], 3 C1Ph , 2 Fu [67], H2N [55],
PhNH , CI2N [55], MeO [5б, 57], McOC(==O)O [58], KO [59],
F [49, 60], Cl [БНiЗ].
References
1. Н. Susi and Т. ZcH, Spec/rocIlim. Ас/а, 19, 1933 (1963).
2. W.C. Harris, О.А. Сос and W.O. Gcorge, Spec/roc//im. Acta, Parl А, 32А, 1 (1976).
7,1 Carbollyl Compoипds
173
3. M.G. Oahlqvisl and К. Euranto, Speclroc//im. Ас/а, Par/ А, 34А, 863 (1978).
4. Н. Susi and J.R. Scherer, Spec/roc//il1l. ACla, Par/ А, 25А, 1243 (1969).
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22. O.L.Powcll, P.Кlaboc and O.H.Christensen, J. Мо/. Slrllcl., 15,77 (1973).
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27. G.A. Crowder and О. Jackson, SpeClroc/lim. Асla, Par/ А, 27А, 1873 (1971).
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29. W.J. Ray and J.E. Kalon, Spec/rocllim. Ас/а, Par/ А, 36А, 793 (1980).
30. J.к. WilП1shurs\ and J.F. Horwood, AlIs/. J. С//ет., 24,1183 (197]).
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(1975).
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33. J.R. Ourig, S.c. Brown and S.E. Hannum, J. С//ет. PI/ys., 54, 4428 (1971).
34. S.W. Charlcs, G.l.L. Jones, N.L. Owen and L.A. WCSI, J. Mol. Strиc/., 32, 111 (1976).
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36. W.L. Wal'on and R.B. Hughes, J. АI1l. С//ет. Soc., 79, 3985 (1957).
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39. W.O. Georgc, О.У. Hassid, W.c. Harris and W.F. Maddams,J. С//ет. Soc. Perkill Tralls.
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42. т.R. Manlcy and c.G. Martin, Spec/roc//il1l. Acta, Par/ А, 32А, 357 (1976).
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44. С. тeHcz, R. Кnudscn and О. Sala, J. Mol. S/rllcl., 67, 189 (1980).
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174 Nor1ll/l1 Vibralio//s a//d Absorplio// Regio//s о/ с(==х) у
47. G. WilliаП1S and N.L. О\усп, Tralls. Farat/ay Soc., 67, 950 (]97]).
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49. G. Williams and N.L. О\усп, Tralls. Far//(/ay Soc.. 67, 95О (1971).
50. G. Vаrs(шуi, AssigllIIIell/sfor Vibra/iolla/ Spec/ra ofSel'ell H/lIIl/"C'/ Bellzelle Deril'a/il'cs,
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52. F.J. Bocrio and S.K Bahl, Spec/roc/lim. Асщ Par/ А, 32А, 987 (1976).
53. J.H.S. Grccn and D.J. Harrison, Spec/rocl1im. Ас/а, Par/ А, 33А, 583 (]977).
54. М.М. Radhi al1d М.Е EI-Bcrrnani, Spec/roclrim. Acta, Рш'/ А, 46А, 33 (1990).
55. J.C Cartcr and J .Е. Dcvia, Spcc/rocl1im. Acta, Part А, 29А, 623 (1973).
56. В. Colling\vood, Н. Lcc and J.K. Wilmshurst, Лr/S/. J. C/lem., 19, 1637 (1966).
57. J.E. Katon and М.О. Collcn, Сшr. J. C/lem.. 53. 1378 (1975).
58. P.L. Liang and J.E. Ка'оп, J. Мо/. S/r//c/., 172, 113 (1988).
59. R. Mat'cs and К. Scho1tcn, Spec/roc//im. Ас/а, Part А, 3IА, 1307 (1975).
60. J.R. Durig, T.S. Littlc and CL. Тоllсу, Spec/rocl1im. Ас/а, Par/ А, 45А, 567 (1989).
61. R.A. Nyquist and W.J. Potts. Spec/roc/lim. Ас/а, 17,679 (1961).
62. J.C Evans and J. Ovcrcnd, Spec/roclrim. Ас/а, 19,701 (]963).
63. R.A. Nyquist, Sрес/юсl1iт. Ас/а, Рап А, 28А, 285 (1972).
64. W.A. Sc'h Раиl and А. Уап Duysc, Spec/rocl/im. Ас/а, Par/ А, 28А, 2] 1 (1972).
65. R.A. Nyquis', Арр/. Spec/rosc., 26, 81 (1972).
66. J.E. Saundcrs. J.J. Lucicr and ЕЕ Bcntlcy, Арр/. Spectrosc., 22,697 (1968).
67. М. Senechal and Р. Saumagnc,J. C/lim. PI/ys., 69,1246 (1972).
68. C.J. Pouchert, Т/lе AltIric/, Library о/ FT-/R Spectra, Aldrich Chcmical Соmрапу, ls'
edn. (1985).
7.1.9 Ethoxycarbonyl
The 18 vibrations of cthyl (sec Scction 3.5.1), togcthcr with I/С==О, I/C(==O) O,
1/0 C, ьс==о, I с==о, o-c(==o) o, bC O C and two torsions, make ир
thc 27 vibrations of C(==O)OEt.
Mcthyl and mcthylcnc strctching vibrations
Thc fivc cthyl СН strctching vibrations absorb wcakly to moderately bctween 2995
and 28БО cm 1. Thc antisymmctric strctchings are activc betwecn 2995 and 2930
cm 1 and thc symmctric countcrparts bctwccn 2930 and 28БО cm 1.
с==о strctching vibration
Thc wide rangc (1750 :i: 80 cm 1) in which thc I/С==О in cthyl esters is active is
due to thc cstcrs of halogcnatcd acids such as FC(==O)OEI (1829), CIC(==O)OEt
(1779), ХзСС(==О)ОЕt (1775 :i: 15) and Х2СНС(==О)ОЕI (1760 ::1: 15 cm 1) (Х
= F, CI, Br). Thc majority of ethyl cstcrs of Q-saturated acids wcrc found 10 givc
this //с==о in the rcgion 1740 :i: 15 cm 1. This band shifts 10 lower frcquencics in
cslers of a-unsaluratcd and aromatic acids (1715 :i: 15 cm 1). Compounds wilh ап
intramolccular hydrogen bridgc such as 2- and 4-НОРhС(==0)ОЕt (lб74) absorb
а! lowcr wavenumbcrs, just as КОС(==О)ОЕ! (lб70 cm 1).
7.1 Carbollyl Coтpoullds
175
Mctllyl and mcthylcne deformations
Thc I1igll absorption region of the mcthylcnc scissors (1475 :!: 15 cm J),
comparabIc with that of the ethyl cthcrs (Scction 10.1.З), is rcmarkabIc. Thc mcthyl
antisymmctric dcformations, which often occur а! the samc wavcnumbcr (1455 :!:
20 cm 1), absorb а! the low frcqucncy sidc of thc ЬСН2 region. lп contrast (о
mcthyl esters, thc methyl symmctric deformation occurs in the 'normal' rcgion
1385 :!: 15 cm J. lп ethyl acctatc this bsMc appears wcakly а! 1392 cm l. Thc
stronger absorption at 1374 cm ! is due to thc bsMc of thc МсС(==О) fragment.
Mcthylene wagging and twisting vibration
Ethyl cstcrs show the methylcne wag а! higher wavcnumbcrs (13БО :!: 25 cm t)
than the wag in hydrocarbons. This band, occurring somctimcs as а shoulder оп
the bsMc absorption, has medium intcnsity. Thc СН dcformation of C(==O)H,
iPr and cPr also appcars in this neighbourhood. Ethyl cthcrs absorb in thc rcgion
1345 :!: 35 cm 1. lп cthyl acetatc the shouldcr а! 1361 cm 1 оп thc 1374 cm I
band is assigned to this wag.
Thc methylcne twist is weakly to modcratcly activc in thc rangc 1285 :!: 45
cm l. The absorption а! 1301 cm ) in thc spcctrum of cthyl acctate is probabIy
duc (о this СН2 twist.
Thc c(==o) o stretching vibration
Thc c(==o) o stretching vibration providcs а modcratc to strong band in thc
region 1245 :1: б5 cm 1 and is, togcthcr with the I/С==О, of practical use in
clucidating the ester structurc. Thc uppcr limit is providcd Ьу 2-РуС(==0)ОЕ!
(1307) and F2CHC(==O)OEt (1305 cm 1) and thc lowcr limit Ьу CIC(==O)OEt
and Ме(СН 2 )вС(==О)ОЕ! with 1178 cm l, followcd Ьу МсСН==СНС(==О)ОЕ!
with 1184 cm I. Ethyl formatc absorbs а! 1189 and cthyl acctate а! 1241 cm 1.
Mcthyl rocking vibrations and O C/C C stretching vibrations
Usually thc highest absorption region (11б5:1: 30 cm 1) is assigned to thc methyl
rock, Ьи! thc litcrature does по! agrcc in assigning the othcr rcgions. Thc lowcst
rcgion (890 :1: 50 cm l) is dcrivcd from thc I/C C [З, 4, б, 9,11, 15] or vC O
[1, 2, 1б] or рМе [10]. The qucstion is that thcsc vibrations arc couplcd in such а
way as to make it difficult to dctcrmine which vibration provides the grcatcst part
in а distinct absorption [7, 8, 13].
17б Noтral Vibтliolls ат! AbsOIplioll Regiolls о/ С(==Х)У
Тhc highcst valucs for the рМе are foul1d in tlle spectra of EtC(==O)OEt (1 ]91)
and PIIC(==O)OEt (]]76, altllOugll 1125 cm 1 is preferabIe) alld the lowest in
thosc of H2C==C(CN)C(==O)OEt (1145) al1d НС=СС(==О)ОЕ! (1148 cm I).
Tllc rеПlаiпil1g ethyl estcrs absorb а! 1160 :!: 15 cm 1. Tl1is рМе in ethyl acetate
appcars а! 1160 cm 1.
Tlle СОПlроuпd CIC(==O)OEt displays tlle р'Ме а! 1142 cm l. FCH2C(==O)OEt
absorbs а! 1083 cm 1 and cthyl acctate weakly а! 1098 cm l.
Tlle cthyl esters ехЫЫ! а modcrate to strong band in tlle region 1060 :!: 40 cm 1
duc to а skclctal strctcl1ing vibration with а contribution from thc c o and thc
C C bOl1ds. Ethyl aCctatc I13S ап absorption а! 1048 cm l wl1ich is assigned to
thc mcthyl rocking vibration of the acctyl fragment and to the c o stretching
vibration. In tllc spectra of somc RC(==O)OEt compounds (R = Н, F, CI, N=C
and НС=С) а band \vith mcdium to strong intcnsity in the abovc-mentioned region
is attributcd to thc C C strctching vibration [1, 2, 16], but for most of the ethyl
estcrs thc absorption in this rcgion is assigncd to the I/C O.
Тhc rangc 890 :!: 50 cm 1 is attributed to thc ethyl C C stretching vibration
which is undcr thc inftucnce of thc I/C O. Ethyl acetate absorbs weakly а! 847
cm 1, а valuc which aIso mау Ьс assigned to thc I/C C of thc acetyl fragment.
Тhis vibration is somctimes called thc I/ s COC, and in cthyl ethers is activc а! 875
:!: б5 cm 1.
Mcthylenc rocking vibration
Thc mcthylcnc rock is active in thc rcgion 800 :!: 25 cm l. EthyI acetatc absorbs а!
78б cm 1, cthyl chIoroacctatc а! 805 cm 1 and cthyl trichIoroacctate а! 803 cm l.
Тhe с==о dcformations
Ignoring (\vithout rejccting) thc high values of 920 cm l in the spectrum of
НС(==О)ОЕ! [1] (Scction 7.1.1) and 821 cm 1 in that of KOC(==O)OEt, the с==о
dcformations group thcmselvcs in two rcgions: б90 :!: б5 and б25 :!: 75 cm '. In
this \vork thc highcr wavcnumber is assigncd to thc с==о in planc deformation and
thc lo\vcr to the с==о out of plane dcformation. Ethyl acetate absorbs near б34
cm 1 (ЬС==О) and 607 cm 1 ('УС==О), cthyI formate а! 920 cm 1 ('УСН/С==О)
and б72 cm l (ЬС==О).
Skclctal dcformations
Тhc C(==O) O rocking vibration is wcakly to moderately active in thc rcgion
430:!: 55 cm 1, in good agrecmcnt with that of C(==O)OH and C(==O)OMc.
Тhc wavcnumbcr 579 cm 1 in thc spcctrum of КОС(==О)ОЕ! is outside this region.
Saundcrs el al. [22] found а band а! 4б5 :!: 20 cm 1 for ten aliphatic cthyl esters.
7.1 Carbollyl Соmро/шds
177
Thc skelctal O C C deformation occurs at 350 :i: 45 cт 1 with а wcak to
moderate intensity. Saunders el а/. gave З80 :i: 15 cm 1 for cthyl cstcrs. Ethyl
acctate shows this vibration at 378 cm 1.
The skeletal C O C deformation is assigncd at 310 :i: БО cm l, а region
comparabIe with that of methyl csters (320 :i: 70 cm I). 'П RC(==O)OEt
compounds (R = Н, Ме, CI, CN) this skclctal dcformation is assigned respcctively
at 325, 3 J 4, 292 and 254 cm 1. For а series of aliphatic cthy\ esters Saundcrs el
а/. [22] note ап absorption а! 330 :!: 20 cm 1, which mау Ьс corrclated with thc
C O C skeletal deformation.
ТаЫе 7.9 Absorp\ion rcgions (cт 1) of thc normal viЬrаtiопs of C(==O)OE!
Vibration Rcgion Vibralion Region
Ila Mc 2985 :!: 10 р'Мс 1115 :i: 35
I/ Mc 2975 :!: 15 1/0 C 1060 :i: 40
l/ о СН 2 2945 :!: 15 I/C C 890 :i: 50
I/sMc 2910:1:: 20 рСН2 800 :i: 25
1/ 5 СН 2 2885 :!: 25 ЬС===О 690 :1: 65
I/С==О 1750 :!: 80 ,С==О 625 :i: 75
ьсн, 1475 :!: 15 b(p) C(==O) O 430 :i: 55
boM 1460 :!: 15 bo c c 350 :i: 45
b Mc 1450 :!: 15 bC O C 310:!: 60
bsMc 1385 :!: 15 torsion Мс 245 :i: 35
"" СН 2 13 60 :!: 25 torsion Е! 160 :i: 40
ТСН2 1285 :!: 45 torsion ОЕI
I/C(==O) O 1245 :!: 65 torsion С(==О)ОЕ\
рМс 1165 :!: 30
R C(==O)OEt molecules
R = H [1, 2], Me [3 5], СDз [4], Et , nPr , Mc(CH2)8 ,
CICH2CH2 , FCH2 [3], CICH2 [3, б, 7], BrCH2 [3, б], 'CH2 ,
N=CCH2 [8], MeC(==O)CH2 , EtC(==O)CH2 , ЕtOС(==О)СН2 ,
cPr , F2CH , CI2CH , Br2CH and C\FCH [9], МеСН(Сl) and
McCH(Br) [10], FзС , СlзС [11], McC(==O) ,
ЕtOС(==О) , H2NC(==O) [12], H2C==CH [13], McCH==CH
[13], H2C==C(CH2Br) , H2C==C(CN) [14], MC2C==CH ,
ЕtO(О==)ССН==СН [15], HC=C [lб], N=C [1], Ph [17, 18],
4 EtO(O==)CPh [18], 2 H2NPh , 3 02NPh and 2 and 4-НОРh [20],
2 , 3 and 4 Py , 2 Th [19], 2 Fu [23], H2N , ЕtO , KO [21],
F [16], Cl [1].
References
1. S.W. Char1es, G.1.L. Jones, N.L. Owcn, S.J. Cyvin and B.N. Cyvin,J. Мо/. S/rиc/., 16,
225 (1973).
2. M.G. Oahlqvis\ and К. Ешап\о, Spectroc//iт. Ас/а, Par/ А, 34А, 863 (1978).
178 Normal Vibтliol/s al/d AbsOIpliol/ Regiol/s о/ С(==Х) У
3. М.А. Raso, М.У. Garcia аl1(l J. Morci1lo, J. Мо/. S//'IICI., 115,449 (1 \184).
4. У. Mido, Н. SlliОП1i, Н. Matsuura, М.А. Raso, М.У. Garcia al1d J. MorciHo, J. Mol.
S/rllc/., 176, 253 (1988).
5. Т.-к На, С. Раl al1d P.N. Ghosh, Spec/roc/rilll. Асш, Par/ А, 48А, 1083 (1992).
6. N. Dul)c, Р. POl\val and Р. Prasad,J. Ralllall Spec/rosc., 19, 18\1 (1988).
7. У. Mido, N. Kakiza\va, Н. MatSIlUra, М.А. Raso, М.У. Garcia and J. Morcillo, J. Мо/.
S/rllc/., 220, 169 (1990).
8. S.W. CI13rlcs, G.1.L. JOI1CS and N.L. О,усп, J. С//ет. Soc. Fтщ/а)' Т/'аIlS. 2, 69, 1454
(1973).
9. М.А. Raso, М.У. Garcia and J. Morcillo, J. Мо/. S//'IIc/., 142,41 (1986).
10. N. Dubc and R. l'rasad. Spec/roc//im. Ас/а, Par/ А, 43А, 83 (1987).
11. У. Mido, Т. Kawasllita, К Suzuki, J. Morcillo and М.У. Garcia, J. Mol. S/rllc/., 162,
169 (1987).
12. Н.О. Dcsscyn, ЕК Vansant and B.J. Уап dcr Vckcn, Spec/roc//im. Ас/а, Par/ А, 31А,
625 (1975).
13. A.J. Bo\vlcs, W.O. Gcorgc and О.В. Сuпliffс-Jопсs,J. CI/em. Soc. В, 1070 (1970).
14. S. Rcynolds, О.Р. Oxley al1d R.G. Pritchard, Spec/rocl/im. Ас/а, Par/ А, 38А, 103 (1982).
15. О.А.с. СОП1рlOп, W.O. Georgc and A.J, Porter, J. С//ет. Soc. Perkil/ Т/ш/s. 2, 400
(1975).
16. S.W. Charlcs, G.1.L. Joncs, N.L. О\усп and L.A. Wcst, J. Mol. S/rrtc/., 26, 249 (1975).
17. J.H.S. Grccn and D.J. Harrison, Spec/roc//im. Ас/а, Рт'/ А, 33А, 583 (1977).
18. F.J. Bocrio and S.K. Bah1, Spec/l'ocl1illl. Ас/а, Рт'/ А, 32А, 987 (1976).
19. J.J. Pcron, Р. SаUП1аgпс and J.M. Lebas, Spec/rocl/im. Ас/а, Part А, 26А, 1651 (1970).
20. О. Varsanyi,Assig/llllell/sfor Vibra/iolla/ Spec/m ofSevell HI/I/dre(/ Bel/zel/e Deriva/ives,
J.Wi1ey & Sons, Nc\v York (1974).
21. R. Mattcs and К Scholtcn, Spec/roc//illl. Асш, Par/ А, 31А, 1307 (1975).
22. J.E. Saundcrs, J.J. Lucicr and ЕЕ Bcntlcy, Арр/. Spec/rosc., 22, 697 (1968).
23. М. Senecl131 and Р. Saumagne, J. C//im. PI/ys., 69, 1246 (1972).
7.2 АМINО(ТНIO)СARВОNУL COMPOUNDS
HC(==X)NH2 (Х = о or S, formamidc or thioformamidc) is the simplcst molccule
with а C(==X)NH2 structurc unit. Тhc compound givcs 3N б = 12 normal
vibrations (9а' + 3а") of which thrcc (2а' + а") arc considcrcd for the extcrnal
СН vibrations Ьу паmс I/СН (а'), ЬСН (а') and ""СН (а") (sce Scction 7.1.1).
Тhe rcmaining ninc arc dcrivcd from thc C(==X)NH2 fragmcnt. А compound
such as McC(==X)NH 2 has 3N б = 21 normal vibrations of which ninc arc
mcthyl vibrations. If опс torsion is rcplaccd Ьу а C C stretching vibration, the
remaining tweIvc vibrations arc duc 'о thc C(==X)NH2 group. То thc nine normal
vibrations of formamidc or thioformamidc arc added two skeletal deformations and
опе torsion:
а': l/ o NH2, I/ s NH2, I/С==Х, bNH2, I/C N, pNH 2 , ЬС==Х, b C N;
а": TNH2, wNH2, I'С==Х and torsion.
Somc of thc above mcntioned normal vibrations arc mixcd in such а way as 'о
makc thcm difficul\ \0 dcscribc. Тhc skclcta1 (С==Х) dcformation, ап in planc
7.2 Aтillo(IIIio)carboпyl Compollпds
179
dcformation in csscnce, is found in the litcraturc as ЬСХ. ЬССХ, bNCX or pNCX.
The NH2 wag is also namcd NH2/CX wag, 1IСХ or 1INCX. In addition, thc аЬоус-
mcntioncd vibrations arc difficult to distinguish from thc cxtcrnal R C(==X)
deformations, thc wavcnumbcrs of which dcpcnd оп thc C(==X)NH2 fragmcnt
as wcB as оп thc R substituent. Somctimcs thcsc mixcd viЬrаtiопs arc dcscribcd in
terms of amide vibrations [21]:
amide 1:
amide 1/:
amidc Ш:
amide 'У:
I/С==Х
t5 NH 2
I/C N
ЬС==Х
amide У:
amidc YI:
amide УН:
wNH2/CX
"'(С==Х
TNH 2 /CX
In the solid or liquid statc the NH2 and с==о vibrations arc associatcd to some
degrec and give risc to broad bands.
7.2.1 Carbamoyl (aminocarbonyl)
Formamidc possesses twclve normal vibrations (9а' + 3а") of which ninc are
assigncd to C(==0)NH2:
l/ o NH2 а' 3330 p NH 2 а' 1090
I/ s NH2 а' 3200 TNH2 а" 750
I/С==О а' 1б87 wNH2 а" б57
bNH2 а' 1б11 ЬС==О а' б08
I/C N а' 1309
and three to thc C(==O)H fragment (Scction 7.1.1):
I/СН
ЬСН
wCH/C==O
а'
а'
а"
2882
1391
1050
instcad of а torsion
instcad of in-planc dcformation
instcad of "'( с==о
The NH2 stretching vibrations
Thc NH 2 antisymmetric strctching vibration in thc associatcd statc givcs risc to а
strong broadish band in thc rcgion 3390 ::!: БО cm 1. High valucs originatc from thc
spectra of McHNC(==0)NH2 (3450), H2NC(==O)NH2 (3441), McOC(==O) NH 2
(34З4) and NaOC(==O)C(==O)NH 2 (3420 cm 1) and low valucs from thosc of
HC(==0)NH2 and DC(==O)NH 2 (3330 cm I). Most primary amidcs sho\v thc
l/ o NH2 bond а! 3370::!: ЗО cm t. 'П dilutc solutions thc frec l/ o NH2 appcars sharply
and strongly а! 3530 ::!: 30 cm 1.
The NH2 symmetric strctch in thc associatcd statc makes its appcarancc in
thc rcgion 3210 ::!: БО cm 1 with а somcwhat wcakcr intensity than that of its
antisymmetric counterpart. Compounds absorbing а! thc HW sidc of this region
arc the a halogen substituted amidcs (3250 ::!: 10), McOC(==O)NH2 (3262) and
180 No,.,,/(/l Vibтliolls alld AbsOIptioll Regiolls о/ С(==Х) у
N==:CC(==O)NH2 (3260 cm t) and а! thc LW sidc McSC(==O)NH2 (3150) and
H2NC(==O)C(==O)NH2 (З153 and З185 cm 1). For most of thc primary amidcs
this rcgion сап Ьс rcduced (о 3190 :!: 30 сш t. 1п dilutc solution the frce I/ s NH2
occurs а! 3420 :!: 20 сш 1.
The intcnsity of both NH2 strctching vibrations is grcater thal1 that of the aliphatic
amines and reachcs tl13t of thc Ьспzспашiпеs. Ovcrtol1cs of thc amide II absorption
intcnsificd Ьу Fсrшi rcsonancc mау ассоmрапу tllcse bands. lf both 11ydrogcn atoms
arc unbondcd or cquaBy bondcd, l.la = 0.89 I/. + 484 [56]. In dilute solutions thc
diffcrcl1cc il1 wavcnumbcr bctwccn thc (о NH2 stretching vibrations approaclles 115
сш l,
The с==о strctcl1ing vibration
Тhc с==о strctching vibration (amidc 1) in the associatcd state appears strongly
а! 1б80 :!: 40 cm 1. Тhc highcst valucs arc obscrved in the spectra of amidcs
in which thc Q-carbon is halogcnatcd, such as CI2(CN)CC(==O)NH2 (171З),
F з СС(==О)NН 2 (1710) and СlзСС(==О)NН2 (1695 cm 1). Low wavenumbers are
found in thc spcctra of McSC(==O)NН2 (1640) and in those of aromatic amides
\vith, as cxtrcmes, 2 CIPhC(==O)NH2 (lб42) and 3 ТllC(==O)NH2 (lб47 cm I).
Тhe majority of thc invcstigatcd molccu1cs wcrc found to give this I/С==О in the
rcgion 1670 :!: 20 cm l. The absorption occurs in the high frequency wing of the
ашidс 11 band and is sometimcs partly mcrged with it. In dilute solutions the amide
1 band is shifted to а 40 сш 1 higher wavcnumbcr and that of the amide 11 band
to а 20 cm l lowcr wavenumbcr so that the bands arc clearly separated from each
othcr. If in solution two absorptions for thc amidc 1 band arc obscrvcd, that with the
highcr {Iowcr} wavcnumbcr is assigncd to the frce {associated} с==о strctching
vibration. Rotational isomcrs also show morc than опс с==о band.
Тhc NH 2 dсfоrшаtiоп
Тhe NH2 dcformation (amidc II) appcars in the rcgion 1610:!: 30 cm '. Thc highest
values arc furnishcd Ьу FзСС(==О)NН2 and McC(==O)NHC(==O)NH2 (1б40
cm l) and thc lowcst Ьу KOC(==O)C(==O)NH2 (1580), NaOC(==O)C(==O) NH 2
(1584), McHNC(==O)NН 2 (1585) and McHNC(==S)C(==O)NH2 (1585 cm 1).
Most primary amidcs display tllC amide 11 band а! 1610 :!: 20 cm l. In thc solid or
liquid statc this band appcars somctimcs as а shouldcr with а 1110dcratc to strong
intcnsity оп the I/С==О absorption. In di1utc solutions the NH2 scissors absorbs
with а 30---50% lowcr intcnsity than that of thc с==о stretch, and is wcB scparated
from it.
Тhe C N stretching vibration
Тhc C N strctching vibration (amide Ш) is only weakly to modcratcly active in
thc rcgion 1385 :!: 85 cm l and is thercforc difficult to detcct. Formamide gives
7.2 Aтi"o(IIIio)carbollY! CompOItllds
181
this amide III band а! 1309 cm 1, acetamide а! 1398 cm l, propanamidc and but-
anamide а! about 1420 cm l. Urca and F з СС(==0)NН 2 scorc high (14б5 cm I).
Most absorptions соmе within the rcgion 1390:1: 40 cm 1, in which a]so thc mcthyl
or methylenc deformations are active. Тhis vibration is couplcd to thc R C(==O)
stretch and in some degree also to the NH2 dcformation. 'П dilutc solutions а small
shift to higher wavcnumbers occurs.
The NH2 rocking, twisting and wagging vibration
The in-p]ane NH 2 rock absorbs weakly to moderatcly in thc rcgion 1125 :1: 45
cm 1. 'П the spectrum of formamidc this vibration is assigncd а! 1090 cm 1
in thc liquid state and а! 1150 cm 1 in the vapour phasc. Тhe NH2 rock in
acctamidc, propanamide and butanamidc occurs rcspcctivcly а! 1152, 1142 and
1144 cm 1. High valucs are found in thc spcctra of 1CH2C(==0)NH2 (1170 а';
ТСН2: 1150 cm ' а") and McHNC(==0)NH2 (11б9 cm I). Low values in thc
ncighbourhood of 1080 сm I arc assigncd in thc spcctra of НОС( ==О)С( ==0)NH2,
KOC(==0)C(==O)NH2 and R2NC(==O)C(==0)NH2. Most rocks arc situatcd а!
1130:1: ЗО cm 1.
Тhe amide УН band, absorbing in the rcgion 7б5 :1: 55 cm l, is mainly assigncd
to the NH2 out of planc twist and is a]so undcr thc influcncc of thc с==о out
of plane deformation. Нigh wavenumbers in thc ncighbourhood of 815 :1: 5 cIп l
are assigned in the spcctra of HOC(==O)C(==0)NH 2 , EtOC(==0)C(==0)NH2,
McC(==O)NHC(==O)NH2 and XCH2C(==0)NH2 (Х = F, CI, 1). Тhc wcak broad
band а! 810 cm 1 in the spectrum of acetamidc is attributed to this twist. То thc
LW sidc of the above-mentioncd rcgion шса absorbs а! 717 and 7В9 cm l. Most of
thc primary amides give ап oftcn broadish band with а wcak to modcratc intcnsity
in thc range 770 :1: 30 cm l. 'П thc vapour statc thc frcc torsion absorbs in thc
neighbourhood of 2БО cm l.
The amide V band (б70 :1: БО cт 1) is а mixcd vibration assigncd to thc
NH 2 wag (wNH2 or 7fNH2) with а contribution from thc с==о out-of-plane
dcformation. Нigh values are sccn in thc spcctra of MC2NC(==0)NН2 (725),
(CD3)2NC(==O)NH2 (720), MeHNC(==0)C(==0)NH2 (724), MeC(==0)NH2
(715), MeHNC(==O)NH 2 (712) and СDзНNС(==0)NН2 (710 cm 1) and low
values in those of N:=CC(==O)NH2 and AzC(==0)NH2 (б20 cm I). Thc NН2
wag, usually absorbing in the rcgion бб5 :1: 35 cm 1 and clcarly scparatcd from
thc twist, is easy 10 recognizc Ьу its broad band structurc.
The с==о dcformations
Primary amides give the с==о in planc dcformation (amidc IV) in thc rcgion
610 :1: 70 cm 1 with а weak to moderatc intcnsity. MeHNC(==0)C(==O)NH 2 ,
R2NC(==O)C(==O)NH2, EtOC(==O)C(==0)NH2, McOC(==0)NH2 and
Mc(CH2)9NHC(==O)NH2 absorb аl аЬои! б75 cm 1 and MOC(==0)C(==0)NH2
182 Noтtal Vibтliol/s al/(I Absorpliol/ Regiol/s о/ с(==х) у
(М = Н, К, Na), H2NC(==S)NHC(==O)NH2 апд NзС(==О)NН2 in tllc vicinity of
550 сш I, For tlle rcmaining R C(==O)NH2 compounds tllc ьс==о is silualed
а! бlО:i: 50 cm t, аl tllc LW side of tlle amidc Vabsorpliol1,
Tlle \vcak (о mсdiuш and sошсliшсs broadish band in 111C rcgiol1 560 :i: 70 cm 1
is assigned to 111C с==о out-of plal1c deforn1alion ()' с==о, 1fC==O or amide
Vl) with а contribution from 111C NH2 wag. For Me2NC(==O)C(==O)NH2 Illis
absorption is observed а! 626 сш l, for H2NC(==O)C(==O)NH2 аl 617 and 526
cm 1 (R) and for NaOC(==O)C(==O)NH2 and KOC(==O)C(==O)NH 2 аl about
490 cm 1, Most of Ille l' с==о deformations arc active а! 550:!: 50 cm t. Thc out
of planc and in-plane с==о dсfоrпшtiоп сап absorb а! the same wavenumbcr, as
for is 111C casc in ассtашidе (584 cm t). Spectra structurc corrclations of aliphalic
amidcs in thc 700---250 cm 1 rcgion arc given Ьу Kalon el al. [57].
In planc skclctal deformation
Thc in planc skclctal dсfоrшаtiоп is а mixcd vibration described as the external
C N dcformation or p C(==O) N, comparable with the c(==o) o
rocking vibration in carboxylic acids or estcrs. For XC(==O)C(==O)NH2 (Х = H2N,
RNH, R 2 N, НО, КО, NaO) and MeHNC(==S)C(==O)NH 2 this skcletal dcformation
is obscrvcd а! 475 :i: 25 cm 1 and for acctamidc, propanamidc and butanamide а!
respcctivcly 4бб, 479 and 4б8 cm 1.
Torsion
Thc C(==O)NH2 torsion in acctamide occurs а! 155 cm 1, and in а few othcr
R C(==O)NH2 compounds а! 145 :i: 55 cm 1. In the уарош рlшsе the free NH2
torsion absorbs а! about 2БО cm 1.
ТаЫе 7.10 Absorplion rcgion (cm 1) of Ihc поrrnаl vibra'ions of C(==0)NH2
Vibra,ion a sa'uratcd с==о bound a unsaturaled N, О or S
C==S bound aromatic bound
l/ o NH2 3370 :i: 40 3380 :i: 40 3370 :i: 30 3400 :i: 50
I/ s NH2 3205 :i: 45 3205 :i: 55 3180:!: 30 3210:!: 60
I/С==О (1) 1680 :i: 35 1675 :i: 25 1660:!: 15 1670 :i: 30
bNH2 (11) 1615 :i: 25 1595 :i: 15 1610:!: 10 1610:f: 30
I/C N (Ш) 1380 :i: 80 1395 :i: 55 1385 :i: 40 1400:f: 70
p NH 2 1130 :i: 40 1100 :i: 20 1115 :i: 25 1130 :i: 40
TNH2 (УП) 765 :i: 45 775 :i: 45 780 :i: 40 765 :i: 55
u; NH 2 (У) 670 :i: 50 685 :i: 45 660 :i: 50 675 :i: 55
ьс==о (IV) 600 :i: 50 610:!: 70 605 :i: 35 610 :f: 70
1'С==О 550 :i: 50 560 :i: 70 535 :i: 35 550 :i: 40
b C N 430 :i: 50 475 :i: 25 475 :i: 55
'orsion 130 :i: 40 150 :i: 50 160 :i: 40
7.2 A11IillO(lhio)carbollyl Coтpouпds
183
R C(==O)NH2 molecules
R = H [1 10], o [1], Mc [9 14], СDз [11, lЗ, 14], Et [15,
16], СНзСD2 [15], nPr , H2NC(==O)CH2CH2 , N=CCH2 [17,
18], PllCH2 [55], FCH2 [19 24], C]CH2 [17, 19, 20, 24],
'CH2 [20 23], iPr , cPr [25], Br(CN)CH [18], F2CH and
CI2CH [24], tBu , CI2(CN)C and Br2(CN)C [18], FзС [21,
23, 24, 26], СlзС [24], 4 CIPhC(Mc)2 , H2NC(==O) [27 29,
40], McHNC(==O) and MC2NC(==O) [27], RNHC(==O) and
R2NC(==O) [17], HOC(==O) [17, 28 30], ЕtOС(==О) [17],
NaOC(==O) [17, 28, Зl], KOC(==O) [28---31], H2NC(==S) [32],
McHNC(==S) and СDзНNС(==S) [33], H2C==CH [9], Ph [З
37, 55], 2 FPh , 2-СIРh , 2 and 3 Fu [38], 3 Th [38],
pyrazine [391, N=C [17], H2N [41.-45, 59], HDN [41],
MeNH and СDзNН [4б], Mc(CH2)9NH [47], McC(==O)NH and
СDзС(==О)NН [48], H2NC(==O)NH [58], H2NC(==S)NH [49,58],
Me2N and (CD3)2N [50], Az [51], NЗ [52], 02N , McO [53],
McS and СDзS [54].
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(1962).
36. S. Yoshida, CllCIl/. Р/IIlПl/. BIIII., Il, 628 (1963).
37. J.1-I.S. Grccn and D.J. Harrison, Spec/rosc//im. Acla, Parl А, 33А, 583 (1977).
38. G. Alberghina, S. Fisichalla and S. Occhipinti, Spectroscltiт. Acta, Par/ А, 36А, 349
(1980).
39. M.J.M. Dc1gado, F. Marqucz, Н.1. Suero and J.1. Marcos, Spec/rosc. Lett., 21, 841
(1988).
40. Т.А. Scot, Jr. and E.L. Wagncr, J. С//ет. P//ys., 30, 465 (1959).
41. А. Yamaguchi,J. CI/em. Soc. JplI., 78,1467 (1957).
42. J.E. Stcwart, J. CI/em. P/,yS., 26, 248 (1957).
43. J. Arcnas and R. Parcllada, J. Мо/. Strllc/., 10,253 (1971).
44. О. Hadzi, J. Кidric, Z.V. Кnczcvic and В. Barlic, Speclrosc//im. Ас/а, Par/ А, 32А, 693
(1976).
45. W. Kulzelnigg and R. Mcckc, Z. E/ektrocl/em., 65, 109 (1961).
46. У. Saito, К Machida and Т. Uno, Spec/rosc//im. Acta, Part А, 31А, 1237 (1975).
47. У. Mido, S. Кimura, У. Sugano and К. Machida, Spec/rosc//iт. Ас/а, Par/ А, 44А, 661
(1988).
48. У. Saito and К, Machida, Spec/rosc//im. Ас/а, Part А, 35А, 369 (1979).
49. К. Gcclharani and D.N. Sathyanarayana, Spectrosc//im. Ас/а, Par/ А, 32А, 227 (1976).
50. У. Mido, К. Tanasc and К, Кido, Spec/rosc//im. Ас/а, Part А, 45А, 397 (1989).
51. H.L. Spcll and J. Laanc, J. Mol. S/ТIIC/., 14, 39 (1972).
52. W. Budcr and А. Schmidl, Spec/rosc//im. Ас/а, Par/ А, 29А, 1429 (1973).
53. J.c. Cartcr and J.E. Dcvia, Spec/rosc//im. Ас/а, Parl А, 29А, 623 (1973).
54. L. Zhcngyan, R. Mallcs, Н. Sсhпбсkе1, М. Тhuпсmапп, Е. Hunting, U. Нбпkе and С.
Mcndcl,J. Мо/. S/rllc/., 117, 117 (1984).
55. G. Varsanyi, AssigllIIIell/s [or Vibratiol/al Spectra o[Seve" HIII/dred Be"ze"e Derivalives,
J.Wi1cy & Sons, Ncw York (1974).
56. P.G. Puranik and KW. Ramiah, Nalllre, 191,796 (1961).
57. J.E. Kalon, W.R. Fcairhellcr Jr. and J.V. Puslingcr Jr., Allal. С//ет., 36,2126 (1964).
58. R.H. Sullivan, J.S. Kwialko\vski and J. Leszczynski,J. Мо/. S/rllct., 295, 169 (1993).
59. А. Vijav and D.N. Salhyanarayana,J. Мо/. Slrllcl., 295, 245 (1993).
7.2.2 Thiocarbamoy\ (aminothiocarbonyl)
Thioformamide providcs 12 normal vibrations (9а' + За"). Nine find а р\асе in thc
tablc with C(==S)NH2 vibrations:
7.2 AтillO(ll1io)carbollyl COl1lpou"ds 185
//oN H 2 а' 3287 I/C==S а' 843
I/, NH 2 а' 3165 TNH2 а" б7З
bN H 2 а' 1612 wNH2 а" б20
I/C N а' 1443 bC==S а' 439
pNH 2 а' 1125
and three belong 'о the C(==O)H vibrations:
,/СН а'
ЬСН а'
""CH/C==S а"
2905
1325
985
instead of а torsion
instead of in planc dcformation
instcad of 'у C==S
Thc C==S vibrations in primary thioamides arc mixcd in such а way 'о makc thcm
difficul1 to describc. Thc literature is по! unanimous in assigning thcsc vibrations.
Thc NH2 stretching vibrations
Thc absorption rcgions of the NH 2 strctching vibrations (1/0: 3340 :i: БО; I/s: 31БО
:i: 80 сm 1) arc situatcd 50 сm 1 lower than thosc of thc соrrеsропdiпg amidcs.
Thc intcnsity of 1hcse bands is fairly strong. Thioacetamide absorbs а! thc LW
sidc of these regions: 3295 and 3080 cm 1. An ovcrtonc of thc NH2 dсfоrmаtiоп
intensificd Ьу Fermni resonance сап ассоmрапу thcsc normal vibrations.ln solution
both strctching vibrations mоуе 'о wavcnumbcrs highcr Ьу 100 cm '.
Thc NH2 deformation
The NH2 scissors or thioamide II vibration is obscrvcd а! 1б20 :i: 30 cт 1
with а modcrate to strong intensity. ln thc spcctra of thioacctamidc and
bcnzcncthioamide, the bNH2 occurs а! rcspcctivcly 1б48 and 1б23 cm 1, and in
thosc of R C(==X)C(==S)NH2 and R XC(==S)NH2 compounds (Х = о or S)
in thc narrow region 1БОО :1: 10 cm 1.
Thc C N stretching vibration
With thc exception of the dithiocarbamatc ion H2NC(==S)S (1325 cт 1),
thc I/C N or thioamide III or NCS 1 band is found in thc rcgion 1420 :i:
БО cm 1 with а moderate intensity. Нigh values (1480 cm 1) arc listcd for
H 2 NHNC(==S)NH 2 and McHNC(==S)NH2 and low valucs for СDзС(==S)NН2
(13БО) and MeSC(==S)NH2 (13б5 cm 1). Thc rcmaining compounds givc this
I/C N at 1435 :1: З5 cm 1, that is, somcwhat highcr than for amidcs.
186 Normal VilJтliol/s ат! AlJsol]Jliol/ Regiol/s о! С(==Х) У
The NH 2 rocking vibration
ll1е NH 2 rock or NCS 11 band is variabIe in tlle range 1195 ::1: 110
cm l. ll1е I1igllest \vаvепuшЬсrs are assigned in tllc spectra of thiоассtашidс
d o and dз (1303), McOC(==S)NH2 (1303), Me2NC(==S)C(==S)NH2 (1286),
H2NC(==S)NHC(==S)NH2 (1280 and 1120), H2NC(==O)NHC(==S)NH2 (1285
сПl ') and tllc lo\vcst in tllOsC of tl1iourca (1084 and 1114) and tl1iоfоrшашidс
(1125 СПl l). ll1С rcmaining сошроипds give tllC NH2 rock а! 1210 ::1: 70 cm 1.
This region is broadcr and а! I1igllcr wavenumbcrs tl13n tllat of thc corresponding
amides (1125::1: 45 СПl t).
Thc C==S strctching vibration
Thc C==S strctching vibration (thioamidc 1 or NCS Ш) is assigned in the broad
rcgion 800 ::1: 130 cm l, иSl1ally with а modcrate intcnsity. Since the S atom is
lcss clcctroncgativc tl13n the О atom, the C==S group is по! as polar as the с==о
group and 1css prone to form bridges. Тhc I/C==S absorption is sharper and по!
as intcnse as thc ,/с==о absorption. Тhe broad region results from thc fact that
this absorption is always mixcd, схсср! for thiоfоrПlаmidе, for wl1ich the band а!
843 cm 1 is dиc to thc almost рше I/C==S. Tlle low wavenиmber of the C==S
strctcl1ing vibration is attributcd to thc grcater contribиtion of the resonance form
(11) [4, 1б]:
>N C==S
(1)
>+N==C S
(11)
Thc C N bond оп thc contrary is fortified so tl13t thc I/C N and the pNH2 that
is coиplcd to it absorb а! higher wavcnumbers. Тhe C==S stre1ching vibration
is not only rcsponsiblc for thc absorption in thc neigllbourhood of 780 cm '
Ьи! сап also contributc to thc band а! about 980 cm 1 (I/C C), 1200 cm 1
(pNH2) and сусп to tlle I/C N around 1420 cm 1, so that а1l thcsc bands
сап Ьс associatcd with thc I/C==S. In this text the C==S strctching vibration is
considcrcd to Ье located а! 780 ::1: 80 cm 1. Thc rather strong band at 719 cm 1
in the spcctrum of thioacctamide is assigncd to tlle I/C==S. Thc high values for
the compounds MC2NC(==S)C(==S)NH2 (929), MeHNC(==O)C(==S)NH2 (924),
KOC(==O)C(==S)NH 2 (918) and H2NC(==O)C(==S)NH2 (911 cm 1) [4] arc not
takcn into account, Ьи! for thc last two compounds the va1ucs 802 and 784 cm 1
are not cxcluded.
Тhc NH 2 t\visting and wagging vibrations
Thc NH 2 twist (thioamidc У1I) is ап oиt of p1ane dcformation and gives а band
that is wcak to modcrate Ьи! oftcn broad in thc region 705 ::1: 65 cm 1. Тhe weak
7.2 AlIIillo(ll/io)carbollyl Compo/lllds
187
broad absorption а! 760 cm 1 in the spectrum of thioacctamide is attributcd to this
vibration. High wavenumbers originatc from thc spectra of urca (769 and 729 cm l)
and СD з SС(==S)NН 2 (765 cm 1), and low valucs flOm thosc of N=CC(==S) NH 2
(648) and thioformamide (673 cm I). Thcrc is а rcalistic chancc that thc NH2 twist
occurs а! 720 :f: 30 cm t, approximately 50 cm 1 lowcr thап thc 1wist in primary
amidcs.
Thc NH 2 wagging vibration (thioamidc V), also ап out-of-planc dсfоrmаtiоп,
is weakly to modcratcly (Ьи1 broadly) active in the rcgion б45 :f: б5 cm 1 and
pcnctratcs far into thc rcgion of thc NH2 twist. Thioacetamide-d o and -d з (709),
N=CCH2C(==S)NH2 (696) and EtOC(==O)C(==S)NH 2 (б8б cm l) givc thc
I1ighcst valucs in this rcgion, and McSC(==S)NH2 (588) and McHNC(==S)NH 2
(600 cm 1, al1hough БЗ7 is considcred as wcll) arc rcsponsibIc for thc lowcs1
wavenumbers. The rcmaining thioamidcs display thc NH 2 wag а1 б40 :f: 30 cm 1,
аЬои! 25 cm 1 lowcr than thc NH 2 wag in primary amides.
Thc C==S deformations
Thc wcak (о moderatc absorption in the rcgion 510 :f: 90 cm l is usually assigncd
to thc in plane C==S dcformation (thioamidc IV), couplcd (о thc in planc skclctal
dcformation and oftcn described as bCS or bNCS. Undcr thc influcncc of thc hcavicr
S atom, thc bC==S absorbs а! 100 cm l lowcr wavcnumbcrs than thc ЬС==О. In
thc spectrum of thioacetamide the C==S in-planc dcformation is assigncd а! 471
cm 1.
Primary thioamides givc the C==S out-of planc dcformation in thc rапgс 420
:f: 100 cm 1, often describcd as the 7rNCS. А! thc HW sidc of this rcgion thio-
acctamide absorbs (514 cm l) and а! the LW sidc McSC(==S)NH2 (320 cm l).
This region is considerabIy lower than that of thc I с==о of amidcs.
In-plane skeletal deformation
Thc in-planc skcIctal dcformation is wcakly to modcratcly activc in thc rcgion 325
::1: 85 cm 1. This mixed vibration is dcscribcd as thc cxtcrnal C N dcformation
or p C(==S)N and is under thc influcnce of bC==S. For thioacctamidc this
vibration is assigned а! З77 cm 1.
Torsion
Thc torsion in thioacc1amide is located а! lб2 cm 1 and that in McSC(==S)NH2
а! 13б cm l. А few torsions are obscrved in thc Dcighbourhood of 120 cm 1.
188 Normal VilJrllliolls ат! AbsOlplioll Regiolls о/ с(==х) у
ТаЫс 7.11 ЛЬsоrptiоп rcgiulI (СП1 I) of tllc попnаl vilтl'iOJIS of C(==S)NH2
Yibration Rcgion Vibralion I cgion
l/ o NH2 3340 :1: 60 TNI-[z (VII) 705 :1: 65
v s NH 2 3160:1: 80 wNHz (У) 645 :1: 65
bNH2 (11) 1620:1: 30 bC==S (IV) 510:1: 90
I/C N (111) 1420 :1: 60 I C==S (VI) 420 :1: 100
p NH 2 1195:1: 110 b C N 325 :1: 85
/JC==S (1) 780 :1: 80 torsion ::::::120
R C(==S)NH2 molcculcs
R = H [1-4, 40], Mc [3 12], СDз [8 10], N=CCH2 [З, 13],
PhCH2 [24], СFз [14], KOC(==O) [4, 15], ЕtOС(==О) [4],
H2NC(==O) [4, 1б], MeHNC(==O) and MC2NC(==O) [4],
H2NC(==S) [3, 4, 17 19], McHNC(==S) [4, 20], СDзНNС(==S) [20],
MC2NC(==S) [4], N=C [3, 4, 21, 22], Ph [23, 24],
H2N [3, 25 27], McHN [3, 28, 29], EtHN , Me(CH2)15HN [29],
McC(==O)HN , PhHN , H2NHN [3, 30 33], H2NC(==O)HN [З4,
40], H2NC(==S)HN [35, 3б, 40], McO and СDзО [37], MeS [3,
38], CDзS [38], H2NC(==S)S , S [З, З9].
References
1. М. Oavies and W.J. Joncs,J. С//ет. Soc., 955 (1958).
2. 1. Suzuki, 8//1/. С//ет. Soc. JP/I., 35,1286 (1962).
3. K.R.G. Ocvi, O.N. Sathyanarayana and S. Manogaran, Spec/roscIJim. Асщ Par/ А, 37А,
31 (1981).
4. Н.О. Ocsscyn, B.J. Уап dcr Vckcn and М.А. Нспnап, Appl. Spectrosc., 32, 101 (1978).
5. 1. Suzuki, 8//11. С//ет. Soc. JplI., 35,1449 (1962).
6. W. Walter and Н.Р. Kubcrsky, Liebigs АII1/. C/lem., 694, 56 (1966).
7. к,А. Jcnscn and Р.Н. Niclscn, Ас/а С/lет. Scalld., 20, 597 (1966).
8. А. Ray and O.N. Sa'hyanarayana, 8//11. С//ет. Soc. JplI., 47, 729 (1974).
9. W. Waltcr and Р. Staglich, Spec/rosc//im. Ас/а, Part А, 30А, 1739 (1974).
10. М. Hargittai, S. Samdal and R. Scip,J. Мо/. S/ТIICI., 71, 147 (1981).
11. U. Anthoni, Р.Н. Nielscn and О.Е Niclscn,J. Мо/. S/rиct., 116, 175 (1984).
12. U. Anlhoni, Р.Н. Niclscn and О.Н. Chrislcnscn, Spec/roscIJim. Ас/а, Par/ А, 41A, 1327
(1985).
13. А. Ray and O.N. Salhyanarayana, 8//11_ С//ет. Soc. JplI., 46, 1969 (1973).
14. Е. Lindcr and U. Kunzc, Z. Allorg. AIIg. С//ет., 383, 255 (1971).
15. Н.О. Dcsscyn, B.J. Уап dcr Vckcn, A.J. Aarts and М.А. Непnап, J. Мо/. S/r/lc/., 63,
13 (1980).
16. Н.О. Oesseyn and М.А. Нсrrnап, Spec/rosc//im. Ас/а, Рат/ А, 23А, 2457 (1967).
17. ТА Scoll Jr. and E.L. Wagncr, J. С//ет. P//ys., 30, 465 (1959).
18. А. Ray and O.N. Sathyanarayana,llIdia J. С//ст., 12, 1092 (1974).
19. Н.О. Oesscyn, B.J. Уап dcr Vckcn and A.J. Aarts, Ca/l. J. SpeclI'osc., 22,84 (]977).
20. Н.О. Ocsscyn, A.J. Aarts and М.А. Нсrrnап, SpectroscIJim. Ас/а, Par/ А, 36А, 59 (1980).
7.3 Mell/y/a1lliIl0(II/io)carboпy/ C01llpOllllds
189
21. У.Е Ouckwor'h and R.L. Wcrncr, Aиs/. J. CJ/em., 18, 129 (1965).
22. Н.О. Oesscyn, ЕК. Vansant and B.J. Уап dcr Vckcn, Spec/rosc//im. Ас/а, Par/ А, 31А,
625 (1975).
23. A.J. Aar's, Н.О. Oesseyn, B.J. Уап der Vckcn and М.А. Неrrnап, Call. J. Spectrosc.,
24, 29 (1979).
24. G. Varsanyi, A.vsigllтell/s [or Vibra/ioпa/ Spectra ofSeveп Hиlldred Bellzeпe Derivatives,
J.Wilcy & Sons, Ncw York (1974).
25. О. Hadzi, J. Kidric, Z.V. Knczevic and В. Barlic, Spec/rosc//im. Ас/а, Рат/ А, 32А, 693
(1976).
26. J.E. Stewart, J. С//ет. P//ys., 26, 248 (1957).
27. А. Yamaguchi, R.B. Penland, S. Mizushima, T.J. Lзпс, С. Curran and J.V. Quagliano,
J. Amer. С//ет. Soc., 80, 527 (1958).
28. К. O\varakanath and O.N. Salhyanarayana, Виll. Chem. Soc. JpII., 52, 2084 (1979).
29. У. Mido, S. Kimura, У. Sugano and К. Machida, Spec/roscl1im. Acta, Part А. 44А, 661
(1988).
30. G. Kcresztury and М.Р. Marzocchi, С/ШII. P//ys., 6, 117 (1974).
31. G. Kcrcszlury and М.Р. Marzocchi, Speclrosc//im. Ас/а. Par/ А, 31А, 275 (1975).
32. O.N. Sa'hyanarayana, К. Volka and К. Gcclharani, Spec/rosc/lim. АС/а, Part А, 33А,
517 (1977).
33. А. Vijav and O.N. Sa'hyanarayana, Spec/roscl1iт. Ас/а, Par/ А, 48А, 1601 (]992).
34. К. Gectharani and O.N. Sathyanarayana, Spec/rosc//im. Ас/а, Рап А, 32А, 227 (1976).
35. W. Malavasi, А. Pignedoli and G. Peyroncl, Spectrosc//im. Acta, Par/A, 37А, 663 (1981).
36. G. Pcyronel, А. Pigncdoli and W. Malavasi, Spec/roSC/lim.Ac/a, Рат/ А, 38А, 971 (1982).
37. L. Zllengyan, R. Mattcs, Н. Sсhпбсkсl, М. ThUncmann, Е. Hunting, U. Нбпkе and С.
Mendel,J. Мо/. S/Т/lc/., 117, 117 (1984).
38. R. Mattcs, L. Zhengyan, М. ThUncmann and Н. Sсhпбсkеl, J. Мо/. S/rиct., 99, 119
(1983).
39. J. Кnoeck and J. Witt, Spec/roscl1iт. Acta, Par/ А, 32А, 149 (1976).
40. R.H. Sullivan, J.S. Kwialko\vski and J. Lcszczyiiski,J. Мо/. S/rиc/., 295,169 (1993).
7.3 МЕТНУLAМINО(ТНIO)СARВОNУL COMPOUNDS
N Monosubstitutcd amides exist mainly with thc NH and с==о bonds in thc
Iralls configuration. In thc С . structurc HC(==X)NHMc (N mcthylformamidc, N
mcthylthioformamide) possesscs 3N б = 21 normal vibrations which arc dividcd
into 14а' and 7а" spccics of vibration. Sctting asidc thc extcrnal СН vibrations
(2а' + а"), the following 21 (13а' + 8а") typcs of vibrations arc considercd for the
С(==Х)NНС'Нз structure unit:
а': I/NH, I/ Me, I/ s Me, I/С==Х, bNH, b Mc, bsMc, I/C N, vN C', р'Ме,
ЬС==Х, b C(==X) N, bC N C';
а": 1/ 0 Ме, ЬоМс, рМс, r NH, r С==Х and thrcc torsions.
The vibrational analysis of McC(==X)NHMc (N-mcthylacctamide, N-mcthyl-
thioacctamide) reveals 30 normal vibrations (19а' + 11 а") of\vhich ninc (5а' + 4а")
arc due (о the Ме group. If опе torsion (а") has Ьсеп rcplaced Ьу а C C stretching
(а') vibration, thc remaining 21 vibrations arc thc samc as those mentioncd аЬоус.
190 Nотшl Vib/'aliolls ат! ЛЬsо/'рliОIl Regiolls о/ с(==х) у
Just as in рriшаrу ашidсs, sошсtiшсs tllC typica\ ашidс viLlrations arc trcatcd as
ашidс bands (l Vl) with thc skclctal C N C' dcformation as ашidе УН.
7.3.1 Metllylc31'bal11oyl (mсtllуlашiпосаrЬопуl)
ТаЫе 7.12 Nomlal vibralions of tral/S N-П1с'hу1fоrшаП1idе and N-П1сthуlассtаП1idс
Vibration HC(==O)NHMc McC(==O)NHMc Vibration HC(==O)NHMc McC(==O)NHMc
14 а' 19 а' 7 а" 1 J а"
/INH 33000 3306" 1/0Мс 2981
/1 Mc 2994 I/омс 29440 298]0
Y Mc 2944" 2944" Ь"Мс ]4670 14720
I/sMc 28800 29]50 ЬоМс 145/
I/sMc 2935 р'Мс 10400 11140
I/СН 2854 р'Мс 1044
/IC==O (1) ]6700 ]6600 wCH 1015
bNH (11) 15400 15690 ,. NH (У) 7100 7250
b Mc 14580 14580 f С==О (VI) 6200 6000
Ь:,Мс 1426 torsion 192
bsMc 14100 14140 torsion 14з 0 ,с
bsMc 1374 torsion ]оз о . с 121°'С
Ьсн 1392
I/C N (111) ]2440 13000
рМс 11480 1/610
I/N C' 9550 10950
рМс 1044
I/C C 980
Ьс==о (lV) 76з0 6280
b C N (VlI) 439
bC N C' 3680 2890
о wavcnumbcrs of lhc inlcrnal vibrations of C(==O)NHMc
с calculalcd
Тhe NH strctching vibration
Thc hydrogcn bondcd NH strctch appcars strongly and fairly broad in the region
3З15 :!: 45 cm l, with а wcakcr absorption ncar 3080 cm 1 attributcd to
ап ovcrtonc of thc amidc 1I band cnhanced Ьу Fcrmi resonancc. 'П solution
thc band bccomcs narrower and shifts to highcr waventlmbcrs, for cxample in
R C(==O)NHMc molcculcs in which R = Ме (3478), FзС (3470), СlзС (3462)
and ВrзС (3450 cm 1).
Mcthyl strctching vibrations
Both mcthyI апtisушmеtric strctching vibrations oftcn coincidc and absorb bctwccn
2995 and 2900 cm l. Тhc symmctric stretch is found in the rcgion 2870 :!: 45
cm 1, clcarly scparatcd from the antisymmctric countcrpart, with high valucs for
Iralls McC(==O)NHMc (2915) and low valucs for N=CC(==O)NHMe (2825)
7.3 Mell/ylaтi//o(llIio)carbollyl Coтpoullds
191
and N,N' dimcthylurca (2840 cm I). Most R C(==O)NHMc compounds givc
а typical sharp pcak in thc rcgion 2865 :!: 25 cm 1.
Thc с==о strctching vibration
TllC с==о strctching vibration (amidc 1) givcs risc (о а strong band in the rangc
1680:!: 60 cm t. Thc highcst valucs, namcly in thc ficld of cstcrs and kctoncs,
arc found in thc spcctra of R C(==O)NHMc with R = С1 and Br: ::::::173б cm 1
(Scction 7.1) and thc lowcst, а! аЬои! 1б25 cm l, in thosc of N,N' -alkylmcthylurca.
The remaining compounds absorb а! 1655 :!: 30 cm l. In dilutc solution this band
shifts to higher wavenumbers and often givcs ап ovcrtonc in thc ncighbourhood of
ЗЗ70 cm 1, which somctimcs is takcn for thc I/NH of thc cis form.
Thc NH in planc dcformation/C N stretching vibration
Thc NH in plane deformation/C N strctch (amidc 11) absorbs only for the Iralls
configuration in thc rcgion 1550 :!: 50 cm t. In this mixcd vibration the 6NH
is coupled to the I/C N Ьи! in most of thc sccondary amidcs thc bNH makcs
thc larger contribution. Оп dcutcration thc band shifts (о lowcr wavcnumbcrs. Thc
often strong pair of bands (1 and 1I) forms а charactcristic pattcrn in thc spcctra of
tra//s sccondary (poly)amidcs and is thcrcforc of diagnostic intcrcst. As а mattcr of
coursc опс has (о usc grcat carc in vicw of thc N02 or С0 2 absorptions which arc
also strongly active in thc above mentioncd region. Thc amidc 11 band in N mcthyl
acctamide (liquid: 15б9; solution: 1525 cm t) cxists to ап cxtcnt of ::::::48% [15,
17] or ::::::БО% [8] as а NH in plane dcformation. N,N' AII.;ylmcthylurcas display thc
amidc 11 band strongly а! 1565 :f: 35 cm 1. In thc Icss соmmоп cis configuration
thcsc vibrations arc less mixed and thc bNH is obscrvcd а! I4б5 :!: 20 cm l.
Mcthyl deformations
Thc mcthyl antisymmetric deformations arc usually sccn as опс wcak absorption
bctwccn 1480 and 1410 cm 1. Thc symmctric dcformation appcars with а strongcr
intcnsity bctwecn 1425 and 1З75 cm t, but most R C(==O)NHMc compounds
absorb in thc narrower rcgion 1415 :!: 10 cm 1.
Thc C N strctching vibrationlNH in planc dcformation
Just likc the amidc II band, the I/C N/bNH (amidc Ш) is а mixcd vibration
which appcars moderatcly to strongly in thc rcgion 1270 :!: 55 cm t. For most
of thc sccondary amidcs it is gencrally assumcd that thc vC N dominatcs
in this absorption. Thc highest valucs arc found in thc spcctra of N-mcthyl
ассtаmidс dз (1325) and N methylacctamidc (1300 cm l) and thc lo\vcst in those
of BrC(==O)NHMe (1215) and CIC(==O)NHMc (1222 cm t). Thc rcmaining
192 No/'//ral Vibтliolls ат! AlJSOIplioll Regiolls о/ С(==Х) У
examincd compoul1ds give tl1c amidc 1lI bal1d а! 1265 :1: 35 cm t , а region situated
шuсl1 lower tlщп that of tl1e I/C N il1 рriшаrу ашidеs (1390 :1: 40) or sccondary
tl1iоашidсs (1325 :1: 45 cm 1). (п solutiol1 tl1e ашidе 1lI band sl1ifts to higher
\vаVСl1uшЬсrs.
Methyl rocking vibratiol1s and N Me stretcl1
Thc mcthy\ rocks, coupled to thc N Me stretching vibration, absorb weakly
rathcr than moderatcly. Thc рМе occurs а! 1155 :1: 30 cm 1 with the highest
\vavcl1umbcr in thc spectrum of cHcxHNC(==O)NHMe. The rcgion of the р'Ме
is more extcnsivc (1100 :1: б5 cm 1), becausc of CIC(==O)NHMe (11б4),
BrC(==O)NHMc (11б2) and cHcxHNC(==O)NHMc (1160 cm 1) оп the опе side
and sBuHNC(==O)NHMc (10З5 cm l) оп the other. Тl1e р'Ме in the rcmaining
сошроuпds tcstcd falls in 1hc rcgion 1085 :1: 50 cm 1.
The N Mc strctch, in а sensc thc symmctric counterpart of the amidc ll\
vibration, сап Ьс found in the rcgion 1015 :1: 95 cm '. The intensity fluctuates
between wcak and moderatc. Disrcgarding the high values around 110б cm 1
for H2NC(==O)C(==O)NHMc al1d H2NC(==O)NHMe, coincident with thc methyl
rock, and the lo\v valucs for cHexHNC(==O)NHMc (920) and BrC(==O)NHMe
(988 cm '), thc majority of invcstigatcd moleculcs display thc I/C N in the region
1050 :1: 45 cm l.
Thc NH out of plane dcformation
Тhe 1 NH/C==O or wNН/C==O (amide V) is ап out of plane skcletal deformation
which is modcrately but broadly activc in the region 735 :1: БО cm 1. With
this vibration thc О and Н atoms mоус simultancously ои! of the plane in thc
samc dircction. Whethcr the 1 NH or the 1 с==о contributes in greatcr degrcc
to this vibration still rcmains undccided, Tl1is deforrnation mау Ье compared
with thc wNH 2 /C==O in primary amides. Тhe highest valucs are furnished
Ьу BrC(==O)NHMc and MeHNC(==S)C(==O)NHMc with 793 cm 1 followcd
Ьу CIC(==O)NHMc with 788 cm 1, and the lo\vcst Ьу N=CC(==O)NHMe
(б75), H 2 NC(==O)C(==O)NHMc (б87), HSCH2C(==O)NHMc (б93) and finally
McOC(==O)C(==O)NHMc and EtC(==O)NHMc both with б99 cm 1. Most
R C(==O)NHMc compounds absorb in thc rcgion 745 :1: 35 СП1 I. N' AJkyl
dcrivativcs of N methylurca give this amide V absorption а! 7б5 :1: 15 cm 1, and
thc band is assigned to 7/C==O/NH [32].
Тl1c с==о deformations
Thc с==о in-plane dcformation (amide IV) is obscrved in the region б95
:1: 75 cm 1 with а modcratc to strong intcnsity. Тhe rcgions of thc amidc
IV and amide V bands ovcrlap. Тhcir wavcnumbers are close togcthcr
7.3 Melllylaтillo(IIIio)carbollyl Coтpoullds
193
and по! infrequcntly both deformations arc assigncd а! thc samc wavc
numbcr. Thc highcst values ( 770 cm 1) сап Ье found in thc spcctra
of thc compounds McOC(==O)C(==O)NHMc, MC2NC(==O)C(==O)NHMc and
MeHNC(==O)C(==O)NHMe. N' Alkyl N mc1hylurcas R'HNC(==O)NHMc (R'
== Et, nPr, пВи) give this ЬС==О in thc ncighbourhood of 7БО cm l
[32]. Low valucs are assigned in thc spcctra of cHcxHNC(==O)NHMe (б20),
HSCH2C(==O)NHMe (б2б) and MeC(==O)NHMc (б28 cт 1). Тhc rcmaining
compounds show 1his БС==О а! 715 :!: 45 cm 1.
Tlle с==о out of planc dcformation 'у C==O/NH or 1Iс==отн (amidc У\)
absorbs moderatcly in thc rcgion 600 :!: 70 cm ]. With this vibration thc О and Н
atoms mоуе simultaneously ои! of the planc in thc oppositc dircction. Thc highcst
wavcnumbcrs (655 :!: 15 cm t) arc assigncd in thc spcctra of R'HNC(==O)NНMc
compounds (R' = Ме, Et, nPr, пВи, iPr, iВи, tBu) and thc lowcst in those of
H2NC(==O)C(==O)NHMe (530) and McHNC(==O)C(==O)NHMc (532 cm 1).
Thc rcmaining molccules display thc amidc У\ band in thc rangc 595 :!: 45 cm 1.
Skclctal dcformations
Thc extcrnal C(==O) N skelctal deformation appcars wcakly 10 modcratcly in
thc wide range 450 :!: 100 cm 1. For R'HNC(==O)NНMc thc region narrows to
500 :!: 50 cm l with 550 cm l for R' == nPr and пВи. For R C(==O)NНMc
compounds (R = ОС(==О), NC(==O), Мс, Et) thc rcgion bccomcs 420:1: 70 cm 1
\vith thc lowest values (350 and 392 cm 1) for McHNC(==O)C(==O)NHMc. \п
primary amides the corresponding skeletal dcformation is found а! 455 :1: 75 cm 1.
Thc lowest а' vibration is thc skelctal С N С'Нз dcformation, absorbing in
thc rcgion 315 :!: 55 cm ' with а weak to modcra1c intcnsity. Thc lowcst valucs
are assigned in the spectra of McHNC(==O)C(==O)NHMc (2БО and 2б5 cm l)
and MC2NC(==O)C(==O)NHMc (280 cm l).
ТаЫе 7.13 Absorp'ion rcgion (cm 1) of Ihe поrrnаl vibralions of
С(==О)NНС'Нз
Vibralion Region Vibration Region
I/NH 3315:!: 45 р'Мс 1100 :!: 65
l/а МС 2970 :!: 30 I/N C' 1015 :1: 95
I/ Мс 2945 :!: 45 'у NН (v) 735 :1: 60
I/sMc 2870 :!: 45 ьс==о (1V) 695 :1: 75
I/С==О (1) 1680 :!: 60 'у С==О (VI) 600 :1: 70
bNНlCN (11) 1550 :!: 50 b C(==O) N 450:1: 100
ЬаМс 1450 :!: 30 bC N C' 315:1: 55
Ь:,Мс 1445 :!: 35 torsion 230 :1: 50
bsMc 1400 :!: 25 torsion
I/C NlbNH (111) 1270 :!: 55 torsion
рМс 1155 :!: 30
194 Nотшl Vib1'llliolls ат! ЛЬSOl'рliо" Regio"s о/ С(==Х) У
R C(==O)NHMc пюlССl1lсs
R = H [1---6], D [3], Mc [4--1.8], СDз [11 15], Et [19], HSCH2 апd
HSCH2CH2 [20], ХзС (Х = F, CI, Br) [21], MeOC(==O) [22],
KOC(==O) [23], H2NC(==O) [24], McHNC(==O) [24, 25],
MC2NC(==O) [24], MeHNC(==S) [26, 27], N=C [28], H2N [29],
McHN [30 32], Etl--IN , пРrНN апd nBuHN [32, 33], iBuI--IN ,
sccBuHN and tBuHN [33], cHexHN [З4], NЗ [35], Cl and
Br [3б].
References
1. R.L. Joncs, J. Mol. Spec//'Osc., 2, 581 (1958).
2. Н.Е. Наllаm and Ch.M. Joncs, Tralls. FarQ(la)' Soc., 65, 2607 (1969).
3. 1. Suzuki, 8//11. С//е1ll. Soc. JplI., 35, 540 (1962).
4. R.L. Jones,J. Мо/. Spec/rosc., 11, 411 (1963).
5. S. Ataka, Н. Takeuchi and М. Tasumi, J. Мо/. S/l'IIc/., 113, 147 (1984).
6. А. Balazs, Acta C//im. Acad. Sci. H/II/g., 108, 265 (1981).
7. А. Balazs,J. Мо/. S/l'IIc/., 153, 103 (1987).
8. Т. Miyaza\va, Т. Shimanouchi and S. МizuslliП1а, J. С//е1ll. P//ys., 29, 611 (1958).
9. 0.0. Bonner, KW. Bunzl and G.B. Woolscy, Spec/rosc//illl. Acta, 22, 1126 (1966).
10. У. Grcnic, М. Avignon and С. Garrigou-Lagrange, J. Mol. S/rиc/., 24, 293 (1975).
11. В. Schncidcr, А. Horcni, Н. Pivcova and J. Honzl, Collec/. Czec//. C/rem. СоттШI., 30,
2196 (1965).
12. Н. Pivcova, В. Schncidcr and J. S'okr, Collect. Czec/I. С//е1ll. СОlllт/II/., 30,2215 (1965).
13. А. Warshcl, М. Levit\ and S. Lifson, J. Мо/. Speclrosc.,33, 84 (1970).
14. J. Jakcs and S. Krimm, Spec//'OscIIiIll. Ас/а, Parl А, 27А, 19 (1971).
15. М. Rcy-Lafon, М.Т. Forcl and С. Garrigou-Lagrangc, Spec/roscl1im. Асщ РQI'/ А 29А,
471 (1973).
16. N.G. Mirkin and S. КriП1m, J. Мо/. Slr//c/., 236, 97 (1991).
17. N.G. Mirkin and S. Кrimm, J. Ат. С/,ет. Soc., 113, 9742 (1991).
18. Т.с. Chcam, J. Мо/. S/r//c/., 257, 57 (1992).
19. J. Jakcs and S. КriП1m, Spec/rosc//illl. Ас/а, Par/ А, 27А, 35 (1971).
20. G. Zuppiroli, С. Pcrchard, M.L. Baron and С. de Loze, J. Мо/. Sll'IIct., 69, 1 (1980).
21. R.A. Nyquist, Spec/roscl1illl. Ас/а, 19,509 (1963).
22. Н.О. Ocsscyn, B.J. Уап dcr Vckcn and М.А. Нсnnап, ВuН.Sос.СI1iП1.Всlg. 84, 1057
(1975).
23. Н.О. Ocsseyn, B.J. Уап der Vekcn, A.J. Aarts and М.А. Нсnnап, J. Mol. Strllcl., 63,
13 (1980).
24. Н.О. Ocsseyn, B.J. Уап dcr Vckcn and М. Нсnnап, Spec/rosc//im.Ac/a, 33А, 633 (1977).
25. R.A. Nyquist, R.W. Chrisman, C.L. Putzig, R.W. Woodward and B.R. Loy,Spec//'OscIIim.
Асш, Part А, 35А, 91 (1979).
26. Н.О. Desscyn, J.A. Le Poivrc and М.А. Неnnап, Spec/rosc//im. Асщ Part А, 30А, 503
(1974).
27. Н.О. Ocsscyn, A.J. Aarts and М.А. Неnnап, Speclrosc//im. Асш, Part А, 36А, 59
( 1980).
28. Н.О. Ocsscyn and B.J. Уап dcr Veken, Spec/rosc//illl. Ас/а, РQI'/ А, 31А, 641 (1975).
29. У. Saito, К. Machida and Т. Uno, Spec/rosc//illl. Acla, Part А, 31А, 1237 (1975).
30. C.N.R. Rao, G. Chaturvcdi and R.K Gosavi, J. Мо/. Spec/rosc.. 28, 526 (1968).
31. KR.G. Ocvi and O.N. Salhyanarayana, 81111. С//ет. Soc. J p/l., 53, 2993 (1980).
7.3 MCII/y/aтi/lo(tllio)carbo/lyl CompOllllds 195
32. У. Mido, F. Fujita, Н. Matsuura and К. Machida, Speclrosc//im. ACla, Par/ А, 37А, 103
(1981).
33. У. Mido, Spec/ro.l'c//ill1. Acla, Par/ А, 28А, 1503 (1972).
34. У. Mido, Spec//'O.I'c//ill1. Асш, Par/ А, 32А, 1105 (1976).
35. W. Budcr and А. Schmidt, Spec/rosc/lim. Ас/а, Par/ А, 29А, 1429 (1973).
36. W. Budcr and А. Schmidt, Spec/ro.l'cl1iт. ЛС/а, Parl Л, 29А, 1419 (1973).
7.3.2 Methylthiocarbamoyl (methylaminothiocarbonyl)
Thc NH slrctching vibration
Thc NH stretching vibration gives rise to а modcrate to strong absorption in the
rcgion 3250 :!:: 70 cm l. In dilute solutions thc band shifts to highcr wavc
numbcrs, for ехаmр]е З425 cm 1 for McC(==S)NHMc and 3450 cт 1 for
МсОС( ==S)NHMe.
Mcthyl strctching vibrations
Both methyl antisymme1ric strctching vibrations absorb betwecn 3000 and 2920
cm 1. Thc symmetric stretch is activc а! 2875 :i: 45 cm 1, wcll scparatcd from its
antisymmetric counterpart.
Thc NH in plane deformation/C N stretching vibration
The mixcd vibration bNH/I/C N (thioamidc 11) is strongly activc in thc rcgion
1535 :f: 35 cm 1. Aftcr dcutcration this thioamidc 11 band shifts to lower wavc-
numbers in such а way as to indicatc that thc bNH dominatcs. Thc vibration bcars
а good rcsembIance to the amidc 11 vibration in sccondary amidcs (1550 :f: 50
cm 1). N Mcthylthioformamidc {N methylthioacctamidc} absorbs а! 1550 {15б4}
cm 1. Extreme valucs arc found in thc spcctrum of McHNC(==S)NHMc (1570
and 150б cm 1).
Methyl deformations
Thc methyJ antisymmetric dcformations arc obscrvcd Ьс!\уссп 1475 and 1410 cm 1
and the symmctric counterpart betwccn 1425 and lЗ75 cm t.
The C N stretching vibration/NH in planc dcformation
Thc I/C N/bNH (thioamide 111) is а mixcd vibration occurring in thc region 1325
:i: 45 cm 1 with а moderatc to strong intcnsity. This vibration is assigned as
much to thc I/C N as to the bNH but thc band is Icss scnsibIe to deutcration than
thc thioamide 11 band. N Methylthioformamidc {N-mcthylthioacctamidc} givcs this
vibration strongly а! 1334 {135б} cm l.
19б Noттl Vibraliolls ат! Absorplioll Regiolls о/ С(==Х) У
Metllyl rockil1g vibrations and N Me strctch
TI1C coupled vibrations pMe//JC N and p'Me/I/C N arc usually seen in the
rangcs 1145:1: 45 and 1075:1: 40 cm 1, comparablc \vith tllOse of tlle corrcsponding
secondary amidcs.
Just as in sccondary al1lidcs, the N C' stretch is in а scnsc thc symmctric
countcrpart of thc thioamidc 1II vibration and is activc in tllC rcgion 1000 :1: 50
cm 1. In N mcthyIthioformamide {N mctllylthioacctamide} this vibration occurs
а! 987 {950} cm l. Thc I1igllcst valuc, Ьу contrast, is found in thc spectrul1l of
KOC(==O)C(==S)NHMe (1045 cm l).
Thc C==S strctching vibration
The C==S strctching vibration (thioamidc 1) in secondary thioamides is а mixed
vibration (scc Scction 7.2.2), locatcd in thc rcgion 795 :1: 110 cm l with modcratc
intensity. This region is so cxtcnsive because of thc cxtrcmc valucs 905 and
б88 cm 1 in thc spcctrum of MeOC(==S)NHMe assigncd rcspectively to thc
cis and thc IrallS form. High wavenul1lbcrs arc also found in the spcctra of
MeHNC(==S)C(==S)NHMc (870) and HC(==S)NHMe (865 cm 1) and low wave
numbcrs in thosc of McC(==S)NHMc with 700 cm 1 for thc (,'alls (95%) and 722
cm 1 for thc cis form (5%). The rсmаiлiпg compounds show thc thioamidc 1 band
at 780 :1: БО cm 1.
Thc NH out of planc dcformation
Thc 1 NH/C==S or wNH/C==S (thioamide У) usually providcs а broad band
with а moderatc to strong intcnsity in thc rangc бб5 :1: 55 cm l. With this
vibration thc S and thc Н atoms mоус simultancously out of thc plane in thc sal1lc
direction. For N methylthioformamide {N methylthioacetamide} thc thioamidc V
absorbs а! 700 {б90} cm 1. Thc HW side of the abovc mentioned region is
limited Ьу 720 cm 1 from thc spcctrum of KOC(==O)C(==S)NHMc and 715 cm 1
(coincident with amide У) from H 2 NC(==O)C(==S)NHMc. Thc LW side is covered
Ьу McHNC(==S)NHMc (610 and 642 cm t). The rcmaining compounds display
thc thioamidc V band at 670 :1: 30 cm 1.
Thc C==S dcformations
Thc C==S in-planc deformation (thioamide IV) exhibits only wcak to I1lcdium
intensity in thc rcgion 585 :1: 55 cm 1, that is, 100 cm 1 lowcr than the
region of thc amidc IV absorption. Thc highcst wavcnumbcrs are due to
KOC(==O)C(==S)NHMe (б40) and McHNC(==O)C(==S)NHMc (б34 cm l) and
thc lowcst has Ьсеп 1raccd in thc spcctrum of H 2 NC(==S)C(==S)NHMe: 5З5
cm 1 for both thioamidc lV bands. Most RC(==S)NHMc compounds display this
7.3 Mell/y/aтillo(ll/io)carboпyl Coтpo/Illds
197
thioamidc IУ band а! 580 :1: 30 cm 1, with N methyIthioformamidc (БОО) and
N methylthioacetamide (555 cm 1) as examplcs.
Тhe I C==S/NH or 7fC==S/NH (thioamide VI) is а mixcd vibration, wcakly to
moderately active in the rcgion 470 :1: 70 cm 1. With this vibration thc S and
thc Н atoms mоус ou1 of the plane in 1he oppositc dircction. Ву contrast wi1h
thc NНlC==S wag (thioamide У), thc contribution of thc C==S in this vibration
is grcatcr than the contribution of the NH. А high wavcnumber is obscrvcd in
the spcctrum of MeC(==S)NHMe (533) Ьи! H 2 NC(==S)NHMc (400 cm 1) is
responsible for the lowcst valuc. Most RC(==S)NHMe compounds display thc
thioamide УI band at 470 :1: 30 cm 1.
Skclctal dcformations
Тhc ех1еrnаl C(==S) N skcletal dcformation is locatcd in thc rangc 395 :i: 55
cm l. Тhe absorption а! 370 cm 1 in the spectrum of N mcthylthioacetamidc is
assigned to this skeletal dcformation but describcd as pNCS [3], bCS [2] or БСС
[1 ].
The lowest а' vibration of the C(==S)NHMc group is thc skcletal C N C'
dcformation at 265 :1: 65 cm 1 with, as cxamplcs HC(==S)NHMc (2БО) and
McC(==S)NHMe (285 cm 1).
ТаЫе 7.14 Absorption rcgions (cm l) оС the поrrnаl vibrations
of С(==S)NНС'Нз
Vibration Rcgion Vibration Rcgion
I/NH 3250 :1: 70 р'Ме 1075 :i: 40
l/а Ме 2970 :1: 30 I/N C' 1000 :i: 50
I/ Me 2945 :1: 25 I/C==S (I) 795 :i: 110
I/sMc 2875 :1: 45 I NH (У) 665 :i: 55
bNH (11) 1535 :1: 35 bc==s (IV) 585 :i: 55
ЬаМе 1450 :1: 25 I C==S (VI) 470 :i: 70
b Mc 1435 :1: 25 b C(==S) N 395 :i: 55
bsMc 1400 :1: 25 bC N C' 265 :i: 65
I/C N (1II) 1325 :1: 45 torsion 195 :1: 50
рМс 1145 :1: 45 torsion
torsion
R C(==S)NHMe molecules
R = H [1 3], Mc [1--4], MeHNC(==O) [З, 5], KOC(==O) ,
H2NC(==O) and H2NC(==S) [3], McHNC(==S) [б], Ph [3],
H2N [7, 8], MeHN [9 11], Mc(CH2)flHN (п== 1 15) [10],
MeO [12], MeS [13],
198 No,."ta! Vibтlio"s a"d ЛЬsо/рliОIl Regiolls о/ С(==Х) у
Refel'ences
1. 1. Suzuki, B/I/I. C/lem. Soc. JplI., 35, 1456 (1962).
2. C.N.R. Rao and G.c. Chaturvcdi. Spec/lVscl1im. Ас/а, Pat.t А, 27А, 520 (1971).
3. Н.О. Ocsscyn, A.J. Aarts and М.А. Нст13П, Spectrosc//im. ACla, РtlI'/ А, 36А, 59
( 1980).
4. S. A'aka, Н. Takcucl1i. 1. Harada and М. Tasumi, J. P/,ys. CI/em., 88, 449 (1984).
5. Н.О. Ocsscyn, J.A. Lc Poivrc апd М.А. Hcrn13n, Spcctrosc//im. Асш, Par/ А, 30А, 503
(1974).
6. Н.О. Ocsscyn, A.J. Aarts, Е. Esmans and М.А. Нсrrnап, Spec/rosc//im. Acta, Part А,
35А, 1203 (1979).
7. К, O\varakana,h and O.N. Sathyanarayana, B/I/I. С//ет. Soc. JplI., 52, 2084 (1979).
8. KR.G. Ocvi, O.N. Salllyanarayana and S. Manogaran, Spec/rosc//im. Acta, Par/ А, 37А,
31 (1981).
9. K.R.G. Dcvi and O.N. Sathyanarayana, B/I/I. CI/em. Soc. JPI1., 53, 299 (1980).
10. У. Mido. Н. Mizuno and К. Machida, Spec/rosc//im. Ас/а, Parl А, 44А, 445 (1988).
11. R.K. Ri'chic, Н. Spcdding and О. Stcele, Spec/rosc//im. Ас/а, Part А, 27А, 1597
(1971).
12. G.c. Chaturvcdi and C.N.R. Rao, Spectrosc//im. Асщ Pat.t А. 27А, 65 (197]).
13. K.R.G. Ocvi, O.N. Sathyanarayana and S. Manogaran, Spectrosc//im. ACla, Part А, 37А,
633 (1981).
7.4 CARВOXYLATE
Тhc C02 structurc unit, occurring in thc salts of carboxylic acids or as а dipolar
ion in amino acids, has six normal vibrations. According to the position of the
planc of symmctry with the О atoms in (i.p.) or pcrpcndicular to (о.р.) this plane,
thc distribution is as follows:
Point group l/ а СО 2 I/ s C0 2 ЬСО 2 wC02 р СО 2 torsion
С 2 ,. О.р.) Ь 2 а) а} Ь 1 Ь 2 а2
С . (i.p.) а' а' а' а" а' а"
С2,. (о.р.) Ь 1 а1 аl Ь 2 Ь 1 а2
C s (о.р.) а" а' а' а' а" а"
Whcn а carboxylic acid changes into а carboxylatc the с==о and c o arc
rcplaccd Ьу two cquivalent carbon oxygen bonds which arc intcrmcdiate in force
constant bctwccn thc с==о and c o. Thc I/С==О, occurring in а carboxylic
acid а! 1725 cm l, shifts to а wavcnumbcr lower Ьу ::::::130 cm 1 and the I/C O,
occurring а! 1250 cm 1, to ::::::130 cm 1 highcr wavcnumber 10 give the СО2 anti
symmctric and symmctric strelching vibration.
7.4 Carboxylate
199
Thc С02 stretching vibrations
With thc cxception of СF з СО;, thc СО; antisymmctric strctching vibration (or
"СО 1) absorbs strongly and broadly in thc rcgion 1600:!: 75 cm l. Thc highcst
valucs originatc from thc spectra of Х з ССО; (Х = F, CI, Br) with rcspectively lб80,
1675 and 1664 cm 1 and the lowest from thosc оС 2 McPhCO;, 2 Pyr CO; -d 1
with 1525 cm 1, 2 Pyr CO; do with 1529 cm 1 and sodium bcnzoatc-ds with
1534 cm 1. The l/ а СО; in salts of aromatic carboxylic acids is reported in thc
rangc 15б5 :I: 40 cm 1, Ьи! the remaining R CO; compounds absorb а! 1БОО :I:
БО cm 1.
The СО; symmetric stretching vibration (or I/СО 11) providcs а mcdium to
strong band in the rcgion 1385 :::1: 65 cm 1 with thc highcst wavcnumbcrs Crom
FзССО; (1450), H2C==CHCOi (1450) and 2-Руr СОi (1445 cm I). Thc
lowcst wavenumbcrs havc Ьееп traced in thc spcctra of sodium oxalatc (1321
and 1340) and sodium oxamatc H2NC(==0)CO; (135б [3б] with I/C N а! 1448
or 1323 cm 1 [34]). For tlle remaining compounds, thc I/ s C0 2 is assigncd in thc
region 1440:::1: 40 cm l. Sodium acctate absorbs а! 1422 cm l, sodium bcnzoatc
а! 1413 and glycine а! 1415 cm 1. А good numbcr of substitutcd bcnzoatcs and
amino acids in the zwittcrion form show this I/ s C0 2 around 1410 cm 1.
Both typical broad absorptions arc vcry uscful for identification purposcs,
although R N0 2 compounds (Section 9.5) absorb also in thcse rcgions but по! so
broadly.
Thc С0 2 deformations
Thc СО;;- scissors, а mixed vibration, is activc in thc cxtcnsivc rcgion 735 :I: 125
cm 1 \vith moderate intensity, although а fcw invcstigators assign thc СО; wag
in this region. The HW side is limitcd Ьу 4-X substitutcd sodium bcnzoates (Х =
Н, О, Ме, F, Cl, Br, СО;) (850 ::1: 10 cm l) and CiS 02CCH==CHC02 (855
and 738 cm l). The lowest values are from McCOi -d з , EtCO; -d з and -ds and
McHNC(==S)CO;;- do, dl and dз with valucs in thc ncighbourhood оС 610 cm l.
Thc remaining m;Ieculcs display bCOi in thc rangc 725 :I: 100 cm l. Sodium
acctate absorbs а! 651 cm 1, sodium propanoatc а! б47 and glycinc а! б9б cm 1.
Thc COi wagging vibration givcs risc to а band with variablc intcnsity in thc
range 575 :::1: 125 сm 1 . А few invcstigators rcscrvc this rcgion for the С0 2 scissors.
Thc highcst wavenumbers are duc to 4 X substitutcd sodium bcnzoatcs (Х = Н, О,
Мс, F, Cl, Br) (б90 ::1: 10 cm l) and С1зССОi (б89 cm l), and thc lowcst havc
Ьссп traced in thc spectra of а fcw (thio)oxamatcs such as D2NC(==0)C02 (450),
H 2 NC(==0) CO i (485), McHNC(==S)CO; (4б5), McHNC(==O)CO; (490) and
in that of BrCD2CO;;- (479 cm t). Thc rcmaining compounds absorb in thc rcgion
595 :I: 90 cm 1, cxa plcs being sodium acctatc (620), sodium bcnzoate (б83) and
glycine (б07 cm 1). A1though thc rcgions of ЬСО; and ""СО; overlap, coincidcnt
wavcnumbcrs are cxceptions rathcr than thc rulc.
200 Norlllal Vibтliolls атl AbsOI'plioll Regiolls о/ с(==х) у
Thc СО;- rocking vibralion is localed in Ihc region 470 :1: 120 cm 1 wilh
а \veak 10 П1еdiuП1 inlcnsilY, well separaled from Ille wag. Zwitterions (530 :1:
60), salls of aromalic carboxylic acids (515 :1: 65) and 111e three iSОП1еrs of
О2ССН==СН Cl-I==СН СО;- ( 540 cm l) are rcsponsibIe for Ihe high
values, The LW side of the region is limiled Ьу ICH2CO;- (359), N=CCl-1 2 СО;-
(371) and BrCH2CO;- (377 cm l). Most of the rocks have Ьесп observcd аl 460
:1: 60 сm 1. Sodium acelatc absorbs аl 463 сm 1, sodium benzoale а! 526 and
glycine а! 503 cm l.
ТаЫе 7.15 Absorption rcgions (cm ') оС Ihc поrrnаl vibralions оС co;-
Vibra,ion Q salurated Q halogen с==о, C==S Q unsalur. aromalic z\vittcrion
l/ а С02 1580 :1: 30 1630 :1: 45 1640 :1: 20 1585 :1: 35 1565 :1: 40 1585 :1: 25
1/., С0 2 1395 :1: 40 1400:1: 50 1385 :1: 65 1405 :1: 45 1410:1: 35 1410:1: 30
ЬС02 700 :1: 90 735 :1: 85 700 :1: 90 740 :1: 115 795 :1: 65 739 :1: 90
WC02 565 :1: 60 600 :1: 90 540 :1: 90 515 :1: 75 670 :1: 30 625 :1: 55
рС 0 2 430 :1: 60 440 :1: 80 395 :1: 45 480 :1: 70 515:1: 65 530 :1: 60
torsion 140:1: 60 195 :1: 50
R CO:;- М+ molcculcs (М+ = Na+, К+)
R = Н...::... [1---4], Mc [4---11], CH2D , CHD2 and СDз [5],
Et [9, 12], Et d2 , dЗ and d5 [12], HOCH2CH2CH2 and
DOCH2CH2CH2 [13], HO(O==)CCH2CH2 [14, 15],
DO(O==)CCH2CH2 [14], HO(O==)CCH2 [1б], 02CCH2 [17],
McCHOHCH2 and MeCHODCH2 [13], EtCH==CHCH2 [18J,
N=CCH2 [9, 19], HSCH2 , EtCHOH and EtCHOD [13],
cPr [20], cBи [21], сРспt-dо and d, [22], tBu
[9], HO(O==)CCH2CH2C(Me)2 , DO(O==)CCH2CH2C(Me)2 and
02CCH2CH2C(MC)2 [23], HO(O==)CC(MC)2 and 02CC(Me)2
[24], FCH2 [9], CICH2 [9], BrCH2 [9, 25], BrCD2 [25],
ICH2 [9, 2б], CI2HC and Br2HC [9], FCIНC do and d1 [27J,
FзС [9, 28, 29], СlзС [9, 30], ВrзС [9], MeC(==O) [31,
32], H2NC(==O) [33 Зб], D2NC(==O) [Зб], MeHNC(==O) do and
dl [3БJ, H2NC(==S) do and d2 [3б], McHNC(==S)-dо ,
d1 and dЗ [З7], McOC(==O) [37], 02C [4, З8,
39], CH2==CH [40], nPrCH==CH [18], HO(O==)CCH==CH
[41, 42], McO(O==)CCH==CH [4З], 02CCH==CH [17, 44],
02CCH==CHCH==CH [45], HC=C do and dl [46], Ph [47
50], 2 XPh (Х = Мс, F, Сl and Br [47], 02C [51], НО [50]), 3 XPh (Х
= Ме, F, Сl and Br [47], 02C [51], H 2 N [52]), 4 XPh (Х = D [48], Ме, F,
Сl and Br [47], 02C [51, 53, 54]), Ph-d5 [48], PhF5 [55], 2 Fu and
5 X 2 Fu (Х = Cl, Br) [5б], 2 Pyr do and dl [57],
7.4 Carboxylale
201
R C02 molecules
R = +НзNСН2 and +DзNСН2 [58---67], +H2DNCH2 and +HD2NCH2
[62], +НзNСD2 and +DзNСD2 [64], +НзNСН2СН2 and
+DзNСН2СН2 [68, 69], +Н з NСН 2 С(==О)NНСН z -d о , -d2 , -d4 ,
-d6 and dR [70], +НзNСН(Мс) and +DзNСН(Мс) [71
75], +DзNСН(СDз) [73], НОСН2СН(NНз) , HOCD2CD(NНj) and
DОСН2СН(NDз) [76], HSCH2CH(NНj) and DSСН2СН(NDз) [7б],
СIСН2СН(NНз) and CICH2CH(NDj) [7б], +НзNСН2СН(ОН) and
DзNСН2СН(ОD) [77], З +НзNРh and 3-+DзNРh [52].
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7.4 Carboxylale
203
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8
Normal Vibrations and
Absorption Regions of
Alkenes and Alkynes
8.1 ALКENES
Since thc поrП1аl vibrations of alkencs arc derivcd from those of ethene, it is helpful
to have just а look а! this spcctrum. Ethcnc bclongs to thc point group D2II' Thc
twclvc normal vibrations are dcscribcd as in ТаЫе 8.1. Only five vibrations arc
infrarcd activc.
ТаЫс 8.1 Norrna] vibrations of cthcnc [1---6]
Vibration ОУI cm 1 Vibration 02/. СП1 1
I/ s CH 2 a g 3026 WCH2 b2g 950
I/С==С 1623 l/ о СН 2 Ь2/f 31060
ЬСН2 1342 Р СН 2 810.
ТСН2 а/f 1027 l/ о СН 2 b3g 3103
I/ s CH 2 bl/f 2990 о Р СН 2 1236
ЬСН2 14440 wCH2 Ь3/f 9490
О 1nfrared activc
8.1.1 Vinyl (ethenyl)
Thc simplcst compounds with а CH==CH2 structure unit are those of the type
ХСН==СН2 (Х == F, Cl, Br and 1). In the C s symmctry the 3N б = 12 normal
vibrations arc dividcd into 9а' + 3а" spccics of vibration. If the I/СХ (а') is
substitutcd Ьу а torsion (а"), thc Jwelve normal vibrations are dcscribed as follows:
В.] Alkeпes
205
а': l/аСН2, I/СН, I/sCH2, I/С==С, ЬСН 2 , ЬСН, рСН 2 , b C==C;
а": c.vCH, c.vCH2, ТСН 2 and torsion.
'П some cases the three СН groups arc simply conccivcd as isolatcd bonds, giving
thc following СН vibrations: 3I/СН, 3ЬСН and З""СН.
Thc СН stretching vibrations
The СН strctching vibrations occurring аЬоус 3000 cm 1 normally iпdiсаtс thc
prcscnce of sp2 hybridizcd СН bonds. Usually l/аСН2 and I/СН absorb аЬоуе 3000
cm 1 and I/sCH2 around зооо cm '. Оипсап rcportcd а corrclation ЬСlwссп thc
scparation of the СН 2 stretching frcqucncics and thc НСН anglc [147).
Тhc l/ а СН 2 is observed in thc rcgion 3070 :!: 70 cm 1. Thc highcst wavc-
numbcrs arc those duc to PhSCH==CH2 (3140), F З СС(==О)ОСН==СН 2 (3138),
МсОСН==СН2 (3132) and FCH==CH 2 (3130 cm 1). Thc lowcst valucs arc from
2-РУСН==СН2 (3005) and 3-ХРhСН==СН2 (Х = Br and Мс) with 3010 CПJ 1, that
is, in the rcgion of the aromatic СН strctching vibrations. Most vinyl compounds
absorb а! 3085 :1: 40 cm 1 .
Thc HW sidc of the rcgion of I/СН (3045 :!: б5 cm l) is limitcd Ьу values from
thc spcc1ra of F З СС(==О)ОСН==СН 2 (3110), FCH==CH 2 (3100), CICH==CH2
(3090), BrCH==CH 2 (3087), vinyl formatc (3095) and vinyl aCctatc (3090 CПJ 1).
Thc LW side is covered Ьу 3-СIРhСН==СН2 (2982), 3-ВrРhСН==СН2 (2988),
НзSiСН==СН2 (298б) and DзSiСН==СН2 (298З cm t). For thc rсmаiпiпg
compounds the region З040 :1: 40 cm 1 applics.
Thc I/ s CH 2 is reportcd in the range 3000 :!: 70 cm l with, а! the HW
sidc, СFЗС(==О)ОСН==СН2 (30б9), FC(==O)OCH==CH2 (3058) and FCH==CH 2
(3045 cm 1) and а! thc LW sidc 3-МсРhСН==СН2, 3-СIРhСН==СН2 and 2- and
4-РУСН==СН2 with ::::::2930 cm l. Thcre is а rcalistic chancc of спсоuпtсriпg this
vibration а! 3000 :1: 40 cm l, somctimcs going bchind thc sp3 CH absorptions.
Thc С==С stretching vibration
Thc I/С==С gives а good group vibration in thc rcgion 1б25 :!: 45 cm ! but thc
intcnsity is mcdium rather than strong. Thc unsaturatcd hydrocarbons with tcrminal
vinyl groups usually absorb а! 1б45 :1: 10 cm 1. 'П conjugatcd systcms, this С==С
strctch falls in the range 1610 :!: 30 cm l, that is, in thc ficld of aromatic ring
strctching vibrations. 1,3-Butadienc absorbs а! 1б40 and 159б cm l.
Thc СН in-plane deformations
Thc ЬСН 2 is locatcd in the rcgion 1400 :!: 40 cm l. Thc highest valucs
arc furnishcd Ьу FЗССН==СН2 (1440), l,3-Ьutаdiспс (1440 and 1385),
НОС(==О)СН== СН 2 (1430) and H2NC(==O)CH==CH2 (1428 cm l). The lowcst
20б No/'//тl Vibтliolls ашl AbSOl7JliOll Regiolls о/ Alkclles а1/{! Alkynes
valucs arc from FЗСС(==О)ОСН==СН2 (1364), NaOC(==O)CH==CH2 (1370) and
НС(==О)ОСН==СН2 (1373 cm t). Mosl of 111C vinyl сошроuпds absorb а! 1400
:1: 25 cm 1 so Ihat Ihis band is usually а good indicator for tl1e prcscnce of the
CH==CH2 fragmcnl.
Тhe ЬСН appears а! 1285 :1: 45 cm 1. Disregarding sошс cxtrcme valucs in the
spectra of DзСОСН==СН2 (1328) and МеОСН==СН 2 (1324 сш t) оп tl1c опе
sidc and in thosc of II'alls-Н2С==СНСН==СНСН==СН2 (1245 and 12ВО), S-l1'alls
FCH2CH==CH2 (]243), BrCH==CH 2 (1258) and DзSiСН==СН2 (1260 cm l) оп
thc olher, thc ЬСН is observcd а! 1295:1: 25 cm l.
The vibrational analysis of R CH==CH2 compounds rcveals the sccond ЬСН2,
oftcn assigned as the СН2 rocking vibration, in tl1C region with thc greatest
sprcad: 1095:1: 85 cm '. Tl1is region narrows 10 10б5 :1: 55 cm l if somc high
wаvспuшЬеrs in thc spcclra of Н2С==СНСН==СНСН==СН2 (1180 and 1080),
Mc(CI)CHCH==CH2 (1178), МеСН==СН2 (1 172), Ira11S CICH==CHCH==CH2
(l1БО), cis-CICH==CHCH==CH2 (1130), (Н2С==СНСН2)ЗР (1160),
(Н2С==СНСН2)3Лs (1150), МС2С==СНСН==СН2 (1148), trans
N=CCH==CHCH==CH2 (1140) and Х(О==)ССН==СН2 (Х = Н, F, Cl, Br) (1140
:1: 20 cm 1) arc по! takcn into account. Тhc Ira1lS isomers (conformers) absorb а!
higher \vavcnumbcrs than the cis isomcrs (conformcrs). Thc C C== strctching
vibration, occurring in thc ncighbourllOod of 900 cm 1, mау also cOnlribute to the
absorption in thc abovc mcntioned region, and thc РСН2 providcs а contribution
to thc absorption а! ::::::900 cm 1, so that somc invcstigators refer this РСН2 to thc
rcgion 900 :1: 50 cm 1 [77, 83, 86, 9З].
Тhe СН out-of planc dcformalions
Ву far thc most uscful infrared bands to clucidatc thc CH==CH2 structurc are
thc strong absorptions а! ::::::915 and ::::::990 cm 1 \vith а wcak ovcrtone а! ::::::1830
and а vcry wcak опс а! ::::::1980 cm 1. Togcther with Ihe С==С strctching vibration,
thcsc out-of-planc dcformations arc vcry charactcristic.
Тhc СН wagging vibration, occurring а! 975 :1: 35 сm ', is somelimcs describcd
as thc in phase II'allS СН==СН wag and is lcast scnsitivc 10 thc Q alom. Si bondcd
vinyl scorcs high (::::::1000) and halogen bonded vinyllow (::::::950 cm t), followed
Ьу o and S-bondcd vinyl (::::::970), R'C=CCH==CH2 and N=CCH==CH2 (970
:1: 10 cm 1). 1,3 Butadicnc shows both СН wags а! 991 and 967 cm t. Most of
thc R CH ==СН 2 compounds wcrc found to givc this wagging modc in thc rcgion
990:1: 10 cm l, and alkcnes wilh thc formula МС(СН2)"СН==СН2 (ll = 0---15)
сусп а! 990:1: 5 сш 1 [151].
Тhe СН2 wagging vibration is assigncd а! 895:1: 85 cm 1 and is more scnsitive
to thc influencc of thc Q-atom. Тhc highcst values (9БО :1: 20 cm t) arc obscrvcd
in thc spectra of Si-substitulcd vinyl, followcd Ьу carbonyl subslituted viny! (950
:1: 30) and FЗССН==СН2 (965 cт 1). Thc СН 2 wag in halogcn bondcd (885 :1:
25) and 0- and S-bonded vinyl (855 :1: 45 cm l) is shiftcd to !owcr values. The
В.] Alke/les
207
remaining molcculcs display this СН2 wag in thc rcgion 915 :f: 20 cm l. For thc
scrics МС(СН2)"СН==СН2 (п = 15) this rcgion is rcduced (о 910 :f: 5 cm !
[151 ].
Thc wCH, occurring in thc cxtcnsivc rcgion 565 :f: ]55 cm l, is often dcscribcd
as thc СН2 twisting vibration or as thc cis сн==сн wag and is most undcr thc
influcncc of thc Q atom. I! is а wcak (о modcratc band of minor importance as а
diagnostic tool.
Skclctal C==C dcformation
As а mattcr of coursc this cxtcrnal skclctal dcformation is vcry scnsitive to thc
influcncc of the Q-atom, which cxplains thc broad rcgion. Thc highcst valucs arc
obscrvcd in the spcctra of Q-saturatcd vinyl compounds (490::!: 110 cm l) with БОО
cm ] for the S-cis conformcr of FCH2CH==CH2 (S-tra/ls: 430), so that the rcgion
460::!: 80 cm 1 also givcs satisfaction. Low valucs arc rcponed in thc spcctra of
Si bonded vinyl (ззо :f: 80) and с==о bondcd vinyl (345 :f: 95 cm 1) cxamplcs
bcing ХС(==О)СН==СН2 (Х = F, CI, Br) compounds (270 :f: 20 cm 1).
ТаЫе 8.2 Absorption rcgions (cm l) of thc norrnal vibrations of CH==CH2
Vibralion
Q-sa!.
С==О conjugatcd aromatic
bondcd
о and S Si-bonded Hal-bondcd
bonded
l/ о СН 2 3095 ::1:: 15 3105::1:: 20 3085 :f: 45 3045 :f: 45 31]5::!: 25 3070 :f: 20 3120::!: 10
I/сн 3025 ::1:: 25 3040 ::1:: 40 3035 ::1:: 35 3005 :f: 25 3070 :f: 40 3010 :f: 3О 3090 :f: 10
I/ s CH 2 2990 ::1:: 20 3015::1:: 25 2990 ::1:: 40 2965 :f: 35 3030 :f: 40 2970 :f: 20 3035 :f: 10
I/С==С 1650::1:: 20 16зо:f: 20 1610::1:: 30 '6ЗО:f: 10 1620::!: 35 1605::!: 25 1630 :f: 25
ЬСН2 1420 ::1:: 20 1400 :f: 3О 1410::1:: 30 1410 :f: 20 1390::!: 3О 1410::!: 20 1375 :f: 05
Ьсн 1275::1:: 35 1285::1:: 15 1280 :f: 40 1305 :f: 15 1300 :f: 3О 1270::!: 20 1280::!: 20
ССН, 1100::!: 80 1090::1:: 70 1095 :f: 85 1055 :f: 35 1060 :f: 50 1020::!: 10 1070 :f: 50
""CH 990::!: 10 985::1:: 15 980 :f: 20 985::!: 10 970 :f: 25 1000::!: 10 950 :f: 10
""сн, 935 ::1:: 30 950 :f: 3О 910 :f: 40 920 :f: 20 855 :f: 45 960 :f: 20 885 :f: 25
тсн; 600 :f: 80 605 ::1:: 60 615 ::1:: 90 600 :f: 50 650 :f: 70 475 :f: 65 645 :f: 65
b ё==c 490::1:: 110 345 ::1:: 95 390::!: 100 470::!: 80 480::!: 110 330 :f: 80 440 :f: 50
torsion '40::1:: 60 140::1:: 50 150::!: 50 140::!: 50 110 :f: 40
R CH==CH2 compounds
R = Mc [6---11], DзС [8], Et [б, 1 1З], пВи [14], Mc(CH2)" (п =
2 15) [11], Cl(CH2)" [15, 16], Br(CH2)" [15, lб], H2C==CHCH2 [17,
18], H2C==CHCH2CH2 , N=CCH2 [13, 19 21], HOCH2 ,
DOCH2 and HOCD2 [22], McC(==O)OCH2 [23], ONOCH2
and 02NOCH2 [24], OCNCH2 and SCNCH2 [146],
H2NCH2 [25 28], D2NCH2 [2б, 28], H2NC02 [2б], NЗСН2 [29],
HSCH2 [30], CH2==CHCH2SSCH2 [31], (H2C==CHCH2)2PCH2 and
(H2C==CHCH2)2AsCH2 [З2], FCH2 [33 36], CICH2 [33, 37--41],
208 Nor11lal Vibтlio/ls ат! Absorplio/l Regio/ls о/ Alke/les a/lc/ Alky/les
CICD2 [33, 38], BrCH2 [зз, 37, 42], 'CH2 [33, 43], iPr [11],
cHex , Me(NC)CH [13], Me(CI)CH [44, 45], tBu [11], FзС
[9, 46], СlзС [47], Н(O==)C [5, 48 52], D(O==)C [5, 50,
52], Me(O==)C [49, 53 56], HO(O==)C [57 59], MeO(O==)C
[БО---Б5], ЕtO(о==)с [62], NaO(O==)C [57], H2N(O==)C [66],
MC2N(O==)C [б7], P(O==)C [68, 69], CI(O==)C [б8,
70 72], Br(O==)C [б8], H2C==CH [5, 48, 50, 51, 73 81],
H2C==CHCH==C==CH [82], H2C==CHCH==CH [83 7],
McCH==CH [88], McCH==CHCH==CH [84], H2C==C==CH [89],
CICH==CH [90], N=CCH==CH [91], H2C==C(C=CН) [92],
MC2C==CH [9З], H2C==C(Mc) [79, 94], H2C==C(CI) [53, 70, 95,
9б], HC=C [97 99], DC=C [99], NaC=C [98], N=C [98, 100],
CIC=C [101], CN [102], Ph [11, 103 108], 2 XPh (Х = Ме [11,
103,109], Сl and Br [11,103], F [103, 110]), 3 XPh (Х = Ме [103, 109],
Р, CI, Br and 02N [10З], Е! and НО [11]), 4 XPh (Х = Мс [11, 109],
Et, iPr, tBu, Р, CI, Br, НО and N=C [11 ]), F5Ph [111], 2 Py and
4 Py [10б], McO [112 119], СDзО [114, 116], ЕtO [120---
123], FЗССН20 [124], HC(==O)O [125], PC(==O)O [12б],
McC(==O)O [бl], FзСС(==О)О [127], H2C==CHO [128],
МсзSiO and (СDз)зSiO [119, 129], HS [130], McS [131, 132],
PhS , H2C==CHS(==O)2 [148, 149] НзSi and DзSi [133, 134],
McH2Si [135], CIН2Si [135, 136], FH2Si [135], МезSi [137],
McCI2Si [138], FзSi [4б, 139], СlзSi [140], p [11, 141 14З],
Cl [11, 143 145, 150], Br [11, 143, 145].
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212 Norl1lal Vibтlio"s аl/{l Abs01plio" Regio"s о/ Alke"es a"d Alky"es
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149. N.L. Allingcr and У. Fan, J. Сотрllf. С//ет., 14, 655 (1993).
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cdn. (1985).
8.1.2 Vinylidene (ethenylidene)
Тhe compound CI2C==CH2 bclongs to thc point group С2У and thc twelve normal
vibrations arc dividcd among 5а) + а2 + 2Ь, + 4Ь2 typcs of vibration. The а2
vibration is forbiddcn.
ТаЫе 8.3 NorrnaI vibrations of 1,1-dichloroclhcne
Vibralion С21' cm 1 Vibralion С2у cm 1
I/ s C H 2 аl 3035 WCH2 Ь) 872
I/С==С 1614 WCCl2 435
ЬСН2 1391 l/ о СН 2 Ь2 3130
I/ s CCI 2 601 Р СН 2 1076
bCCl2 298 l/ о СС1 2 793
ТС Н 2 а2 p CCl 2 370
If thc two halogcn atoms arc diffcrent, thc symmctry is lowcrcd from С2у to
C s and thc а) + Ь2 vibrations Ьссоmс а' and thc а2 + ы vibrations Ьссоmс а"
vibrations. In this work only опе frcc bond in thc СН2==С< group is takcn into
considcration, so that for this fragment 3N 6 = 9 vibrations arc takcn into account:
В.1 A/kefles
213
I/ О СН 2 , I/sCH2, I/С==С, ЬСН 2 , рСН 2 , ""СН2, ТСН2, 'Y C==C and b C==C
or simply: I/СН (2), I/С==С, БСН (2), ""СН (2) and skclctal dcformations (2).
Thc twclvc vibrations of CH2==C(X) arc found Ьу adding опс C X
strctcl1ing vibration, опс C==C X dcformation and опе torsion to thc ninc
vibrations of СН2==С<. Thc absorption frcqucncy of the C==C X deformation
is comparabIc with that of the similar cxtcrnal skelctal deformation and is addcd
to thc tabIe as 'alternativc skclcta! dcformation'.
Thc СН stretching vibrations
Thc СН strctching vibrations arc obscrvcd bctwccn 3150 and 2990 cm 1 with а
wcak to modcrate intcnsity. Although thc absorption regions ovcrlap cach othcr,
the two СН strctching vibrations arc rarcly assigncd а! thc samc wavcnumber.
The highcst СН strctching vibration, oftcn callcd I/.СН2 (3105 :1: 45
cm 1), is assigncd а! З144 cm l in thc spcctrum of FC(==0)(F)C==CH2,
followed Ьу the values in the spcctra of Mc(F)C==CH2, CI(Br)C==CH2 and
H2C==CCl(Br)C==CH2 with 3140 cm 1 and (NC)2C==CH2 and CI(NC)C==CH2
with 3135 cm l. The lowcst values appcar in thc spcctra of H2C==CF(F)C==CH2
(3062), Mc(NCCH2)C==CH2 (306б), H2C==CCI(F)C==CH2 and F(CI)C==CH 2
with 30б9 cm 1 and Н 2 СН(СI)С==СН 2 with 3070 cm J. The rcmaining
compounds absorb а! 3100 :1: 30 cm 1.
Thc СН stretching vibration absorbing in thc rcgion 3030 :1: 40 cт 1, is соп
sidercd as the I/sCH2. The HW sidc of this rcgion is limited Ьу FC(==O)(F)C==CH2,
Et(Mc)C==CH 2 , iPr(Mc)C==CH2, НОСН2(МС)С==СН2 and BrCH2(Mc)C==CH2
with valucs in the ncighbourhood of 3070 cm l. Low wavenumbers ( 2990
cm t) arc observcd in Ihc spcctra of МС2С==СН2, (BrCH2)2C==CH2,
Н2С==СН(МС)С==СН2, МССН==СН(МС)С==СН2, НС=С(МС)С==СН2 and
НОС( ==О)(Ме )С==СН2'
Thc С==С strctching vibration
With the cxccption of high values for F2C==CH2 (17ЗО) and F(Mc)C==CH2
(lб87 cm 1), thc С==С strctching vibration occurs а! 1625 :1: 50 cm l with
а modcratc intensity. In consequcncc, misintcrpretation of а tluorine-substitutcd
doubIe bond as а carbonyl group is по! cxcludcd. High vaIucs originatc also from
the spcctra of H2C==CF(F)C==CH2 (lб75) and МСО(МС)С==СН 2 (lб70 cm 1).
The lowcst wavcnumbcrs have Ьесп traced in thc spcctra of conjugatcd alkcncs such
as Н 2 С==СН(НС=С)С==СН 2 (157б), H2C==CBr(Br)C==CH2 (1577 and 1603),
H2C==CCl(C!)C==CH2 (1581 and 1607) and H 2 C==CH(Cl)C==CH 2 (1585 and
1635) and in thc spcctrum of Br2C==CH2 (1593 cm 1). Thc rcmaining molcculcs
display !his I/С==С at 1630 :1: 30 cm l.
214 No,."tal Vibтliolls alld AbsOllJlioll Regiolls о/ Alkelles атl AlkYlles
Thc СН in planc dеfоrnшtiОJ1S
Тl1е ЬСН2 is rcportcd in thc rangc 1395 :!:: 45 cm t. Pll(Mc)C==CH 2 and
4-FРh(Мс)С==СН2 show this СН in-planc dсfоrП1аtiоп а! 1440 cm ] and
НОС(==О)(МС)С==СН2 а! 1432 СП1 l. The compounds Н2С==СХ(Х)С==СН 2
\vitll Х = Br (1352 and 1392), СI (1357 and lЗВ6) and F (1365 and lЗВ5) and
Н2С==СН(Сl)С==СН2 (1365 or 1420 cm 1) arc rcsponsibJe for thc low values.
Usually this ЬСН2 is assigncd in the region 1400 :!:: 30 cm 1. As the ЬСН2 in
R CH==CH2 compounds also absorbs in this rcgion, thc СН in-plane deformation
in 2 substitutcd 1,3-butadicncs is assigncd without spccification of the group.
Gcncrally tl1c СН2 rocking vibration is assigned in the rcgion 1000 :!::
90 cm l. А fc\v investigators situatc tl1is РСН2 а! higl1er wаvеПUП1Ьсrs:
Et(CI)C==CH2 (1171) and EI(Br)C==CH2 (1161) [БЗ], N=C(Cl)C==CH2 (1165)
[48], CICH2(CI)C==CH2 (1132) [З5, 37], CICH2(Br)C==CH2 (1127) [38] and
(cPr)2C==CH 2 (1172 СП1 l) [39]. For thc abovc-mcntioncd compounds thc values
of, rcspectivcly, 1007, 99б, 930, 938 [З4], 941 [36] and 958 cm l mау also
Ьс considcrcd for tl1is РСН2. Thc СН2 rock as \усll as tl1e C C strctching
vibration contributc to both absorptions. High valucs for this РСН 2 are found in the
spcctra of CI2C==CH2 (1088) and BrCH2(Br)C==CH2 (1090 cm 1) and low wave
numbers in thosc of BrCH 2 (Mc)C==CH 2 (910) and Mc(I)C==CH2 (927 cm l).
Such compounds as H2C==CI(CI)C==CH2 arc active а! both sidcs of this rcgion
(1080 and 915 cm 1). RR'C==CH2 molecules in which R and R' equals СН2 or
СН з show this РСН2 in а narrowcr rcgion (975 :!:: 15), for instancc: (МС)2С==СН2
(974), Et(Mc)C==CH2 (989), nPr(Mc)C==CH2 (990), НОСН2(МС)С==СН2 (9б4),
N=CCH2(Me)C==CH2 (9б4), (CICH2)2C==CH2 (985) and (BrCH2)2C==CH2
(985 cm 1).
Thc СН out-of planc deformations
The СН 2 wagging vibration givcs rise to а modcratc to strong band in thc
region 875 :!:: 75 cm l and for C( C)C==CH2 compounds in thc SП1аllсr
rcgion 895 :!:: 50 cm l, oftcn around 890 cm 1 with а weak ovcrtonc а! ::::::1780
cm 1. Thc rcgion for 1,1-halogcn substitutcd dcrivativcs is situated а! 10wcr
wavcnumbcrs (845 :!:: 45 сm 1). Thc I1ighcst wavcnumbers arc observcd in thc
spectra of C==O-Subslitutcd vinylidcne compounds such as НС( ==О)(Ме)С==СН 2
(948), НОС(==О)(Ме)С==СН 2 (948) and МсОС(==0)(МС)С==СН2 (945 cm l).
Thc lowcst valucs arc from 1,l difluorocthcnc (803), F(CI)C==CH 2 (836),
H2C==CCI(F)C==CH2 (83б) and МСО(МС)С==СН2 (830 cm I). The rеП1аiпiпg
compounds absorb in thc rcgion 890 :!:: 45 cm l. This "-'СН2 is, together with thc
I/С==С, thc most uscful infrarcd band for rccognizing thc vinylidcnc group.
Thc СН2 twist, absorbing in thc rcgion 70S:!:: 105 cm 1, is of minor importance
as а diagnostic tool. With thc exccption of the highcst and lowcst valucs summarizcd
in TabJe 8.4, thc ТСН2 is assigncd а! 70S:!:: 55 cm 1.
В.] A/keпes 215
ТаЫе 8.4 СН2 twisting vibra'ion in RR'C==CH2 compounds
R R' cm 1 R R' cm 1
Мс FC(==O) 808 F С1 607
FCH2 СI 804 F Н2С==ССI 607
cPr cPr 771 F Мс 629
Ме CIC(==O) 769 СI C 1CH 2 633
Ме НС=С 765 Br BrCH2 637
C1CH2 С1СН2 765 Ph Ph 638
Skelctal deformations
The cxtcrnal out of planc skclctal deformation is assigncd in а region (475 :f: 85
cm 1) limitcd Ьу thc compounds summarized in ТаЫс 8.5.
ТаЫе 8.5 , C==C in RR'C==CH2 compounds
R R' cm 1 R R' cm 1
Br H2C==CBr 559 Br FCH2 390 (s cis)
Мс Н2 С ==СМе 558 Br BrCH2 397 (s tr)
Ме НОСН2 557 Br C1CH2 398 (s /r)
N=C СI 557 1 Мс 400
Ме НО(О==)С 555 Br Br 404
СI Н2С==ССl 554 Br Мс 409
The extcrnal in pIane skcletal dcformations сап Ьс found in thc region 325 :f:
145 cm 1: gcncrally а b C==C а! З95:f: 75 and а sccond 'altcrnativc' b C==C
а! 290 :f: 110 cm l. Thc lowest valucs arc observed in the spectra of halogcn
substituted vinylidcnc compounds.
ТаЫс 8.6 Absorption rcgions (cт 1) of Ihc поrrnа1 vibrations of RR'C==CH2
R satura'cd saturatcd conjugaled saluratcd conjugatcd halogen
R' satura'cd conjugatcd conjugalcd ha'ogen halogcn halogen
l/ о СН 2 3095 :f: 35 31О5:!: 20 3005 :f: 30 3120:!: 20 3105 :f: 45 3100 ::i: 40
1/ 5 СН 2 3030 :f: 40 3030 :f: 40 3025 :f: 35 3035 :f: 35 3030 :f: 40 3035 :f: 25
I/С==С 1650 :f: 25 1630 :f: 25 1595 :f: 20 1640 :f: 20 1625 :f: 50 1625 :f: 35
ЬСН2 1410:!: 20 1420 :f: 20 1400 :f: 15 1405 :f: 25 1390 :f: 35 1395 :f: 20
Р СН 2 960 :f: 50 990 :f: 50 970 :f: 40 1005 :f: 85 1000 :f: 90 1015 :f: 75
"" СН 2 890 :f: 45 905 :f: 45 915 :f: 25 890 :f: 45 875 :f: 40 845 :f: 45
ТСН2 720 :f: 60 715 :f: 95 690 :f: 60 720 :f: 90 690 :f: 85 660 :f: 55
, C==C 490 :f: 70 485 :f: 75 510 :f: 50 475 :f: 85 485 :f: 75 475 :f: 75
b c==c 420 :f: 50 385 :f: 65 405 :f: 65 380 :f: 60 370 :f: 50 380 :f: 60
al'cmativc
b c==c 350 :1: 50 310:!: 50 340 :f: 50 320 :f: 60 270 :f: 80 275 :f: 95
RR'C==CH2 compounds
216 Norlllal Vibтlio"s a"d Absorplio" Regio"s о/ Alke"es ат! Alky"es
R
Mc
F H2
CICH2
BrCH2
cPr
H2C==CH
H2C==C(CI)
Ph
N=C
McS
F
Cl
Br
R'
Mc [1, 2, 4], Et [3], nPr [3], N=CCH2 [4-----8],
HOCH2 , CICH2 [8], BrCH2 [7,9], iPr, HC(==O) [10,
11], HOC(==O) , McOC(==O) , пВиОС(==О) and
пОсtOС(==О) [12], nDodccyIOC(==O) [13], FC(==O)
[14, 15], CIC(==O) [16], BrC(==O) [17],
H2C==CH [18, 19], H2C==C(Mc) [20], MeCH==CH
[21], Ph [22], 4 FPh , HC=C , N=C [23], F [24],
Cl [25, 2б], Br [27], I [28], McO [29, ЗО];
CI [31], Br [31];
CICH2 [32, 33], Cl [34-----37], Br [36,38];
BrCH2 [З2], Br (35, З6];
cPr [З9];
HC=C [40], CI [18,41--43];
F , Cl [42, 44], Br ;
Ph [45];
N=C [4б], ЕtOС(==О) [47], Cl [48];
McS [49];
H2C==CF [44], FC(==O) [50], F [51 5б], CI [56];
СDз [26], Et [63], CI2C==C(CI) [42], Cl [54-----62],
Br [б2];
Et [БЗ], Н2С==С(Вr) [44], Br [53, 54, 56, б2].
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46. А. Rosenbcrg and J.P. Ocvlin, Spec/roc/lilll. Ас/а, 21, 1613 (1965).
47. S. Rcyno1ds, О.Р. Oxley and R.G. Pritchard, Spectrochim. Ас/а, Рат/ А, 38А, 103 (1982).
48. S.B. ие and Р. Кlaboe, Spec/roc/liт. Асщ Par/ А, 26А, 1191 (1970).
49. Р. Jandal, Н.М. Scip and Т. Torgrimscn, J. Мо!. S/rиc/., 32, 369 (1976).
50. J .R. Ourig, АА. Wang, T.S. Litllc, Р.А. BrIctic and J .R. Buccnel1, J. C/lem. Phys., 91,
7361 (1989).
51. О.С Smith, J.R. Niclscn and Н.Н. Claasscn,J. C/lem. P/,yS., 18,326 (1950).
52. W.F. Edgcll and C.J. Ultcc, J. С//ет. P/,yS., 22, 1983 (1954).
53. J.R. Schercr and J. Overcnd,J. C/lelll. P/,yS., 32,1720 (1960).
54. J.M. FrсеП1ап and Т. Hcnshal], Call. J. C/lem., 47, 935 (1969).
55. S. Jcyapandian and G.A.S. Raj, J. Мо!. S/rrtct., 8, 97 (1971).
56. О.Е. Мапп, N. Acquista and Е.к. Plylcr, J. С//ет. P/,yS., 23,2122 (1955).
57. Р. Joyner and G. Glock]cr, J. С//е1ll. P/,YS., 20, 302 (1952).
58. S. ЕПОП10tо and S. Echinohe, Nippoll Kagakи Zass/li, 1343 (1958).
59. F. Winlher and 0.0. Hummc1, Spec/roc//iт. Асш, Part А, 23А, ]839 (1967).
60. F. Winther, Z. Natиrforsc//., Teil А, 25А, 1912 (1970).
218 Norтal Vib/'alio"s (тd Abs01plio" Regio"s о/ Alke"es тиl Alky"es
61. Е. O'A1cssio, Е. Silbem13n зпd Е.А. Joncs,J. Мо/. S"'IIC/., 9, 393 (1971).
62. R.A. Nyquist зпd J.W. ТllОП1РSОП. Spec/roc/lim. Ас/а, РOI'/ А, ЗЗА, 63 (1977).
63. G.A. Cro\vdcr зпd N. Sl11yrl,J. Мо/. S/ПlС/., 10,373 (1971).
8.1.3 Vinylene (ethenylene)
The X CH==CH X moleculc in thc cis {I1Ш/S} configuration belongs to thc
point group С 2 ,. {с 2 /,}. Thc twelvc normal vibrations arc being divided into 5а!
+ 2а2 + Ь] + 4Ь2 {5а к + 2а" + Ь К + 4Ь,,} spccies of vibration. The а2 {а к , Ь К }
vibrations are not activc in tllc infrarcd.
ТаЫе 8,7 Norrnal vibr3tions of cis and /ralls 1,2-dichlorocthcne
Vibralion С2,' Су. cis /rOl/s Vibration С2\' Су. cis /ralls
I/СН 31 а к 3080 3073R wCCI 32 3" 406R 225
I/С==С 1590 1580R wCH Ь1 ь к 701 760R
БСН 1180 1272R I/СН Ь2 Ь" 3080 3090
I/ССI 711 844R ЬСН 1296 1200
ЬССl 173 349R I/ССI 845 820
""СН 32 3" 876R 896 ЬССl 568 260
Thc molcculc X CH==CH Y bclongs to tllc point group С 5 . Considcring опс
frce bond, thc twclvc normal vibrations (9а' + 3а") arc rcduced to the following
3N б = 9 vibrations for thc CH==CH structure unit:
I/СН (2), I/С==С, ЬСН (2), wCH (2), b C==C and torsion.
СН strctching vibrations
With thc exccption of thc high valucs obscrvcd in thc spectra of FCH==CHF (cis:
313б; tra"s: 3114), FsPhCH==CHPhFs (3105) and trа"s FзССН==СНСFз (З104
cm l), thc RCH==CHR' compounds display thc highcst I/СН in the region 3055
:1: 45 cm 1.
Thc I/'СН (cis: 3020 :1: 40; Iralls: 3025 :1: 35 cm l) pcnctratcs in the field
of thc sp3 CH strctching vibrations. Thc high wavenumbcrs from FCH==CHF
(cis: 3122; IrallS: 3111), Iralls FsPhCH==CHPhFs (3085), 1/'а"s FзССН==СНСFз
(3084), IrallS BrCH==CHBr (3081) and CICH==CHCl (cis: 3080; Ira"s: З073
cm t) have not Ьееп takcn into account. The lowest wavcnumbcr (2980 cm l)
is notcd in thc spcctrum of cis McCH==CHMc.
The С==С strctching vibration
In thc infrarcd thc cis isomcrs absorb moderatcly but more strongly than thc t/'Q"S
isomcrs. In dclimiting thc absorption rcgion (1620 :1: 60 cm 1), the very high va1ues
В.] Alkelles
219
flOm рсн==снр (cis: 1715; tralls: 1б94) and FзССН==СНСFз (cis: 1б9б; traпs:
1715R) and thc extrcmcly low valucs from 'CH==Cнr (cis: 1545; tralls: 15З7
сm 1) arc по! takcn into ассоип1. For the cis molcculcs high wavcnumbcrs are
obscrved in the spectra of МсОСН==СНОМс (1680), МсСН==СНОЕ! (lбб9) and
МсСН==СНОМе (1668 cm l) and low values in thosc of ХСН==СНС(==О)У
compounds (Х = CI or Br; У = СI or Br) (1575 :f: 15), BrCH==CHBr (1585) and
CICH==CHCI (1590 cm 1). Usually the cis isomcrs rcveal this С==С stretching
vibration а! 1б30 :f: 35 сm 1 .
'П Iralls isomcrs thc intensity of the I/С==С dccrcases strongly in proportion as
thc symmctry of the molecule incrcascs. 'П symmctrical RCH==CHR compounds
this vibration is по! infrared active Ьи! is strongly Raman active. For thc /ralls
molcculcs thc region (lб25 :f: 55 cm t) is limitcd Ьу МсСН==СНМс (lб7б)
and МсОСН==СНОМе (1б70 cm l) а! thc HW sidc and Ьу ХСН==СНС(==О)У
compounds (Х = СI or Br; У = Сl or Br) (1585 :f: 15), CICH==CHCI (1580)
and BrCH==CHBr (1581 cm l) а! thc LW sidc. 'Лlс rcmaining molcculcs display
thc I/С==С а! 1635 :f: З5 cm 1. Oftcn thc Iralls isomcrs absorb а! highcr wavc
numbers than the cis isomers, and thc diffcrcncc in wavcnumbcr bccomcs smaHer
in conjugated diencs, for which this vibration splits into ап in phasc and ап out-of
phasc componcnt: МеСН==СНМс (cis: 16б2; trаш: 1б7бR), МеСН==СНЕ! (cis:
1658; Imlls: 1673R), НО(О==)ССН==СНС(==О)ОН (cis: 1б48; Iralls: 1бб4R),
НО(О==)ССН==СНСН==СНС(==О)ОН (cis...cis: 1/5 1б40, 1/0 1595; trallHralls:
1/5 1б40; 1/0 1615), CICH==CHCH==CHCl (cis...cis: 1/5 1б25; 1/0 1574; Irаш
Iralls: 1/., 1б25; 1/0 1572 cm 1). 'П thc compounds ХСН==СНХ (Х = F, CI, Br,
1), МсСН==СНОМе (cis: lбб8; Iralls: 1659), МсСН==СНОЕ! (cis: 1бб9; traпs:
1659) and МсОСН==СНОМс (cis: lб80; IrallS: 1б70 cm l), howcvcr, the cis
isomcr absorbs а! highcr wavcnumbers than the IrallS isomcr.
'Лlс СН in planc dcformations
Thc absorption region of ЬСН for cis isomcrs is 1345 :f: 80 or gcncraHy 1345 :I: 55
cm l jf the extremc valucs from FзССН==СНСFз (1425), МсСН==СНМе (1425),
НОСН2СН==СНСН20Н (1417), DO(O==)CCH==CHC(==O)OD (141б), cis,cis
CICH==CHCH==CHCl (1415 and 1305) and cis,cis-МеСН==СНСН==СНМс
(12б5 and ] 344 cm 1) are по! takcn into account. Thc vcry low values 1219 and
1254 cm 1 for 'СН==СН1 and BrCH==CHBr faH outsidc thc abovc-mcntioncd
rcgion.
Thc absorption region of ЬСН for Iralls isomcrs is 1300 :f: 40 or gencraHy
1300 :f:: ЗО cm 1. Тhe highcst wavcnumbcrs (1337 cm l) arc duc to
МсСН==СНОМс and МсСН==СНОЕ! and thc lowest values (:::::::12бб cm 1) are
from МсО(О==)ССН==СНС(==О)Х compounds (Х = CI, ONa, ОН and ОО). The
low values 1225 for 'CH==CНI and 1251 cm l for BrCH==CHBr faH outsidc thc
rcgion.
The absorption rcgion of Ь'СН for cis isomers is 1240:!: 55 or gencraHy 1240:!:
220 Noтral Vibralio"s ат/ Abs01plio" Regio"s о/ Alkelles ll//(/ Alkylles
40 сш l. Тltc rcgion is limitcd Ьу МсОСН==СНОМс and МсСН==СНС(==О)Мс
\vithl292 cm 1 and Ьу cis,cis CICH==CHCH==CHCI with /230 and 1 [85 cm l,
if thc [ow valucs for lCH==CНl (1120), BrCH==CHBr (1150) and CICH==CHC[
(1180 cm l) arc по! takcn into account.
Thc absorption rcgion of Ь'СН for Imlls isomcrs is 1260 :!: 45 or
gcncralIy 1260 :!: 30 сш l. Thc upper limit is givcn Ьу МеСН==СНМе
(1305), F5PhCH==CHPltF5 (1305) and Ph-d 5 СН==СНРh-d 5 (1302 cm 1) and thc
lo\vcr liшit Ьу НО(О==)ССН==СНС(==О)ОК (1218) and CICH==CHCH==CH2
(1227 cm 1). Тltc сошроuпds lCH==CНl (1128), BrCH==CHBr (l1БО) and
CICH==CHCl (1200 cm l) absorb outsidc this rcgion.
Thc СН out of planc deformations
For cis I,2 dichlorocthcnc, thc out of plane out of phasc СН dcformation is
forbiddcn in the infrarcd but activc in thc Raman а! 87б cm 1. Iп thc spectra
of cis isomcrs this wCH (925 :!: 75 cm l) has оп [у а \vcak intensity and is of
minor importancc as а diagnostic tool. Disrcgarding thc cxtrcmc vaIues (:::::1000
cm 1) from НО(О==)ССН==СНС(==О)ОН and ОО(О==)ССН==СНС(==О)ОО
and from МсСН==СНМс (852 cm l), thc rcgion is reduccd to 930 :!: 50 cm 1.
The Iralls isomcrs of FCH==CHF (875), CICH==CHCI (89б), BrCH==CHBr
(899) and lCH==CНl (907 cm 1) absorb strongly in the infrarcd but thcsc low
va[ucs falI outside thc rcgion 955 :!: 45 cm l. High wavcnumbcrs in thc vicinity
of 1000 cm ! are found in thc spcctra of НО(О==)ССН==СНС(==О)ОК and
МсО(О==)ССН==СНС(==О)ОМс. Co[thup [б2] rcportcd that fatty acids and
dcrivativcs with Iralls polyene groups absorb strongly in 1hc ncighbourhood of
1000 cm 1, II'alls,ll'Q/ls,ll'alls tricncs ncar 994 and lralls,lmlls dicncs near 98б
cm l. In thc spcctrum of II'alls,II'Q//s CICH==CHCH==CHCI thesc СН out of plane
dcformations arc assigncd а! 955 and 913 cm l. Most of the lralls RCH==CHR'
compounds show thc in phasc СН wagging vibration moderately to strongly in
thc rcgion 950 :!: 30 cm 1. This СН out of plane dcformation providcs the most
uscful infrarcd band to clucidatc thc Iralls CH==CH structurc, cspecialIy if the
intensity of thc С==С strctching vibration fails. Thc strong band а! 961 cm 1 in
the spectrum of IrallS PhCH==CHMc is assigncd to this wCH. Colthup situatcs
this wCH in 1hc spcctra of conjugated polycnes with cis and IrallS fragments in thc
rcgion 950 :!: 50 cm l [б2].
Cis 1,2 Dichlorocthcnc absorbs strongly а! 701 cm 1 and cis 1,2 dif1uorocthcnc
а! 75б cm l. Togcthcr with thc С==С strctching vibration this in phase СН wag
(735:!: 35 cm l) is thc most charactcristic vibration of thc cis CH==CH group,
Ьи! thc intensity of this band is по! always sufficicntly strong. Thcrcfore this
vibration is qualitatively infcrior comparcd with thc IrllllS 955 cm l absorption.
Thc low values from ICH==CНl (б45) and BrCH==CHBr (670 cm 1) falI outsidc
this rcgion.
Thc wCH in IrallS 1,2 dichlorocthcnc is forbiddcn in thc infrarcd and appears
В.1 A/kelleS
221
а! 7БО cm ) in the Raman. Тhis vibration is weakly active or inactive in the
infrared and is of minor importance as а diagnostic tool. The upper Jjmit of the
absorption region (825 :1: 75 cm 1) is formed Ьу МеО(О==)ССН==СНС(==О)Х
compounds (Х = НО, NaO, CI) with values in the neighbourhood of 898 cm 1
and Ьу Х(О==)ССН==СНС(==О)Х compounds (Х = НО, 00, МеО) with wave-
numbers near 895 cm 1 in the Raman. Low values are found in the Raman spectra
of МеСН==СНМе (755), CICH==CHCl (7БО), МеСН==СНСН==СНМе (750) and
CICH==CHCH==CHCI (760 cm 1). GeneraIly, the region 820:1: 50 cm ) is useful
for this out of phase wag. Тhe very low values from BrCH==CHBr (736R) and
'CH==CНI (592R) are по! taken into account.
Skeletal deformations
Тhe vinylene group provides two external skeletal deformations: ап in-plane
deformation and ап out of plane deformation or torsion. The other side of the
CH==CH unit gives ап 'alternative' skeletal deformation. Without further
information it is по! possible to assign these deformations unambiguously. ТаЫе
8.8 gives these extensive absorption regions with а few examples.
ТаЫс 8.8 Vinylcnc skclctal dcforrnations
Vibration Absorption regions (cm 1) МсСН==СНМс McCH==CHC=N
[3,5] [19]
cis-moleculcs /ralls-mоlесuIсs cis /rans cis Irans
b c==c 555 :1: 120 525 :1: 95 566 501 655 555
torsion C==C 420 :1: 100 360 :1: 110 396 260 517 461
altcmative
bc==c 280:1: 115 300 :1: 100 291 294 394 398
Aly el а/. have studied the inftuence of the configuration of CH==CН moIe-
cules оп the skeletal deformations [15].
R CH==CH R' compounds
R R'
Me Me [1---6], Н(O==)C [7, 8, 9], CI(O==)C [10],
Me(O==)C [7], MeO(O==)C [11, 12], ЕtO(О==)С
[11], H2C==CH [13], H2C==C(Me) [14],
MeHC==CH [15, 1б], H2C==CHCH==CH [17],
H(O==)CCH==CH , Н(O==)CCH==CHCH==CH and
H(O==)CCH==C(Me)CH==CH [18], N=C [19, 20],
Ph , 4 MeOPh , MeO [21], ЕtO [21, 22],
MeCH==CHO [23], CI [24];
222 Noтral Vib/'aliolls ат! AbsOlplioll Regiolls о/ Alkelles ат! Alky"es
R
R'
ТаЫе 8.9 Absorption rcgions (СП1 l) оС thc поm131 vibration of cis-
R CH==CH R'
conjugalcd
113logcn
//СН
I/'СН
I/C==C
ьсн
Ь'СН
wCH
w'CH
b C==C
torsion C==C
altcmalivc
bc==c
saturatcd snturatcd conjugaled
saturatcd conjugntcd cOl1jugatcd
(С==С; С==О) (С==С; С==О)
3050 :f: 40
3010:!:: 30
1660 :f: 20
1390 :f: 35
1260 :f: 35
915 :f: 65
735 :f: 55
515 :f: 75
405 :f: 85
265 :f: 45
3045 :f: 25
3025 :f: 25
1630:!:: 30
1330 :f: 65
1255 :!:: 35
930 :f: 50
735 :f: 55
580 :f: 80
435 :f: 85
345 :f: 50
3055 :f: 25
3005 :f: 25
1625 :f: 25
1350 :!:: 60
1245 :f: 45
960 :f: 40
750 :f: 40
555 :f: 120
365 :!:: 45
230 :f: 65
3080 :f: 20
3040 :!:: 20
1595 :f: 35
1360 :!:: 55
1235 :f: 50
940 :f: 40
740 :f: 40
575 :f: 95
425 :f: 75
245 :f: 70
R
R'
Absorption rcgions (cm l) of the поrrnа1 vibrations of /ralls-R CH==CH R'
conjugated
ha10gcn
I/СН
I/'СН
I/С==С
Ьсн
Ь'Сн
wCH
w'CH
b C==C
torsion C==C
altcmativc
bc==c
saturated sаШrаlсd conjugalcd
saturatcd conjugated conjugatcd
(С==С; С==О) (С==С; С==О)
3040 :f: 25
3025 :f: 25
1665 :f: 15
1320 :f: 20
1285 :f: 20
955 :f: 20
800 :f: 50
530 :f: 90
330 :f: 80
270 :f: 40
3040 :f: 25
3015 :f: 20
1640 :f: 30
1310:!:: 20
1260:!:: 30
955 :f: 30
800 :f: 50
540 :f: 90
365 :f: 106
320 :f: 80
3055 :f: 40
3025 :f: 35
1640:!:: 30
1295 :f: 35
1260:!:: 45
970 :f: 30
830 :f: 70
490 :f: 60
350 :f: 100
270 :f: 70
3075 :f: 25
3035 :f: 15
1600 :f: 30
1305 :f: 35
1260 :f: 30
945 :f: 35
810:!:: 50
525 :f: 75
350 :f: 100
300:!:: 100
Et
nPr
HOCH2
CICH2
FзС
H(O==)C
CI(O==)C
Br(O==)C
Et [25], 02CCH2 [26], N=C [20];
02C [26];
HOCH2 ;
CICH2 [27], CI [28];
FзС [29];
NH2 [30];
CI(O==)C [31], CI , Br and I [32];
Cl and Br [32];
HO(O==)C
OO(O==)C
McO(O==)C
ЕtO(о==)с
пВиО(О==)С
KO(O==)C
H2C==CH
O==C==N
N=C
Ph
Ph-d 5
2-, 3 and 4-dРh
4-FРh
F5Ph
MeO
F
Cl
Br
I
8.1 Alkelles
223
HO(O==)C [33], KO(O==)C [34],
HO(O==)CCH==CH [35];
OO(O==)C [33];
C](O==)C [36, 37], HO(O==)C , DO(O==)C and
N<tO(O==)C [371, MeO(O==)C [3б, 38, 39], Ph [40];
ЕtO(о==)с [38];
nBuO(O==)C [38];
KO(O==)C [41];
H2C==CH [17, 42--44], N=C [45], CI [4б];
O==C==N [47];
N=C [48, 49];
Ph [50---53];
Ph d5 [50];
2 , 3 and4 dPh [50];
4 FPh [52];
F5Ph [52];
MeO [54, 55];
F [3, 5б, 57];
CICH==CH [58, 59], Cl [БО, бl];
Br [60];
I [60].
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30. J. Terpinski and J. Oabrowski, J. Mol. S/rиc/., 4, 285 (1969).
31. J.M. Landry and J.E. Katon, Spectroc//im. Acta, Par/ А, 40А, 871 (1984).
32. К. КаП1iспskа-Тrе1а, Н. Baranska and А. Labudzinska,J. Mol. S/rIIct., 54, 59 (1979).
33. J. Maillols, L. Bardet and L. Maury, J. Mol, S/r//c/., 30, 57 (1976).
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(1985).
35. Р. Sоhзr and G. Varsзnyi, J. Mol. SIrIlCt., 1, 437 (1967 8).
36. J.E. Katon and Р.Н. Chu,J. Мо/. Strиc/., 78,141 (1982).
37. J.E. Katon and Р.Н. Chu,J. Мо/. StrIIc/., 82, 61 (1982).
38. О.А.с. Compton, W.O. Georgc and A.J. Porter, J. С//ет. Soc. Perkill Tralls. 2, 400
(1975).
39. С. тellez, R. Кnudscn and О. Sala, J. Мо/. SII'IIC/., 67,189 (1980).
40. M.O.G. Faria and J.J.C. Tcixeira-Oias, J. Ramall Spec/rosc., 22, 519 (1991).
41. J. Maillols, L. Bardet and L. Maury,J. Мо/. S/rиct., 21,185 (1974).
42. E.R. Lippincott and т.Е. Кеппсу, J. А11I. С/,е11l. Soc., 84, 3641 (1962).
43. R. McOiarrnid and S. Sabljic, J. P//ys. С/,ет., 91,276 (1987).
44. Н. Yoshida, У. Furukawa and М. ТаSUП1i,J. Мо/. S/rIIc/., 194, 279 (1989).
45. В.Н. Thomas and W.J. Оrvillс ТhОП1аs, J. Мо/. StrIIc/., 3, 191 (1969).
46. А. Borg, Z. SП1ilh, G. Gunderscn and Р. Кlaboe, Spec/roc//im. Acta, Part А, 36А, 119
(1980).
47. G. L.Carlson, Spec/rocIIi11l. Ас/а, 20, 1781 (1964).
48. ЕА. Miller, О. Sala, Р. Оеуliп, J. Ovcrcnd, Е. Lippcrt, W. Ludcr, Н. Moscr and J,
Varchmin, Spec/roc//im. Асщ Par/ А, 20,1233 (1964).
49. А. Rosenberg and J.P. Ocvlin, Spec/roc//im. Ас/а, 21, 1613 (1965).
50. Z. Mcic and Н. GUstcn, Spec/roc/lim. Ас/а, Par/ А, 34А, 101 (1978).
51. А. Bree and R. Zwarich,J. Мо/. S/rиc/., 75, 213 (1981).
52. Z. Meic and Н. GUslen, Spec/roc/lim. Ас/а, Par/ А, 36А, 1021 (1980).
53. К. Раlmб, Spectroc/lim. Ас/а, Part А, 44А, 341 (1988).
54. H.S. Kimmel, J.T. Waldron and W.H. Snyder,J. Мо/. StrIIct., 21, 445 (1974).
55. J.M. Comcrford, P.G. Anderson, W.H. Snydcr and H.S. Кimme1, Spec/rocIli11l. Acta,
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56. N.C. Craig and Е.А. Entcmann, J. С//ет. P//ys., 36, 243 (1962).
57. R.A.R. Pearce and I.W. Levin, J. С//ет. P//ys., 59, 2698 (1973).
8.2 A!kyпes
225
58. Е. Bcnedctli, М. Aglicllo, Р. Vcrgamini, R. Лrоса, А.У. Rodin, Y.N. Panchcnko and
У.А. Pcnlin, J. Мо/. Str//ct., 34, 21 (1976).
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(1980).
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(1958).
61. К. ТапаЬе and S. Sаёki, 8//11. С//ет. Soc. JplI., 47, 2545 (1974).
62. N.B. Colthup, Арр/. Spec/rosc., 25, 368 (1971).
8.2 ALKYNES
The 15 normal vibrations of ХСН 2 С=СН (Х = F, CI, Br, 1) (Section 3.5.б) are
divided, according to С . symmetry, into 10а' + 5а" vibrations. Nine vibrations
belong to the XCH2 group and six to the C=CH fragment:
а': I/СН, I/С=С, ЬСН, 8 C=C;
aft: [СН, [ C=C;
and the six vibrations of the C=CX fragment are:
а': I/СХ, I/С=С, ЬСХ, 8 C=C;
а": 1СХ, [ c=c.
8.2.1 Ethynyl
СН stretching vibration
With the exception of FC=CH (3З55 cm I), the I/СН gives rise to а sharp
and strong absorption band in the region 3300 ::1: 40 cm l. Тhe intensity of this
band is so strong that it is clearly observable superimposed оп the broad ОН. . .0
stretching band in a1cohols or acids. The inf1uence of the halogen is ilIustrated
Ьу the high values observed in the spectra of CIC=CH (3340), FCH2 C =CH
(3338) and F(O==)CC=CH (3337 cm I). Тhis characteristic absorption is
shifted to lower wavenumbers in conjugated RC=CH compounds such as
Ме(О==)СС=СН (3262), МеО(О==)СС=СН (3271), НС=СС(==О)С=СН
(3275) and NaO(O==)CC=CH (3278 cm 1). Тhe sp CH stretch in the remaining
compounds absorbs а! ЗЗlO ::1: 25 cm 1 and takes а unique place as а group
vibration.
Тhe С=С stretching vibration
Because of the compounds Fз СС =СН (21б5) and NaO(O==)CC=CH (2095),
the absorption region of the С=С stretch (2130 ::1: 35) is somewhat larger than
22б Norl1lal Vibraliolls ат! AbsOlplioll Regiolls о/ Alkelles (111(1 Alkylles
that of рroрупуl (2125 ::1: 25 cm 1), allhough tl1is lattcr rcgion is also usabIc for
most of Ihe RC=CH СОП1роuпds. This I/C=C is а good group vibration bul Ihe
intcnsity is nlOderalc 10 wcak and dccreases progressivcly wllCn thc Iriple bond
П10VСS а\уау frоП1 Ihe tcrminal posilion. lп SУП1mСlriсаl disubstiluled cthynes Ihc
I/С=С is infrarcd forbidden, bUI, very promincl1t in RаП1ап spcctra. The aboYc
П1епliопеd rcgion does поl includcd: FC=CH (2255), Br=CH (2085) and lC=CH
(2060 СП1 t) (see Seclions 8.2.3 and 8.2.4) and thc bUladiynes with, as cxamplcs,
CIC=CC=CH (2071), BrC=CC=CH (2095) and IС=СС=СН (2060 cm 1).
For compounds containil1g 111e C=CC=C fragmenl thc Iwo I/С=С bands
are described as sуmП1еlriс and anlisymmetric C=CC=C stretchings, for
ехаП1рlе in the speclra of НС=СС=СН (1/5: 2172; 1/0: 2005) and МеС=СС=СН
(1/5: 2239; 1/0: 2071 СП1 l).
Тhe СН deformations
Тhe in-plane and out-of-plane СН deformations are active in Ihe regions б75 ::1:
55 and б55 ::1: 45 cm t, \vilh ап inlcnsily that varies from П10dеrаlе 10 slrong.
Usually, Ьиl по! al\vays the in-plane deformalion is assigned а! а higher wave
number than the out-of-plane deformalion. Тhe splitting belween Ihc Iwo bendings
is grealer in unsalurated and carbonyl bonded ethynyl Ihan in RC=CH compounds
in \vhich R is а saturaled frаgП1епt, for which Ihe two deformations often give
rise 10 опе broad absorption (Seclion 3.5.6). 'П the spectra of molecules with
axial symmetry аЬои' Ihe С=СН group, these bending modes arc degenerate and
опlу опе band will Ье observed: МеС=СН (642), FC=CH (578), CIC=CH
(б04), BrC=CH (618) and 'С=СН (б30 cm I). The highest \vаvеПUП1Ьеrs are
observed in Ihe spectra of НС=СС(==О)С=СН (730 and 712), F(O==)CC=CH
(701 and 695), СI(О==)СС=СН (703 and 696), NaO(O==)CC=CH (704 and
652) and Ме(О==)СС=СН (700 and 649 cm l) and the lowest in those of
cPrC=CH (б10 and 648), МеС=СС=СН (614 and 696), Н2С==СНС=СН (615
and 629), PhC=CH (613 and 653), 4-НС=СРhС=СН (618, 615, 646 and 632)
and 2 HC=CPhC=CH (615, 630 and 640 cm 1). There is а large chance of
encounlering both deformations а! 6БО ::1: 40 сm 1.
Skeletal deformations
'П cascs of по axial symmetry about the С=С bond, the two skelelal C=C
deformations are active in Ihe regions 295 ::1: 75 and 215 ::1: 75 cт 1, Usually
Ihe higher wavenumber is assigned to the out-of plane deformation and the lower
wavenumber to the in plane deformation. The 10west wavenumbers are found in the
spectra of carbonyl bondcd elhynyl compounds such as CI(O==)CC=CH (224 and
157», F(O==)CC=CH (229 and 189) and Ме(О==)СС=СН (228 and 183 cm I).
lп the spectra of compounds with axial symmetry аЬои! the С=СН group, only опе
band is observed: МеС=СН (33б), FC=CH (367), СIС=СН (326), BrC=CH
8.2 Alkylles
227
(295) and ,с=сн (262 cm I). Тhe two skeletal deformations of the diacetyI-
enes arc describcd as anlisymmctric and symmetric deformations, Ьи' the wave-
numbcr of thc antisymmctric dcformation falls oulside the higher mentioned region:
нс=сс=сн (484 and 230), МеС=СС=СН (484 and 324), CIC=CC=CH
(463 and 335), I3rC=CC=CH (470 and 355), 'С=СС=СН (47З and 357) and
4 HC=CPhC=CH (477 and 325 cm I).
ТаЫе 8.10 Absorption regions (СП1 I) of the поrrnаl vibrations of C=CH
Vibration propynyl a-saturaled с==о bonded a-unsaturated aromalic
I/сн 3315 ::!: 25 3310::!: 30 3300 ::!: 40 3315::!: 25 3305 ::!: 25
I/С=С 2125 :!:: 25 2130 ::!: 35 2120 ::!: 25 211О::!: 15 2110::!: 10
Ьсн 660 ::!: 30 660 ::!: 30 705 ::!: 25 660 :!: 40 645:!: 15
')'СН 635 ::!: 15 630 ::!: 20 670 ::!: 30 620 :!: 10 620:!:: 10
')' C=C 330 ::!: 35 295 ::!: 75 280 ::!: 60 290 :!: 50 345 :!: 25
b c=c 195::!: 45 195 :!: 45 2]5 :!: 75 195 :!: 45 ]80:!: 30
R C=CH compounds
R = R'CH2 (see Section 3.5.6).
R = Me [1 11, 68], СDз [9], MeC02 and СDзСО2 [12], cPr [13],
cl3u [14], cHex , HOCHO and HOC02 [15], tBu , FзС [11,
16 18], HC(==O) [19 22], OC(==O) [19, 20], FC(==O) [22
24], CIC(==O) [24---26], MeC(==O) [27], HC=CC(==O) [28],
HOC(==O) [29], MeOC(==O) [ЗО, 31], ЕtOС(==О) [32],
NaOC(==O) [29], H2C==CH [33 З5], H2C==C(Me) [3б],
MeHC==CH [36], H2C==CHC(==CH2) [З7], N==N==CH and
N==N==CD [38], HC=C [39, 40], MeC=C [41, 42], CIC=C ,
BrC=C and IC=C [43--45], Ph [1, 4б, 47], Ph-d5 [47], 2 , з- and
4-НС=СРh [48, 49], 4-МеРh , 4-СIРh , MeS [50--52], F [53 55],
CI and Br [5З, 55], l [53].
8.2.2 Chloroethynyl
Тhe С=С stretching vibration
For the small collection of R C=CCI compounds the I/С=С is found in the
region 2230::!: 40 cm 1, that is, 100 cm 1 higher than for R C=CH compounds.
The low value (2110 cm l) in the spectrum of chloroethyne falls outside this
region (Section 8.2.1). Disregarding the Iow wavenumbers from 'С=ССI (2191)
and N=CC=CCl (2194 cm 1), the region is reduced to 2245 :!: 25 cm l.
228 Norll/al Vibralio"s a"d Abs01P/io" Regio"s о/ Alke"es a"d Alky"es
The C Cl stretcl1ing vibration
Тhe C Cl stretch is active in the extensive region 595 :!: 165 cm t, for which
the higll values in the spectra of dihaloethyne СОП1роuпds are по! taken into
account: CIC=CCl (988 and 477), BrC=CCl (923) and IC=CCI (886 cm t).
High \vavenumbers are also assigned in the spectra of НС=ССI (75б) and
FзСС=ССl (723 cm 1) and low wavenumbers in those of МеС=СС=ССI (4З7)
and Н(О==)СС=ССl (473 cm I). Тhe narrower region 590 :!: 70 cm 1 makes
possibIe the use of this vC Cl.
Skeletal deformations
According to the scarce data, the t\VO externaI skeletal C=C deformations appear
in the ranges 395 :!: 75 and З10 :!: 50 cm t. Usually the higher {Iower} wave
number is assigned to the out of plane {in plane} deformation. In the case ofaxial
symmetry only опе band is observed. Self-evidently, the H C=C deformation
(б04 cm 1) in the spectrum of НС=ССI is outside this region (Section 8.2.1).
Тhe =C Cl deformations
Тhe two =C CI deformations are assigned in the regions 230 :!: 105 and 140 :!: 50
cm l, but it is difficult to determine which wavenumber is respectively responsible
for the in-plane or out of plane deformation. Тhe compound Н(О==)СС=СН
shows these two deformations а! 152 and 114 cm 1 and the higher wavenumber
is assigned to the out of plane =C CI deformation. In the spectra of molecules
with axial symmetry аЬои! the C=C Cl group, the bending modes are degenerate
and mзkе their appearance а! the same wavenumber: МеС=СCI (184), CIC=CCl
(172 and 333) and N=CC=CCI (129 cm l).
R C=C Cl compounds
R = H [53], Me [2, 3, 8, 9, 56---58], СDз [2, 9], CICH2 [3, 59],
FзС [БО, 61], H(O==)C [21, б2], H2C==CH [б3], HC=C [43
45], MeC=C [41], N=C [44], Ph [64], Cl , Br and I [б5,
бб].
8.2.3 Bromoethynyl
Тhe С=С stretching vibration
Тhe С=С stretching vibration in R C=C Br compounds appears in the region
2200 :!: 50 cm l. Bromoethyne (2085 cm l) absorbs more in the direction of
the R C=CH compounds (Section 8.2.1). Ignoring the low wavenumbers in the
spectra of N=CC=CBr (2150) and IC=CBr (216б cm l) this region narrows to
8.2 Alkylles
229
2215 :f: 35 сm 1, and occupies the second place in thc serics С=СCI > C=CBr
> С=СI > С=СН.
The C Br strctching vibration
The C Br stretching vibration is located in the region 520 :!: 170 cm t, if
the cxtremc values in thc spcctra of BrC=CBr (832 and 2б7) and IC=CBr
(782 cm 1) are по! taken into account. Ignoring the high wavenumbers from
FзСС=СВr (б86) and BrC=CCH2CH2C=CBr (б30 and 525) and the low values
from MeC=CC=CBr (356 cm I), the region is reduced 'о 520:!: 95 cm 1.
Skeletal deformations
The out of plane and in-plane external skeletal deformations are assigned in the
same regions as for R C=CCl compounds: 395:!: 75 and 310:!: 50 cm l. The
H C=C deformations in HC=CBr are found in ТаЫе 8.10.
The =C Br deformations
Vibrational analysis reveals that the two =C Br deformations are active in the
regions 225 :f: 100 and 120 :f: 50 cm l. 'П the spectrum of H(O==)CC=CBr, the
two deformations are situated а! 143 and 105 cm 1. The соmроuпds with axial
symmetry give rise to only опе deformation, for example MeC=CBr (171) and
BrC=CBr (137 and Зll cm I).
R C=C Br compounds
R = H [53], Me [2,3, 8, 9, 5 58], C03 [9], BrC=CCH2CH2 [б7],
BrCH2 [3], FзС [БО, 61], H(O==)C [21, б2], HC=C [43--45],
MeC=C [41], N=C [44], Ph [б4], CI and Br [б5, бб], ' [б5].
8.2.4 IodoethynyI
The С=С stretching vibration
Ехсер! for the Iow value of 20БО cm 1 from the spectrum of iodoethyne (Section
8.2.1), this С=С stretching vibration is found in Ihe region 2170 :!: 50 cm l, and
occupies the third place in the series С=ССl > C=CBr > С=СI > С=СН.
The C I stretching vibration
With the exception of the extreme values from di-iodoethyne (720 and 190 cm l),
the vCI falls in the region 485 :f: 175 cm 1. Disregarding the high wavenumber of
б60 cm 1 from Fз СС =СI and the Iow vaIue of 310 cm 1 from MeC=CC=CI,
this region is narrowed to 425 :f: 65 cm 1.
230 Noттl VibтliollS от! Abs01plioll Regiolls о/ A/kelles ти! AlkYlles
Skeletal dсfоrшаtiОI1S
TI1e ехtсrпаl skelctal dсfоrшаtiопs in R C=CI СОШРОUl1ds arc locatcd in thc
sаше rcgions as for R C=CCI and R C=CBr compoul1ds: 395 :i: 75 and 310
:i: 50 сш l.
111С =C I dеfоrшаtiОI1S
Wl1en tl1e l1юlесulе has по axial sушmеtrу the two =C 1 dcformations mау Ье
observcd in the regiol1s 200 :i: 100 and 120 :i: 50 сш 1 .
R C=C I compounds
R = H [53], Me [2,8,9, 57], СDз [9], FзС [60, 61], H(O==)C [21,
б2], HC=C [43--45], MeC=C [41], N=C [44], Cl and I [б5,
6б], Br [б5].
ТаЫе 8.11 Absorption regions (cm l) of the norma1 vibrations
of C=C X
Vibration C=C C1 C=C Br C=C 1
vC=C 2230 :i: 40 2200 :i: 50 2170:!: 50
/IC X 595 :i: 165 520:!: 170 485 :i: 175
'Y C=C 395 :i: 75 395 :i: 75 395 :i: 75
b c=c 310:!: 50 310:!: 50 310:i: 50
Ь =C Х 230 :i: 105 225 :i: ]00 200 :i: 100
'у =C Х 140 :i: 50 120:!: 50 120:!: 50
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47. G.W. King and S.P. So, J. Мо/. Spec/rosc., 36, 468 (1970).
48. G.W. Кing and A.A.G. Уап Putlen, J. Мо/. Spec/rosc., 70, 53 (1978).
49. J.F. Arenas, J.I. Marcos and F.J. Ramirez, Spec/roc//im. Ас/а, Рат/ А, 45А, 781 (1989).
50. H.J. Boonstra and L.C. Rinzema, Rec/. Trav. C//im. Pays-Bas, 79, 962 (1960).
51. A.G. Moritz, Spec/rocllim. Ас/а, Par/A, 23А, 167 (1967).
52. О.Н. Christensen and О. den Engelsen. Spec/roc//im. Ас/а, Par/ А, 26А, 1747 (1970).
53. А. Rogstad and S.J. Cyvin,J. Мо/. S/rиc/., 20, 373 (1974).
54. Н. BUrger, W. Schneider, S. Sommer and W. Thiel, J. C/rem. P/,yS., 95, 5660 (1991).
55. G.R. Hunt and М.К. Wilson, J. Clrem. P/,yS., 34, 130] (1961).
56. ЕЕ Cleveland and H.J. McMurry, J. Cl/em. P//ys., 11, 450 (1943).
57. A.G. Meisler, J. C/rem. P/,yS., 16,950 (1948).
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232 Noттl VibrotiOllS от! Abs01P/ioll Regiolls о/ Alkelles от! Alkylles
59. О. Christen, Е Gleisberg, G. Kremer and W. Zeil.J. Мо/. Spec/rosc.. 70,179 (1978).
60. Е. Augdahl, Е. Кloster-Jcnsen. У. Devarajan and S.J. Cyvin, Spec/rocllim. Асш, Рш'/ А,
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68. P.L. Stanghel1ini and R. Rossetti,/lIorg. CI,em., 29,2047 (1990).
9
Normal Vibrations and
Absorption Regions of
Nitrogen Compounds
9.1 AМINO
Methanamine in the pyramidal Sp3 structure belongs to the point group С 5 . The
15 normal vibrations differentiate between 9а' and ба" vibrational modes. After
subtraction of eight methyl vibrations (5а' + За") and the C
N stretching mode
(а'), За' + За" normal vibrations for NH2 remain. Hamburg et 0/. [24] report that
in benzenamine the amine group and the plane of the benzene ring form ап angle
of З8 0 and prefer the C s structure to the plane С2У structure.
ТаЫе 9.1 Aminе vibrations of methanamine and benzenamine
V a NН 2 v s NH 2 b NН 2 p/ rNH 2 ""NН2 torsion
С2У ь. а. а, ы1 Ь2 а,
С . а" а' а' а" а' а;'
Methanamine vapor(C s ) 3427 3361 1623 1195 780 264
Benzenamine(C s . С2У) 3480 3395 1619 1050 670 245
CaIculated according to the equation of Gбtzе and Garbe [79] >HNН = 0.241
ДV + 91.5, in which дv represents the difference Ье!\уееп the two NH stretching
vibrations, the HNH angle in methanamine {benzenamine} is 1070 {112 0 }.
234 Nomт/ Vibratiolls alld Abs01ptioll Regiolls о[ Nit/'Ogell CompOlll/ds
Amil1c strctcl1ing vibrations
In Q-saturatcd liquid aI1lines, tl1c NH2 strctcl1ing vibratiol1s give risc 'о а nearly
symmetrical doubIet \vith а weak to moderatc iI1tensity. А SllOuldcr (3180 :1: 20
cm l) оп (Ье LW side оС tl1e vsNH2 is attributed (о thc ovcrtonc оС 'Ье NH2
scissoring vibration, cnhanccd Ьу Fеппi resonancc [8 3]. 'П thc vapour state and
in solution the absorptions movc 'о higl1er wavcnumbers, Ьесоmе sharper and arc
\усll separated. In primary amines containing t\vo cquivalcnt NH bonds, the changc
оС forcc constant I13S 'Ье same influencc оп tlle SYI1lmetric and antisymmctric
strctching vibration. ВеllаПlУ and WiIliams [84] found а corrclation bctwccn 'Ьс
!\vo vibrations: V s = 0.876 V a + 345.5, and since (Ье value 345.5 approximates (о
v a !10, this cquation has Ьееп reduced to V s = 0.98 V a [85, 86]. For molcculcs in
\vhich а neighbouring group interacts with опс hydrogen of the amine group, this
relationship по longcr holds.
In liquid benzenamines the symI1lctric stretching vibration (LW band) absorbs
more stroпgеlу than 'Ьс antisymmetric counterpart (HW band). ТЬе ovcrtone
band of the NH2 scissors (3210 :1: 50 cm l) is clearly separatcd from the
stretchings. Electron attracting {releasing} groups оп tlle 2 and 4 positions increase
{Iower} the wavenumber оС both strctchings [86, 91, 94, 95, 97]. This effcct is
less pronounced for substituents оп the 3 position. In solution thc wavenumbers
{intensities} of 'Ье stretchings increase {weaken} in order of the following solvents:
acetonitrile, nitromethane, benzene, carbon disulfide and tetrachloromethane [95].
Ал cmpirical correlation between the two strctching vibrations was given Ьу
Кrueger [87] for benzenamines in ,Ье free state: V s = 0.682 V a + 1023, with thc
exccption of some 2 substituted Ьепzепаmiпеs iп which the substituent interacts
with а hydrogen of [Ье amine group.
Iп associated aliphatic and alicyclic primary amincs, 'Ьс NH2 antisymmetric
strеtсhiпg vibration occurs а! 3365 :1: 25 cm 1 [88]. l Butanaminc absorbs а!
3370 cm l, FЗССН2NН2 takes the HW sidc with 3385 cm l, and in amines with
Ьrапсhiпg оп the Q carbon atom this band tends 'о shift (о lower wavenumbers:
tBuNH2 (3348), iPrNH2 (3356) and cPentNH2 (3357 cm l). In dilute solution or
in the vapour state, the v a NH 2 appears а! 3420 :1: 40 cm l. Iп benzenamincs the
vaNH2 is locatcd а! highcr wavenumbers: 3410 :1: 70 cm l, but more usually а!
3440 :1: 40 cm l ехсер! for 2 , 3 and 4 aminophenol, absorbing respcctively а!
3390,3364 and 3345 cm l. In dilute solutions this region bccomes 3470 :1: 50
cm l. For а series of з х and 4-X substituted Ьепzепаmiпеs, Nyquist [97] found
3480 :1: 30 cm l in solution and 3500 :1: 20 cm 1 for а gas, with (Ье highest
values for СFз , N02 and N=C substituted benzenamines and thc lowest for H2N
, Me2N and McO substituted benzenamines. Iп N or S-bondcd NH 2 this band is
observed а! 3350:1: 40 cm 1 as in hydrazines [71, 73,89], thioscmicarbazides [77,
78], N aminoheterocyclic aromatic compounds [83] and sulfonamides [25, 7 76].
AJiphatic and alicyclic primary аmiпеs in thc associated state display thc vsNH2
in 'Ье region 3290 :1: 30 cm l, and а! 3350 :1: 40 cm l as а gas or in dilutc
9. / Amiпo
235
solution. For the associated benzenamines the region becomes 3320 :!: 70 cт 1
or 3345 :!: 45 cm I if Ihc low valucs in the spectra of 4 HOPhNH2 (3285) апd
3 H(O== )CPhNH2 (3254 cm 1) are по! takcn iПIО ассоuпt. In dilute solutions the
Ьспzспаmiпсs absorb а! 3370 :!:: 50 cm l. For а serics of 3 X апd 4 X substituted
Ьспzспаmiпсs Nyquist [97) found З395 :!:: 20 cm 1 iп sоlutiоп апd 3415 :!: 15
cm 1 as а gas, with 'Ьс highest {Iowest} valucs for СFз , 02N and N=C {H2N ,
MC2N and McO } substitutcd Ьспzепаmiпсs.
Amine deformation
Тhe NH2 scissoring vibration gives rise 'о а broad stroпg band iп Ihe rеgiоп 1600
:!: 50 cm l. Disregarding the high value found iп (Ье gas рЬзsе spectrum of
Н2N(FЗС)2СNН2 (1640 and 16/4 cm I), 'Ье associated aliphatic апd alicyclic
amines absorb а! 1615 :!:: 20 cm l. In Ьепzепаmiпеs, еlесtroп withdrawing
{releasing} substitucnts cause а slight shift to highcr {Iower} wavenumbers [90,
91J. Thc highest {Iowest} wavcnumbers for the NH2 scissors are аssigпеd in the
spectra of thioamides (1620 :!:: зо) {sulfonamides (1565 :!: 15 cm I)}.
Amine rocking/twisting vibration
Тhe literature does по! agree in assigning 'Ье аmiпе rock (C 2v ) or twist (C s ) coupled
to anotl1er Ь\ (С 2 \.) or а" (C s ) vibration. Iп mеthапаmiпе this NH2 twist (1195
cm 1) is coupled 10 'Ье methyl rock. 'П aliphatic аmiпеs this vibration is mixed
with tl1c methylene twist and also with the C N strеtсhiпg viЬrаtiоп. lп this work
we ассер! 'Ьа! the p/TNH 2 provides the greatest contribution 'о the absorption а!
1160:!:: 140 cm \. Thioamidcs absorb а! high wavenumbers (1195:!: 110 cm \)
and benzcnamincs in 'Ье region 1070 :!:: 50 cm l, or 1060 :!: 40 cт 1 if the value
of 1050 cm l for benzcnamine [21, 23 25] is preferred to 1115 cт 1 [7J.
Amine wagging vibration
Associated Q saturated primary amines show а characteristic very broad diffuse
band between 1000 and 700 cm l, with maximum absorption а! 840 :!: 55 cm l.
For amines in 'Ье unbonded state this wag appears sharply а! lo\ver wаvепumЬеrs
(770:!:: 30 cm 1). 'П the speclra оС aromatic amines апd sulfопаmides this band is
weak, diffuse and affected Ьу other viЬrаtiопs in such а way 'о mзkе it difficull to
determine the ехас! wavenumber, which explains the ехtепsivе rеgiоп (620 :!: 100
cm I). For benzenamine, various wavenumbers зrе proposed: 700 [7J, 670 [23, 25,
96J,605 [24) and 570 cm 1 [21].
Amine torsion
According 'о the availabIe data, the NH2 lоrsiоп is аssigпеd iп the rеgiоп 290 :!:
130 cm l. In Q saturated amines the rеgiоп is reduced to 280:!: 70 cт 1 [92,93J.
236 Norl1la/ Vibratiolls alld AbsOl.ptioll Regiolls о/ Nitl'Ogell COl1lpO/ll/{/s
ТаЫе 9.2 Absorption regions (cm l) of tl1C ПОП11зl vibr3tions of NH2
Vibration (l sаt\lfзtеd аrОП1аtiс аП1idеs tl1iоаП1idеs N bonded
//a NH 2 3365 :!: 25 3410:!: 70 3390 :!: 60 3340 :!: 60 3350 :!: 40
v s NH 2 3290 :!: 30 3320 :!: 70 3210:!:60 3160:!: 80 3250 :!: 70
6 NH 2 1615:!: 20 1620 :!: 20 1610:!: 30 1620 :!: 30 1620 :!: 20
p/ TNH 2 1195:!: 90 1070 :!: 50 1125 :!: 45 1195:!: 110 1195:!: 90
wNH2 840 :!: 55 620 :!: 100 670 :!: 60 645 :1: 65 830 :!: 50
torsion NH2 280 :!: 70 230 :!: 70 280 :!: 70
sulfопаП1idсs
3355 :1: 35
3250 :!: 20
1565 :!: 15
1160 :!: 30
690 :!: 40
355 :!: 65
R NH2 compounds
R = R'CH2 (see 3.4.1.)
R = Me [1 9], СDз [1 3], iPr [10, 19], cPr [11, 12],
cBu [13], cPent [14], Н2N(FзС)2С [15], H2NCD2CD2 [16, 17],
H2C==CHCD2 and H2C==CDCD2 [18], H2C==CH [69, 70], Pb [7,
21 25, 96], XPb (Х = 2 , 3 and 4 Me [25 27], 2 E! [25], 3- and 4 FзС
[28, 29], 2 , 3 and 4 H(0==)C [30], 3 and 4 Mc(0==)C [25], 2 , 3 and 4
НО(О==)С [25], 4 N=C [25], 2 , 3 and 4 HO [25, 31], 2 , 3 and 4 MeO
[25], 2 and 4 HS [25], 2 , 3 and 4 02N [22, 25, 32, 33], 2 and 4 H2N
[25, 34], 2 , 3 and 4 F [25, 35 39], 2 , 3 and 4 Cl [20, 25, 40, 41], 2 and
4 Br [25, 42]), X 2 MePh (Х = 3 Me [43, 44], 4-Ме [43, 45], 5 and
6 Me [25], 3 CI [46], 3 02N [47], 4 Br [48], 4 HO [49], 4, 6 Me2 [50], 6 CI
[51]), X 2 EtPh (Х = 6 E! [25]), X 2 HOPh (Х = 4 Mc [52], 5 Me
[53], 5 02N [49], 5 CI [53]), X 2 McOPh (Х = 5 MeO [25], 5 Cl [46]),
X 2 02NPh (Х = 4 Me, 4 MeO and 6 02N [25], 4 02N [22, 25], 4 CI
[54,55], 4, 6 (02N)2 [22]), X 2 FPh (Х = 4 F [56], 5 Me [57], 5 F [25,
37]), X 2 CIPh (Х = 3 Cl [46, 58], 4-СI [25], 4-02N [54, 55], 5 Cl [25,
37,46, 58], 6 Cl [25,37,58---60], 4, 6 C12 and 4, 6 Br2 [61]), X 2 IPh (Х
= 4 I [25]), X 3 MePb (Х = 4 Me [43], 4 Br [48]), X 3 FPh (Х =
4 Me [57], 4 Cl [62], 4 F [63]), X 3 Cl Ph (Х = 4 Cl [59], 4 McO [46],
5 Cl [46, 58]), F5Ph [64], CI5Ph [65], X Pym (Х = 2 H2N [66],4,
5 (H2N)2 [67]), X Pyrazine (Х = 2-H 2 N [68]),
R = R'C(==O) (sec Section 7.2.1).
R = R'C(==S) (see Section 7.2.2).
R = H2N [71], H2NC(==S)NH [77, 78], H(O==)CNHC(==S)NH [72], 2,4
(02N)2PhNH [25, 73], MeS02 апd СDзS02 [74], H2NS02 [76],
Me2NS02 [75], 4 MePhS02 [25].
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73. J. Shukla and K.N. Upadhya, II/(lial/ J. P//re АррТ. PI/ys., 11,787 (1973).
74. К. Hanai, Т. Okuda, Т. Uno and К. Machida, Sрес/юсl/iт. Асса, Par/ А, 31Л, 1217
(1975).
75. У. Tanaka, У. Tanaka, У. Saito and к- Machida, Speclrocl/im. Асса, Parl А, 39А, 159
(]983).
76. Т. Uno, К. Machida and К. Hanai, Speclrocl/im. Aela, 22, 2065 (1966).
77. G. Keresztury and М.Р. Marzocchi. Spec/rocllim. Асю, Parl А, 31А, 275 (1975).
78. G. Kcresztury and М.Р. Marzocchi, CI/em. P/,ys., 6, 117 (1974).
79. H,j. Gotzc and W. Garbe, Speclrocl/im. Aela, Parl А, 35А, 461 (1979).
9.2 Me/I/ylaтillo
239
80. Н. Wolff, U. Schmidt апd Е. Wolff, Spectroclliт. Acta, Рап А, 36А, 899
(1970).
8]. L.K. Dyall, Spectrocl,im. Лсtа, Part Л, 25А, ]423 (1969).
82. L.к. Dyall, SpectrocIIim. Лсtа, ?art Л, 25А, ]717 (]969).
83. L.к. Dyall. SpectrocIIim. Лсш, Part Л, 44А. 283 (1988).
84. L.J. Bcllamy and R.L. Williams, Spectroclliт. Лсtа, 9, 341 (1957).
85. J.E. Slewart, J. CI,em. PI,ys., 30, 1259 (1959).
86. Е. Sacher, Spec/rocllim. Ас/а, Par/ Л, 43А, 747 (]987).
87. P.J. Кrucgcr. Na//lre. 194, ]077 (1962).
88. L. Segal and Е У. Eggcrton, Лрр/. Spec/rosc., 15, 112 (1961).
89. О. Hadzi, J. Jап and Д, Ocvirk, Spec/rocllim. АС/а, Part А, 25А, 97 (1969).
90. S.Ca lifапо and R. Moccia, Саи. Cllim. Ita/., 87,805 (1957).
91. AR. Katritzky апd R.A. Jопеs,J. Cllem. Soc., 3674 (1959).
92. S.M. Сrаvеп and ЕЕ Вспtlеу, Лрр/. Spec/rosc., 26, 449 (1972).
93. S.M. Craven, ЕЕ Вспtlсу and О.Е Репsепstаdlеr, Лрр/. Spec/rosc., 26, 647 (1972).
94. С. Laurепсе and В. Wojtkowiak, 8/111. Soc. CI,iт. Fr., 3124 (1971).
95. G. Varsanyi, Vibra/io"a/ Spec/ra о[ 8eпze"e Derivatives, Acadcmic Press (1969). рр.
376-----377.
96. О.Д, Тhоmtоп, J. Coord. CI,em.. 248, 261 (1991).
97. R.A. Nyquist, Арр/. Spec/rosc., 47, 411 (1993).
9,2 METHYLAМINO
According 'о the simplest approximation, the CNHCH frаgmепt in EtNHMe is in
а planc and this compound belongs 'о the point group C s , Тhe 15 vibrations iп
NНСНз differentiatc bctween 9а' + 6а" vibrational modes:
а': vNH, v Me, vsMc, o Me, osMe, oNH, vN C, р'Ме, t5 N C;
а": vaMe, ОаМе, рМе, /NH and two torsions.
Тhe NH stretching vibration
Тhc associated NH stretching viЬrаtiоп iп a: saturated, N or S Ьопdеd NHMe
compounds gives rise to а weak to moderate but broadish Ьапd iп the rеgiоп
3265 :!:: 50 cm l. In dilute solutions or in the vapour state this Ьапd паrrо\vs апd
shifts to higher wavenumbers: 3395 :!:: 45 cm l. lп а: uпsаturаtеd and aromatic
compounds the associatcd vNH appears moderately 'о stroпglу iп the region 3400
:!:: 40 cm l and а! 3450:!:: 30 cm l in the unbonded state, with the highest {Io\vest}
wavenumbers in the spcctra оС N mеthуlЬепzепаmiпеs with ап еlесtrоп аltrасtiпg
{releasing} group оп the 4 position, for example 4 XPhNHMe in \vhich Х = 02 N
(3445), НО(О==)С (3444), Н (3434), Ме (3429) and МеО (3423 cm l) [8, 14,
15]. 'П 2 substituted compounds or in the associated state, hуdrogеп bridges disturb
this rule.
240 No,."ral Vibratio"s a"d Absorp/io" Regio"s о{ Ni/roge" Compo/ll/(/s
Metl1yl strеtсhiпg vibrations
Ехсср! for tl1e 11igl1 \vаvспumЬеrs in the spectrum of 02NNHMe (3016 and 2953
cт 1), (Ьс antisymmetric stretcl1ing vibrations absorb in tl1C rcgions 2970 :!:: 30
cт 1 and 2945 :!:: 45 cm l. ТЬе band inteI1sity varies from weak in N methyl
substituted sulfonamides (о moderatc in N metI1yl substituted amines. ТЬе mcthyl
symmctric stretch absorbs, sharply and clearly scparated from 'Ье antisymmetric
counterparts, in 'Ье region 2855 :!:: 70 cm 1 with а moderatc 'о strong intcnsity
in amines and witl1 а weak intensity in sulfonamides. Thcse low wavenumbers,
attributed 'о а rcduced force constant of 'Ье СН bond under 'Ье influence оС 'Ье
free electron pair of 'Ье nitrogen atom, is typical for N Me compounds [8, 1 20]
but also for methyl ethcrs. N methylmetl1anamine with 2785 cm l in the solid state
and 2791 cm 1 as а gas is responsibIe for [Ье lowcst value and 02NNHMe exhibits
'Ье highest wavenumber: 2923 cm 1.
Тhe NH in plane deformation
In N methylamines 'Ье 8NH should Ье expccted in (Ье region 1530 :!:: 50 cm 1, but
'Ье very weak intensity of 'Ьс band hinders 'Ье assignment. Q Saturatcd secondary
amines show ап unspectacular small shoulder ( 1500 cm l) оп (Ье high frcquency
wiпg of the methyl and methylene deformations. In N substitutcd benzenamines this
8NH almost disappears in 'Ье strсtсhiпg vibrations of the ring 19а (19Ь) ( 1510
cm l) [21] or 8а (8Ь) (1640 :!:: 10 cт 1) [13]. Тhe NH deformation in N methyl
substituted sulfonamides is expected а! lower wavenumbers, so 'Ьа! 'Ьс region
1395 :!:: 25 cm l [11, 13,22] is preferred 'о 1635 :!:: 15 cm 1 [23]. 'П N methyl
substituted (thio)amides this 8NH (amide 11), coupled with (Ье vC N, exhibits а
stronger absorption (Section 7.3).
Methyl deformations
Both methyl antisymmetric deformations absorb weakly to moderately and often
coincide. Тhe region 1410 :!:: 35 cm 1 оС the methyl symmetric deformation is
typical for N methyl substituted amines and (thio)amides alike [24] and approaches
that of R C(==O)OMe (1435 :!:: 15) and ROMe (1445 :!:: 15 cm 1) compounds.
Тhe intensity of the symmetric deformation slightly excccds that of 'Ье anti
symmetric modes.
Methyl rocks and N C stretching viЬrаtiоп
Тhe three weak (о moderate аЬsоrрtiопs in 'Ье rеgiопs 1145 :!:: 45, 1095 :!:: 75 and
1015:!:: 95 cm 1 are due 'о two methyl rocking vibrations and а N C stretching
vibration strongly coupled among themselves. Тhe bands in the above mentioned
9.2 MetJly/amiпo
241
regions arc assigncd (о the N C stretch as well as 'о а methyl rock [21, 25].
Thc absorption ncar 1135 {1070} cm 1 in the spectra of N mеthуIsulfопаmidеs is
attributcd 'о thc mcthyl rock {N C stretch} [11,12].
Тhe NH wagging vibration
Associated N methyl substituted aliphatic amines ехтЫ! а very broad diffuse band
betwcen 950 and 650 cm l with а maximum аЬsоrрtiоп а! 725 :1: 20 cm l,
attributed 'о thc 'у (or c.v)NH. In the spcctra of N mcthyl substituted Ьспzепаmiпеs
and sulfonamides this NH wag is observed а! lowcr wavenumbers: 635:1: 35 cm 1.
Тhe broad band а! 670 cm l in 'Ье spcctrum оС 4 MePhS02NHMe is аssigпеd (о
this wag (13], although Gоldstеiп е! а/. (12] preferred 'Ье аЬsоrptiоп а! 722 cm 1.
Skeletal deformation and torsions
In N methyl substituted aliphatic amines and sulfonamides the БС N С is fоuпd
in the region 360:1: 50 cm 1. In N mеthуlЬепzепаmiпеs this viЬrаtiоп is coupled (о
the substitucnt sensitive Ph N dеfоrmаtiоп. Тhe methyl tоrsiоп is оftеп assigпеd
in the region 230 :1: 30 cт 1 and 'Ье NHMe torsion mау Ье expected iп the
neighbourhood of 100 cт 1 [26,27].
ТаЫе 9.3 Absorption regions (cт 1) of the normal viЬrаtiопs of NНMe
Vibration (l.saturatcd aromatic S02NНMc C(==O)NHMc C(==S)NHMe
N.bondcd (l unsaturalcd
vNH 3265 :1: 50 3400 :1: 40 3265 :1: 50 3315:1: 45 3250 :!: 70
УаМс 2965 :1: 25 2965 :1: 25 2965 :1: 25 2970 :1: 30 2970 :!: 30
v Me 2950 :1: 25 2950 :1: 25 2950 :1: 25 2945 :1: 45 2945 :1: 25
vsMc 2855 :1: 70 2855 :1: 70 2855 :1: 70 2870 :1: 45 2875 :1: 45
БNН 1530 :1: 50 1530:1: 50 1395 :1: 25 1550 :1: 50 1535 :1: 35
бамс 1470:1: 15 1470:1: 15 1470:1: 15 1450 :1: 30 1450 :!: 25
б Ме 1460:1: 15 1460:1: 15 1460:1: 15 1445 :1: 35 1435 :!: 25
бsМе 1410 :1: 35 1410:1: 35 1410:1: 35 1400 :1: 25 1400 :1: 25
pMclvN C 1150::1:: 30 1140::1:: 15 1135:1: 15 1155:1: 30 1t45:!: 45
p'McIVN C 1085::1:: 65 1055 :1: 25 1070:1: 15 1100:1: 65 1075 :1: 40
VN ClpMe 995 ::1:: 75 985 :1: 65 1020 :1: 50 1015:1: 95 1000 :!: 50
')'(c.v)NH 725 ::1:: 20 635 ::1:: 35 635 :1: 35 735 :1: 60 665 :!: 55
БС N С 360 :1: 50 360 :1: 50 315:1: 55 265 :1: 65
torsion Мс 230 ::1:: 30 230 ::1:: 30 230 :1: 30 230 :1: 50 195:1: 50
torsion NHMe 100 :1: 30 <100
R NHMe compounds
R = R'C(==O)NHMe (see Section 7.3.1).
R'C(==S)NHMe (see Section 7.3.2).
242 NO,."lUl Vib,'atio/ls a"d Absorptio/l Regio"s о/ Nit/"Oge" COlI/pOlll/(/S
R = Me [1----4], H2C==CH [5], Ph [6 8, 13], 2 HO(O==)CPh [9],
4 MeOPh [13], 2- and 4-FРh [13], 02N [10J, PI1NH [13J,
MCS02 and СDЗS02 [11J, PhS02 [12], 4 MePhS02 [12, 13].
References
1. G. Gamer and Н. Wolff, Spec/rocIIim. Ас/а, Par/ А, 29А, 129 (1973).
2. M,J. Butt1er and О.с. МсКеап, Spec/roc/rim. Асю, 21, 465 (1965).
3. W.G. Fateley and ЕА. Miller, Sрес/юс/ri/ll. Ас/а, 18, 980 (J 962).
4. АА. Chalnlers and О.с. МсКеап, Spec/rocIIim. Ас/а, 21,1387 (1965).
5. У. Amatatsu, У. Hamada, М. Tsuboi and М. Sugie, J. Мо/. Spec/rosc., 111, 29 (1985).
6. А Perrier Datin and J.M. Lebas, J. СЫт. P/,yS., 69, 59] (1972).
7. АК. Ansari and Р.к. Verma, Illdiall J. Pllre Арр/. P/,yS., 16, 454 (1978).
8. AR. Katritzk-y and R.A Jones, J. C/lem. Soc., 3674 (1959).
9. А Tramer, J. Мо/. S/rlIc/., 4, 313 (1969).
10. M.I. Dakhis, V.G. Dashevsl..-y and V.G. Avakyan, J. Мо/. S/ruc/., 13, 339 (1972).
11. А Noguchi, К. Hanai and Т. Okuda, Spec/rocIIim. Ас/а, par/ А, 36А, 829 (1980).
12. М. Goldstein, М.А Russell and Н.А Wil1is, SpectrocIIim. Ас/а, Par/ А, 25А, ]275
(1969).
13. G. Varsanyi, AssigllIIIell/s for Vibra/iolla/ Spec/ra ofSeI'e" Hlllldred Be"zelle Deriva/ives,
J.Wiley & Sons, New York (1974).
]4. С. Laurence and М. Benhelot, Spec/rocIIim. Ас/а, Par/ А, 34А, 1127 (1978).
15. L.K. Оуаll and J.E. Кетр, Spec/rocIIim. Ас/а, 22, 467 (1966).
16. J.P. Perchard, M. T. Forel and M. L. Josien,J. СЫт. P/,yS., 61, 660 (1964).
17. О.с. МсКеа" and I.A ElIis, J. Мо/. S/rlIc/., 29, 81 (1975).
18. I.A. Degen, Арр/. Spectrosc., 23,239 (1969).
19. R.D. НШ and G.D. Meakins, J. C/lem. Soc., 760 (1958).
20. J.T. Braunholtz, Е.АУ. Ebsworth, F.G. Мапп and N. Sheppard, J. С//ет. Soc., 2780
( 1958).
21. О. Hadzi and М. SkrbIjak, J. C/lem. Soc., 843 (1957).
22. О. Hadzi, J. C/lem. Soc., 847 (1957).
23. Т. Momose, У. Ueda and Т. Shoji, C/lem. P/lOrm. Bllll., 7, 734 (1959).
24. М. Beer, Н.В. Kesseler and G.B.B.M. Sutherland, J. С//ет. P/1YS., 29, 1097 (1958).
25. P.N. Gales, О. Steele and R.AR. Pearce, J. С//ет. Soc. Perki" Tra"s. 2, 1607 (1972).
26. R.A. Kydd and A.R.C. Dunham, J. Мо/. S/rlIc/., 98, 39 (1983).
27. R. Cervellati, G. СоrЬеш. А Оа1 Borgo and D.G. Lister, J. Мо/. S/rlIc/., 73, 31 (1981).
93 ACEТYLAМINO
In the C s symrnetry the 3N 6 = 21 поrrnаl viЬrаtiопs of NHC(==O)Me are
divided into 13а' + 8а" species of vibration:
а': vNH, v Me, vsMe, vC==O, 6NH, 6 Me, 6 s Me, vC N, р'Ме, vC C, 6С==0,
6N C C, 6 N C;
a/l: vaMe, 6 а Ме, рМе, wNH, ,с==о and three torsions.
9.3 Acety/aтillo
243
The NH stretching viЬrаtiоп
The NH stretching vibration in N substituted acctamides appears strongly and
broadly in thc region 3280 :!:: 60 cт l and shifts to highcr wаvепumЬсrs (3410 :!::
70 Cffi l) in dilutc solutions.
Methyl strctching vibrations
ТЬс mcthyl antisymmctric stretching viЬrаtiопs cxhibit а weak band iп 'Ье rеgiопs
2990 :!:: 20 and 2965 :!:: 35 ст 1. ТЬе mcthyl symmetric stretch appcars wcakly
in the range 2900 :!:: 45 cm l.
Thc с==о strctching vibration
ТЬс с==о strctching vibration (amide 1) absorbs strongly iп the rсgiоп 1690:!:: 45
cm l, with thc highcst valucs from the spcctra of imides: McC(==O)NHC(==O)Mc
(1735 and 1701) and MeC(==O)NHC(==O)Et (1734 cm l). Тhe rcmaining
compounds show this vC==O in а rcgion typical for amides: 1675 :!:: 30 cm l.
ТЬс NH in planc deformation
ТЬе NH in plane dcformation (amide П), coupled with the vC N, gives а
strong band in ,Ье region 1540 :!:: 60 cт 1 for ,Ьс trallS сопfigurаtiоп опlу.
Together with the amidc 1 absorption, this БNН shows а characteristic pair of
bands. The highcst wavcnumber is assigned in thc spectrum of N chloroacctamidc
(1597 cm l). Thc lowcst valucs are fоuпd iп the spectra of imidcs (1500 :!::
20 Cffi l): H2NC(==0)NHC(==0)Me (1482) апd McC(==O)NHC(==O)Me (1505
cm 1). Most of the N substituted acctamides display this БNН а! 1545 :!:: 25
cm l.
Mcthyl deformations
The methyl antisymmetric deformations provide а weak to moderatc Ьапd iп 'Ье
regions: 1450:!:: 30 and 1420 :!:: 20 cm l, but they usuaIly coincidc. As contrasted
with 'Ьс vcry weak stretchings, thc mcthyl symmctric dсfоrтаtiоп appcars more
strongly in [Ье region 1365 :!:: 10 cт 1.
The C N stretching vibration
The C N stretching vibration (amide 111), couplcd with the БNН, is moderately
'о strongly activc in the rcgion 1275 :!:: 55 cm l. Тhc imidcs arc rеsропsiЫе for
the extcnsivc rcgion: MeC(==O)NHC(==O)Me givcs risc 'о ап antisymmetric NC2
244 Norl1la/ Vibratiolls а/ll/ Absorptioll Regiolls о/ Nit/'Ogell COl1lpollllds
at 1310 and а sуnзnзеtriс NC2 stretch а! 1222 cm 1. Tl1C N pI1enyl substituted
acetamides (acetanilides) absorb а! the HW side of the region (13 10 :!:: 20 cm l)
and N alkyl substitutcd acetamides а! 1290 :!:: 35 сnз l.
Methyl rocking vibrations and c c strctching vibration
The nзеthуl rocks arc observed as wcak 'о mеdiunз bands in the regions 1090 :!::
40 and 1015:!:: 35 cm l. Tl1e vC C absorbs wcakly to moderately in the region
915 :!:: 65 cm l. N Phenyl substituted асеtаnзidеs display this c c strctching
vibration near 965 сnз 1 .
The NH out of plane dеfоrnзаtiоп
The ')'NH/C==O or wNH/C==O (amide У) is moderately activc with а broad band
in the region 790:!:: 70 сnз l. The N phenyl substitutcd acctamides апd the t/'Шls,сis
imides absorb а! the HW side of this region (840 :!:: 20 cm l) and 'Ье N alkyl
substituted amides and the tralls,tralls imides а! the LW side (760 :!:: 40 cm l).
The с==о deformations
The с==о in plane deformation (аnзidе IV) is located а! 625 :!:: 70 сnз l
as а moderate band. The highest wаvепunзЬеr is observed in the spcctrum оС
MeC(==O)NНCl (693) and the lowest in 'Ьа! of McC(==O)NHC(==O)Me (560
and 648 cm l). N Methylacetamide absorbs а! 628 cm 1.
Usually the с==о out of plane deforrnation ')'C==O/NH (аnзidе VI) is assigncd
in the region 540 :!:: 80 cm l. Нigh values originatc fronз the spectra of
EtNHC(==O)Me апd nBuNHC(==O)Me (620 cm I). А few 4 XPhNHC(==0)Mc
compounds (Х = Н, Br, НО, ЕЮ) absorb а! 485 :!:: 25 cm l.
Skeletal deformations апd torsions
Асеtуlаnзiпо соnзроuпds display 'Ье in plane skcletal N C C deforrnation in
the region 420 :!:: 55 сnз l, for example RNHC(==O)Me compounds in which R =
Ме (429), Е! (427) апd nBu (450cm 1). N Phenyl substituted acetamides absorb
in the neighbourhood of 385 сnз l.
The external N C deformation is found in the range 310 :!:: 65 cm l. The
lowest external N C dcforrnation (а") or NHC(==O)Me torsion depends
largely uроп the R substituent, but for а fcw molecu1es the torsion is assigned at
225:!: 65 cm l. Usually the methyl torsion absorbs at 200 :!:: 65 cm 1 and the
С(==О)Ме torsion at Iower wavenumbers, probabIy at 100 :!:: 40 cm l.
9.3 Acety/aтillO 245
ТаЫе 9.4 Absorption rcgions (cm l) оС (Ье normal viЬrаtiопs of
NHC(==O)Mc
Vibration Region Vibration Region
vNH 3280 :1: 60 рМе 1090:1: 40
v.Mc 2990 :1: 20 р'Ме 1015:1: 35
v Me 2965 :1: 35 vC C 915:1: 65
l/.,Me 2900 :1: 45 ,(w)NH (У) 790 :1: 70
vc==o (1) 1690:1: 45 Бс==о (IV) 625 :1: 70
БNН (11) 1540 :1: 60 /C==O (VJ) 540 :1: 80
Б.мс 1450 :1: 30 БN С С 420 :1: 55
Б Ме 1420:1: 20 Б N С 310:1: 65
Б.,Ме 1365:1: 10 torsion NHC(==O)Me 225 :1: 65
vC N (111) 1275 :1: 55 torsion Мс 200 :1: 65
torsion С(==О)Ме 100:1: 40
R NHC(==O)Me molecules
R = Me [1 15], СDз [8----12], Et [1, 16], nPr and пВu [16],
HOCH2CH2 , HSCH2CH2 [17], MeC(==O) [18----20, 27],
EtC(==O) [21], H2NC(==0) [22], Ph [24, 26], 4 MePh [26], 4--
H2NPh [24], 2 MeC(==0)NHPh [26], 2 , 3 апd 4 02NPh [26], 4--
HOPh , 4 ЕtOРЬ , 2 CIPh [26], 4 CIPh [23], 4 BrPh [24], 2,6
CI2Ph [26], CI [25].
References
1. Т. Miyazawa, Т. Shimanouchi and SA. Mizushima, J. С/,ет. P/,ys., 24, 408 (1956).
2. Т. Miyazawa, Т. Shimanouchi and SA.Mizushima, J. С/,ет. P/,yS., 29, 611 (1958).
3. R.L. Joncs, J. Мо/. Spectrosc., 11, 411 (1963).
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5. S.E. Кrikorian and М. Mahpour, Spectrocilim. Acta., Part А, 29А, 1233 (1973).
6. S. Ataka, Н. Takeuchi and М. Tasumi, J. Мо/. Strllct., 113, 147 (1984).
7. У. Grenie, М. Avignon and С. Garrigou Lagrange, J. Мо!. Slrllct., 24, 293 (1975).
8. М. Rey Lafon, M. T. Forel and С. Garrigou Lagrange, Spectroc/lim. ACla, Part А, 29А,
471 (1973).
9. А. Warshel, М. Levitt and S. Lifson, J. Мо!. Spectrosc.. 33, 84 (1970).
10. В. Schneidcr, А. Horeni, Н. Pivcova and J. Honzl, Collect. Czec/I. С/ШII. CO/ll/llII/I., 30,
2196 (1965).
11. Н. Pivcovii, В. Schneider and J. Stokr, Collect. Czec!l. C/lem. COпIlIllIII., 30, 2215 (1965).
12. J. Jakes and S. Кrimm, Spectrocilim. Acta, Part А, 27А, 19 (1971).
13. А. Baliizs, Acta СЫт. Acad. Sci. HIII/g., 108,265 (1981).
14. А. Balazs,J. Мо!. Strllct., 153, 103 (1987).
15. N.G. Mirkin and S. Кrimm, J. Мо!. Strllct.. 236, 97 (1991).
16. J. Jakes and S. Кrimm, Spectrocilim. Acta, Part А, 27А, 35 (1971).
17. G. Zuppiroli, С. Perchard, M.L. Baron and С. de Loze, J. Мо!. Strllct., 69,1 (1980).
18. У. Kuroda, У. Saito, К. Machida and Т. Uno, Spectrocilim. Acta, Parl А, 27А, 1481
(1971).
246 NOl'lllal Vibratiolls а//(/ Absorptioll Regiolls о[ Nitl'Ogell Соm[JО/lШ/S
19. У. Kuroda, У. Saito, К. Machida aI1d Т. Uno, Spectroc!lil1l. Ас/а, Part А, 29А, 411
(1973).
20. Т. Uno and К. Macl1ida, 8///1. C/rel1l. Soc. JplI., 34. 545 (1961).
21. Т. Uno and К. Machida, 8///1. C/rcl1l. Soc. JplI., 34, 551 (1961).
22. У. Saito and К. Macl1ida, Spcc/roc/ril1l. Ас/а, Par/ А, 35А, 369 (1979).
23. Р. VcnkatacharYl1lu, I.V.S.R.M. SаmlЗ and О. Premas\varup, llIlliall J. PlIre Арр/. P/rys.,
20, 670 (1982).
24. S. Tariq. N. АН and Р.к. Verma, IlIdiтr J. PlIre Арр/. P/,yS., 22, 265 (1984).
25. J.E. Devia and J.c. Carter, Spcc//"Oc/lil1l. Ас/а, Рт'/ А, 29А, 613 (1973).
26. G. Varsanyi, Assiglll1lCI/IS [or ИЬrа/iОllа/ Spec/ra о[ Scvell HIIIIl/rcd Bellzellc Derivativcs,
J.Wilcy & Sons. Nc\v York (1974).
27. F. Ramondo, S. Nunziante and L. Bencivenni,J. Мо/. S/rtlc/., 291, 219 (1993).
9.4 DIMETHYLAМINO
With (Ье Н and N atom оС N methylmethanaminc in the symmetry plane and both
methyl groups situated symmetrically with respect (о this plane, the CNC angle
is bisected. According 'о C s , the 24 normal vibrations differentiate betwcen 13а'
+ l1а" vibrational modes. Substitution of (Ье NH strctching vibration (а') Ьу а
torsion (a/l) results in 12а' + 12а" normal vibrations for 'Ье NMe2 fragment:
а': уйМе (2), vsMe, бйМе (2), бsМе, рМе (2), //sNC 2 , БNС2, wNC 2 , torsion Ме;
a/l: уйМе (2), vsMe, бйМе (2), бsМе, рМе (2), v a NC 2 , pNC2, tоrsiоп Ме and
torsion NMe2.
ТЬе molecular fragments PhNMe2 [9, 10] and S02NMe2 [48,51] are studicd
in this way. If the molecular skeleton and both methyl groups form part of the
symmetry plane, 'Ье normal vibrations are divided into 14а' + 10а" specics of
vibration. In that сзsе (Ье dimethylamino fragment possesses the plane structure,
as in HC(==0)NMc2 [19,20,22] and MeC(==0)NMe2 [25]:
а': уйМе (2), vsMe (2), бйМе (2), бsМе (2), V a NC2, рМе (2), v s NC 2 , БNС2, pNC2;
a/l: уйМе (2), бйМе (2), рМе (2), wNC 2 , torsion Ме (2), torsion NMe2.
Methyl stretching vibrations
AJthough the NMe2 group provides four methyl antisymmetric stretching vibrations,
usually only two are observed: 2990 :1: 30 and 2950 :1: 25 cт 1. ТЬе in phase(a')
and 'Ье out of phase (a/l) vibrations rarely give rise (о separate bands. In delimiting
these absorption regions, the high wavenumbers in 'Ье spectrum of 02NNMe2 (3033
and 2993 cm l) arc поt taken into account. Not infrequently tcrtiary (sulfon)amides
overstep the limit of 3000 cm 1, for iпstапсе: MeS02NMe2 and PhS02NMe2
9.4 Diтe/Jly/aтillo
247
( 3020 cm I), N=CNMe2 (3017 cm l) and СDзС(==0)NМе2 (3016 cm l).
Terliary amines оС the 'урс R NMe2 (R = alkyl or aryl) are activc а! 2980 :1: 15
cm l.
The frce pair of electrons of thc N atom wеаkепs the СН bond parallel 10 the
axis оС this orbital, producing the typical lоwеriпg of the 'symmetric' strеtсhiпg
vibrations, which approach ncar 'Ье region iп which lhe оvеrtопеs апd соmЫпаtiоп
bands of 'Ьс methyl deformations are active [59----63]. Тhe litcrature does поt agree
in assigning thesc symmetrical strеtсhiпg vibrations, which ехрlаiпs the ехtепsivе
regions (2855 :1:: 65 and 2835 :1: 65 cm l). А! the HW side, пеаr 2920 cm l,
опе finds а few N, N dimеthуlЬепzепаmiпеs such as 4 XPhNMe2 (Х = Н(О==)С,
НО(О===)С, 02N), Me2NC(===X)NMe2 (Х = S and Se) апd 0==NNMe2. Low
wavenumbers are observed in the spectra of MeNMe2 апd HC(==0)NMe2 ( 2775
cm l), HNMe2, EtNMe2 and HC(===S)NMe2, which absorb near 2790 cm l. Тhe
highest value (2948 cm I), assigned iп the spectrum of 02NNMe2, is поt taken
into ассоuпt.
Methyl deformations
Occasionally the in plane (а') and out of plane (a/l) viЬrаtiопs are observed
separatcly so 'Ьа! only two bands instead of fош emerge (1465 :1: 25 and 1445 :!:
25 cm I). lПе high wavenumber (1495 cm l) in the spectrum оfNзС(==0)NМе2
falls outside this region. The HW side is covered Ьу RNMe2 (R = N=C, 4 N=CPh
and N=CC(==O) with the value 1488 cm l. Low values in the пеighЬоurhооd of
1425 cm 1 have Ьееп traced in 'Ье spectra ofMe2NC(==Se)NMe2 апd N=CNMe2.
'П the spectrum of N=CNMe2 the methyl symmetric dеfоrmаtiопs are аssigпеd
al 1342 and 1333 cm 1 and iп that of F2PNMe2 а! /443 and 1313 cm l.
Disregarding these low values, the methyl symmetric dеfоrmаtiопs are observed
scparately in the regions 1410 :1:: 35 and 1385 :1: 30 Cт l. High values ( 1442
cm l) originate from the spectra of HNMe2, HONMe2 апd H2NS02NMe2 do and
d2. The LW side is covered Ьу MeC(===S)NMe2, with 1360 cm l.
Skeletal stretching vibrations and methyl rocks
Between 1300 and 700 cm 1 four methyl rocks and two skeletal NC2 strеtсhiпg
vibrations are observed separately in the regions:
pMe/v a NC 2 vaNCz/pMe рМе
рМе
рМе
V s NC2
1250:1::50 1165:1::35 1115:1:651060:1:40 1005:1:65 850:l:150cm 1
lПе highest methy1 rock is coupled with the NC2 strеtсhiпg viЬrаtiоп. Тhe N,N
dimell1ylamides are responsible for the extensive region iп which [Ье v,NC 2 is
248 Nomra/ Vib,.atio//s аl/(/ Absol]J/io// Regio//s о! Ni/юgе// COlI/fJO/ll/(/s
аssigпеd because 111C rcgion 750 :!:: 30 cm 1 is often attributed 10 this vibration [7,
3 32, 38]. Miclke and Barnes [25] and Garrigou L;lgrange and Forel [28] attribule
'Ье \vavenUI11ber 960 {740} cт 1 iп 111C speClrUI11 of N,N dil11ctl1ylacctamide поl
only (о 'Ье v s NC 2 {I/C C}, bul also for а parl 10 111e vC C {V.,NC2}, Most
invesligalors, 11Owevcr, hold (Ье saI11e view 'Ьаl tl1C vC C makcs tl1C grealesl
cOnlribution to (Ьс absorplion а! 750 :!:: 30 cт 1, so Ihat 111C morc convenienl
region 900 :!:: 80 СI11 I is reserved for the NC2 symmctric slrctching vibration. 'П
Ihe speclra оС N,N dimethylbenzenamines Ihc v s NC 2 is found аl 950 :!:: 20 cm l.
Skelelal deformalions
Тhe NC2 in plane deformalion сап Ье found in the region 460 :!:: 65 cm l. Тhe
exlreme values are from HC(==S)NMc2 with 520 СI11 1 and HC(==0)NMe2 wilh
400 cm l. Тhe vibralional analysis of R NMe2 compounds reveals another two
partly external skeletal NC2 deforrnalions: the NC 2 wagging vibralion (360 :!:: 50
cm l) and ,Ье NC2 rocking vibralion (300 :!:: 75 cm l).
ТаЫе 9.5 Absorption rеgiопs (cm l) of the normal
vibrations of NMe2
ViЬrаliоп Region ViЬrаtiоп Region
vaMe 2990 :!:: 30 pMe/v a NC 2 1250 :!:: 50
vaMe 2990 :!:: 30 V a NC 2/pMe 1165 :!:: 35
vaMe 2950 :!:: 25 рМе 1115 :!:: 65
vaMe 2950 :!:: 25 рМе 1060 :!:: 40
vsMe 2855 :!:: 65 рМе 1005 :!:: 65
vsMe 2835 :!:: 65 V s NC 2 900 :!:: 80
ЬаМе 1465 :!:: 25 bNC2 460 :!:: 65
ЬаМе 1465 :!:: 25 WNC2 360 :!:: 50
ЬаМе 1445 :!:: 25 p NC 2 300 :!:: 75
ЬаМе 1445 :!:: 25 torsion Ме 245 :!:: 50
bsMe 1410:!:: 35 tоrsiоп Ме 185 :!:: 55
bsMe 1385 :!:: 30 lоrsiоп NC2 120 :!:: 50
R NMe2 I110lecules
R = H [1---4], o [1, 2], Me [3, 5, 6], EI [7], Pb [8
11, 18], 4 H(0==)CPb [12, 18], 2 HO(0==)CPh [13, 14], 4
HO(O==)CPh and 4 EtO(0==)CPh [15], 4 N=CPh [10], 4
02NPh апd 4 (0==)NPh [18], 4 Mc2NPh and 4 (4
Me2NPh) Ph [11],2- and 4 Py [16], N=C [17], HC(==O) [19
24], MeC(==O) [2 29], СDзС(==О) [27 29], EIC(==O) [30,
31], nPrC(==O) [32], N=CC(==O) [33], Me2NC(==0) [34, 35],
9.4 Diтe/hy/aтi/lo
249
NJC(==) [36], H2NC(==0)C(==0) апd MeHNC(==O)C(==O) [37],
H2C==CHC(==0) [38], H2NC(==0) [39], HC(==S) [21, 40],
MeC(==S) [40, 41J, N=CC(==S) [42], Me2NC(==S) [43,
44], (CDJ)2NC(==S) [44], HC(==Sc) [45], Me2NC(==Se) and
(CDJ)2NC(==Sc) [46], FS(==0)2 and BrS(==0)2 [47], CIS(==0)2
[47, 48], MeS(==0)2 апd PhS(==0)2 [50], H2NS(==0)2
and D2NS(==0)2 [51], H2C==N [52], 02N [53], C==N [54],
НО and oo [55, 56], Cl [57], F2P [58J, (Mc2N)2P and
(Me2N)2As [49].
References
1. G. Gamer and Н. Wolff, SpectrocIIim. Acta, Part А, 29А, 129 (1973).
2. M,j. Buttler and О.С МсКеап, SpectrocIIim. Acta. 21, 465 (1965).
3. W.G. Fateley and F.A. Miller, SpectrocIIim. Acta, 18,980 (1962).
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5. G. Dellepiane and G. Zerbi, J. C/lem. P/,yS., 48.3573 (1968).
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12. J.G. Rosencrance and P.N. Jagodzinski, SpectrocIIim. Acta, Part А, 42А, 869 (1986).
13. К.R.к. Rao and CI. Jose, J. Мо/. Stтct., 18, 447 (1973).
14. Д, Tramer, J. Мо/. Str/lct., 4, 313 (1969).
15. М. Forster and R.E. Hester, J. C/lem. Soc. Faraday Tra"s. 2, 77, 1535 (1981).
16. S.P. Gupta, Д, Salik and R.K. Goe1, I"dia" J. P/,ys., 61В, 427 (1987).
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18. G. Varsanyi, Assig/ll1le"ts [о, Vibratio"a/ Spectra oJSeve" H/I"dred Bellzelle Derivatives,
J.Wiley & Sons, New York (1974).
19. Z. Mielke, Н. Ratajczak. М. Wiewiorowski, A,j. Bames and S,j. Мitsоп, SpectrocIIim.
Acta, Part А, 42А, 63 (1986).
20. Т.С Jao, 1. Scott and О. Steele, J. Мо/. Spectrosc., 92, 1 (1982).
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22. G. Каufrпапп and M.J.F. Leroy, В/I//. Soc. СЫт. Fr., 11,402 (1967).
23. О. Steele and Д, Quatermain, SpectrocIIim. Acta, Part А, 43А, 781 (1987).
24. R.L. Jones, J. Мо/. Spectrosc., 11, 411 (1963).
25. Z. Mielke and A,j. Bames, J. C/lem. Soc. Faraday Tra"s. 2. 82, 437 (1986).
26. G. Ourgaprasad. D.N. Sathyanarayana, СС. Patel and Н.5. Randha\va, SpectrocIIim.
Acta, Part А, 28А. 2311 (1972).
27. С Garrigou Lagrange, С Ое Loze, Р. Bacelon, Р. Combelas and J. Oagaut, J. СЫт.
P/,yS., 67,1936 (1970).
28. С Garrigou Lagrange and M. T. Forel,J. СЫт. P/,yS., 68.1329 (1971).
29. д'М. Owivedi, S. Кrimm and S. Mierson, SpectrocIIim. Acta, Part А. 45А, 271 (1989).
30. К.У. Ramiah, У.У. Chalapathi and СА!. Chary, C/lrr. Sci., 35,350 (1966).
250 Normal Vibratiolls ат! AbsOlptioll Regiolls о[ Nitюgеll Compo/lllds
31. У.У. Chalapatl1i and К.У. Ramiah, C//rr. Sci., 37. 453 (1968).
32. к.у. Ramiah and S.к. Sayee, C//rr. Sci., 38. 457 (1969).
33. Н.О. Desseyn and J.A. Le Poivrc, Spectrocl1im. Ас/а, Pт.t А, ЗIА, 635 (1975).
34. H.L. Spell al1d J. L1ane, Specl1vcl1im. Ас/а, Par/ А, 28А, 295 (1972).
35. К. Ravindranatl1 and к.у. Rаnзiаl1, l",/iт/ J. P//re Appl. P/rys., 15, 182 (1977).
36. W. Buder and А. Schmidt, Spectroc//im. Ас/а, Part А, 29А, 1429 (1973).
37. Н.О. Desseyn, B.J. Уа" der Veken and М.А. Неmшп, Spectroc//im. Ас/а, Part А, ЗЗА,
633 (1977).
38. G.R. Rao and К.У. Rаnзiаh, l",lia/l J. P//re Appl. P//ys., 18,94 (1980).
39. У. Mido, К. Tanase and К. Кido, Spec//"Oc/rim. Ас/а, Pт.t А, 45А, 397 (1989).
40. С.А.I. Сlшry and К.У. Rаnзiаh, Proc. l",/iт/ Aca(l. Sci., 69А, 18 (1969).
41. А. Ray and D.N. Satllyanarayana,B//II. С//ет. Soc. JP/l., 45, 2712 (1972).
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43. R.к. Gosavi, U. Aga!'ovala and C.N.R. Rao, J. Ат. CI/em. Soc., 89, 235 (1967).
44. U. Anthoni, Р.Н. Nielsen, G. Borch, J. Gustavsen and Р. К1аЬое, Spectroc//im. Ас/а,
Par/ А, 3ЗА, 403 (1977).
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46. U. Anthoni, Р.Н. Nielsen, G. Borch and Р. К1аЬое, Spec/rocl1im. Ас/а, Рт'/ А, 34А, 955
( 1978).
47. Н. Biirger, К. Burczyk, А. Вlaschette and Н. Safari, Spec/rocl/im. Ас/а, Par/ А, 27А,
1073 (1971).
48. У. Tanaka, У. Tanaka, У. Saito and К. Machida, B//II. C/lem. Soc. JP/l., 51,1324 (1978).
49. G. Davidson and S. Philips, Spec/rocl1im. Ас/а, Par/ А, 35А, 141 (1979).
50. М. Goldstein, М.А. RusseII and Н.А. Willis, Spec/roc/lim. Acta, Par/ А, 25А, 1275
(1969).
51. У. Tanaka, У. Tanaka, У. Sailo and К. Machida, Spec/roc//im. Ас/а, Par/ А, З9А, 159
(1983).
52. W.c. Harris, F.L. Glenn and L.B. Кnight, Spec/roc/lim. Ас/а, Par/ А, ЗIА, 11 (1975).
53. С. Trinquecosle, М. Rey Lafon and M. T. Forel, Spec//"Ocl1im. Ас/а, Par/ А, ЗОА, 813
(1974).
54. Р. Rademacher and W. Liittke, Spec/rocllim. Ас/а, Par/ А, 27 А, 715 (1971).
55. Н. Bohlig, W. MuIIer Sachs, J. Fruwert and G. Geiseler, Z. P//ys. CJ/em., 266, 415
(1985).
56. Н. B6h1ig, S. Franke and J. Fruwert, Z. P/rys. CJ/em., 268, 355 (1987).
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58. М.А. Fleming, R.J. Wyma and R.C. Taylor, Spec/rocl1im. Ас/а, 21,1189 (1965).
59. R.D. Нill and G.D. Meakins,J. C/rem. Soc., 760 (1958).
60. A.R. Katritzky and R.A. Jones, J. CI/em. Soc., 3674 (1959).
61. J.P. Perchard, M. T. Forel and M. L. Josien, J. CJlim. PJ,yS., 61, 660 (1964).
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9.5 NIТRO
According 'о whcther the N02 plane is in thc symmctry рlапс (i.p) or perpendicular
10 this plane (о.р), the distribution of 'Ьс normal vibrations is as follows:
9.5 Nitro
251
Point group v a N0 2 v s N0 2 БN0 2 wN0 2 pN0 2 torsion
С 2 " (i.p) Ь2 а) а) Ь\ Ь 2 а2
С . (i.p) а' а' а' а" а' а"
С 2 " (о.р) Ь 1 аl а] Ь 2 ы а2
С . (о.р) а" а' а' а' а" а"
ТЬе most characteristic bands in the spectra of nitro соmроuпds are due to the
N02 stretching vibrations, which are the two most useful group frеquепсiеs, по!
only because of their spectral position but also for their Slroпg iпtепsitу. It is very
interesting 'о compare thc absorption regions of N02 with those of CO z .
Antisymmctric stretching viЬrаtiоп
In saturated nitro compounds the antisymmetric stretching vibration is located iп the
region 1580 :1: 80 cm l. Electron wilhdrаwiпg {rеlеasiпg} groups оп the Q carbon,
such as N0 2 or halogcn, result in а high {Iow} frеquепсу shift (16, 38, 93], for
example: FзСNО 2 (1620), ВrзСN02 (1606), CICH2N02 (1577), EtN02 (1560),
iPrN0 2 (1535) and tBuN0 2 (1530 cm I). Evidently the wаvепumЬеr decreases
with increased branching оп the Q atom. Тhe highest values (16ЗО :1: ЗО cm l)
are furnished Ьу tri and poly nitro alkanes and 'Ье lowest (1560 :1: 60 cm l)
Ьу nitroamines. For molecu1es without N02 or hаlоgеп iп the viсiпitу, the rеgiоп
becomes more user friendly: 1570:1: 20 cm l. Nitrоmеthапе gives the V a N02 пезr
1562 cт ] and а! ::::::1586 cт 1 in the уарош state. Molecules with Ьеауу N or О
isotopes absorb at lo\ver wаvепumЬеrs, for example: Me\5N02 (1524) (1, 11] and
MeN\80 2 (1522 cm 1) [11].
With the exception of 'Ье соmроuпds substituted Ьу а stroпg еlесtroп rеlеasiпg
group оп the 2 or 4 position, the пitroЬепzепе derivatives display the VaN02 in
the region 1535 :1: 30 cm 1 апd the 3 nitropyridines а! 1530:1: 20 cm 1 [49]. Тhe
strong band is easy to recognize among the aromatic riпg strеtсhiпg viЬrаtiопs. А
strong electron donating group оп the 2 or 4 position Io\vers this region 'о 1500 :1:
20 cm l, such as in nitrobcnzenamines, nitrophenols, пitrорhепоl ethers апd R'HN
substituted 3 nitropyridines, for ехатр]е: 4 H2NPhN02 (1481), 4 Me2NPhN02
(1484), 2 Me(0==)CHN 3 02N Py (1486), 2 H2NPhN02 (1510), 4 EtOPhN02
(1515) and 4 HOPhN02 (1516 cт ]). NitroЬепzепе absorbs at 1523 cm l and 3
nitropyridine at 1530 cm l. The conjugated nitroalkenes also show the V a N02 а!
1535 :1: 30 cm ] [38] with H2C==CHN02 to the HW side (1565 cm l).
Symmetric stretching vibration
Saturated nitro compounds without N02 or halogen оп the Q саrЬоп display the
N02 symmetric stretching vibration at 1380 :1: 20 cm l. А shift 10 lo\ver \YaYe
numbers occurs when the Q carbon is substituted Ьу N02 or hаlоgеп, for example:
252 NO/'l//a/ \Iibтtio//s a//d A/)sOlptio// Regio//s о/ Nit/'Oge// Compolll/(/s
CH2(N02)2 (1330 and 1292), FзСN02 (1310) and ВrзСN02 (1311 сш I). Thc
lo\vcsl wаvспuшЬсrs arc obscrvcd in tl1C spcctra оС Iri al1d poly nitro compoul1ds:
1295 ::!:: 80 cm l. This VsN02 is, morc llзап thc 1/"N02, couplcd will1 othcr
vibralions of 'Ьс nlOleculc, particularly \vill1 tl1C C N slrclcl1ing vibration. ТЬс
inlcnsily оС 111C v s N0 2 is sошеwlзаt \vcakcr llзап thal оС thc V"N02. Nilroшсlhапс
absorbs in Ihc vicinity of 1400 cm l.
lп subsliluled nitrobcl1zenes 111e l/sN02 appcars strol1gly аl 1345:1: 30 сш l, in 3
nitropyridines аl 1350::!:: 20 сш 1 [49] and in conjugatcd nitroalkenes а! 1345::!:: 15
cт l [38]. With 'Ьс cxceplion of2 H2N 5 CIPhN02 (/350 [75] or 1371 [76]), 2
HO(0==)CPhN02 (1371), 3,4 CI2PhN02 (1370), 3 Cl 4 H2NPhN02 (1367) and
2 Me 3 H2NPhN02 (1367 сш I), this vibration in nitrobcnzcnes is found аl 1345
::!:: 20 сш l. Nitrobcnzcnc itself absorbs аl 1348 cm l. Nilrobcnzenes with а strong
elcctron donaling subsliluenl (NH2, NMe2, ОН, ОМе. . .) givc rise 10 а sccond band
а! 1305 ::!:: 20 сш 1, псх! to the absorplion а! 1345 ::!:: 20 сш 1. This phcnomcnon,
occurring wilh 1, 4 and 10 а lesser extent also wilh 1,2 substilution, mау Ьс duc to
self associalion [57], Fcrmi resonance [58] or а mixed vibration with vC N [91].
Тhe cOnlribulion оС thc VsN02 10 lhis second band cxplains the exlension of the
region 10 lo\vcr wavcnumbcrs: 1325 ::!:: 40 сш l. Тl1e extrcmely low values from the
speclra of 2 H2N I,3 (02N)2Ph (1268 and 1364) and 1,3,5 (02N)з 2,4,6 (Н2N)зРh
(1230,1303 a//d 1322 сш l) are поl taken into accounl.
Dеfоrшаliоп
Iп (Ьс speclra оС поп сопjugаtеd nilro compounds the N02 in planc dсfоrшаtiоп
is assigned in Ihc region 690 ::!:: 85 cm l, usuaHy as а \veak to modcralc band.
For nitroamines lhis region bccomcs 765::!:: 10 сш l [10,11]. High wavcnumbcrs
are also found in 'Ьс spcclra оС cPrN02 (770), FзСNО2 (750), tBuN0 2 (731) and
iPrN02 (724 cm l). For most of thc saturalcd, halogcnalcd or N02 subslilutcd
nilro compounds lhis region is reduced to 650 ::!:: 45, or суеп 655 ::!:: 25 cm l, if
the varying values frош tеtrапitrоmеthапе (690, 668 and 606 cm l) arc not lakcn
inlo ассоuпt. Тhc rcgion 755 ::!:: 10 cm 1 in the speclra оС 'Ье eslers оС nitric acid
is аssigпеd 10 WN02 [38].
ТЬе N0 2 scissors occurs at higher frequcncies (850::!:: 60 cm l) whcn conjugatcd
to с==с or аrошаtiс molecules, according 10 some investigators with а contribution
of the vC N which is expecled near 1120 cт l [3,48,92]. For nitrobcnzenc this
bN02 is reporled at 852 сш l, for H2C==CHN02 аl 890 cm l. Most оС 'Ье
nitrobenzcncs absorb in Ihc rcgion 855 ::!:: 40 cm l, but Ihe foHowing compounds
faH oulsidc this region: 1,3 diпitroЬепzепс (904 and 834), 3 N=CPhN02 and 3
H(0==)CPhN02 wilh 900 cm l аl Ihc HW sidc and 2,4,6 lrinitromelhylbcnzene
(814 [72], 874 and 805 [73]), 2 ТhN02 (813), FsPhN0 2 (812), 1,3 (02N)2 5
НО(О==)СРЬ (811), 2 Mc I,5 (02N)2Ph (836 and 792) and 2 Me I,3 (02N)2Ph
(84/ and 791 сш l) аl Ihc LW sidc.
9.5 Nitro
253
Wagging vibration
Thc WN02 in aliphatic nitro соmроuпds is weakly to moderately active in 'Ье
rапgс 620 :!: 1lO cm 1, disrcgarding the values аrоuпd 400 cт 1 in the spectra of
Х з СN0 2 (Х = F, Cl, Br) assigncd as much to the wag as to the rock [3, 22, 23].
Ехсер! for PhC(==0)CH2N02 d7 (510 cт 1) the R'CH2N02 соmроuпds display
(Ье wN0 2 а! 570 :!: 45 cm l. Secondary апd tertiary соmроuпds give this wag
а! 610 :!: 40 cт l and nitroamines in the rеgiоп 660:!: 70 cm l. Nitromethane
absorbs near 605 cm 1. ТЬс region 700 :!: 20 cm ) iп the spectra of пitrаtеs is
assigned 'о БN02 [38].
In C\' unsaturated and aromatic compounds the WN02 is assigпеd а! 740 :!: 50
cт l with а moderatc to strong intensity, а region in which also the aromatic ")'СН
is active. In the spectrum of nitrobenzene the аЬsоrptiоп а! 794 р03} cт 1 is
assigned to the ,СИ {wN02} although 'Ье two viЬrаtiопs are coupled [5, 14, 40,
43]. И 2 С==СНN0 2 absorbs а! 714 Cffi l. Тhe highest values have Ьееп observed
in the spectra of 2 Me 5 CIPhN02 (790), 4 H2NPhN02 (785 [57] or 750 [45,
48]), 2 MePhN02 (784 [43] or 729 [45]) and 2 HOPhN02 (781 [53] or 747 [45]
cт ). The lowest values are from пitrоЬепzепе d4 (690), 1,2 diпitroЬепzепе (701
and 728), 1,4 dinitrobenzene (710 and 772), 2 HO 6 BrCH2C(==0)PhN02 and
nitrobenzene with 703 cт 1. Мапу WN02 viЬrаtiопs are аssigпеd iп 'Ье rеgiоп
745 :!: 35 cm l.
Rocking vibration
In aliphatic nitro соmроuпds the pN0 2 falls somewhere in the large rеgiоп 495
:!: 125 Cffi l. For molecules without N02 or halogen оп 'Ье Q carbon the rеgiоп
becomes 480 :!: 50 cm 1, а region that splits up into 500 :!: 30 cт 1 for secondary
and tertiary compounds and 465 :!: 35 cm 1 for primary compounds. For example,
cPrN0 2 absorbs а! 528 cт ) and nitromethane а! 480 Cffi l. Тhe highest wave
numbers соmе from nitroamines: 590 :!: 30 Cffi l.
In aromatic nitro compounds the pN02 is active in the region 545:!: 45 cm l,
mostIy еуеп а! 540 :!: 30 cm 1. NitrоЬепzепе show this rock а! 531 cт l but the
pN0 2 in И 2 С==СНN0 2 falls outside this region, а! 652 Cffi l.
Torsion
In aliphatic compounds 'Ье N02 tоrsiоп absorbs probabIy in the neighbourhood of
60 cт l [30]. For aromatic соmроuпds Varsanyi е! а/. [63] found 70 :!: 20 cт l
and Suryanarayana е! а/. [85] 65 :!: 10 cт l. Тhe value 139 cт l iп the spectrum
of nitrobenzene [41] is considered 'о Ье ап оvеrtопе [90J.
254 NO/'//lal VilJт/io/ls а//(/ AlJsorp/io/l Regio/ls о! Ni//'Oge/l CompolI//(/s
ТаЫе 9.6 Absorption regioI1s (cт 1) of thc norl11al vil>ratiOJ1s of N02
Vibration Q saturated Q lшlоgеl1 dil1itro tri and polY l1itro
V a N0 2 1570:1: 20 1590:1: 35 1575 :1: 35 1630:1: 30
V s N0 2 1380 :1: 20 1340 :1: 35 1345 :1: 60 1295 :1: 80
6N02 700 :1: 70 695 :1: 55 660 :1: 30 650 :1: 45
WN02 580 :1: 70 590 :1: 70 580 :1: 70 580 :1: 70
p N0 2 480 :1: 50 450 :1: 80 440 :1: 70 440 :1: 70
torsion N02 ::::::60
Vibration nitroamil1es nitrates Q Ul1saturated arol11atic +1
aromatic
V a N0 2 1560 :1: 60 1635 :1: 20 1535 :1: 30 1500:1: 20
V s N0 2 1325 :1: 25 1285 :1: 15 1345 :1: 30 1325 :1: 40
6N02 765:1: 10 755 :1: 10 (w) 850 :1: 60 855 :1: 40
WN02 660 :1: 70 700 :1: 20 (6) 740 :1: 50 760 :1: 30
p N0 2 590 :1: 30 535 :1: 35 545 :1: 45 540 :1: 30
torsiol1 N02 ::::::80 70 :1: 20
+1 = strong electron releasing group оп the 2 or 4 position.
R N02 compounds
R = Me [1 12], СDз [8 12], Et [2,4,7, 13, ]4], MeC02 , MeCHO ,
СDзСН2 and СDзСD2 [13], nPr [2, 4], nBu , nPent , пНех ,
nOct , nNon and nDec [4], HOCH2CH2 [15], 02NCH2CH2 [7],
PhCH2 [16], PhC(==0)CH2 do , d2 , d5 and d7 [17], iPr [14,
18], cPr [14, 19], tBu [14], CICH2 CICD2 BrCH2 and
BrCD2 [20], EtCHCICHCl , EtCHBrCHBr , MeCCI2 and
EtCHCICCI2 [16], HOCH2CHCl and HOCH2CCI2 [15],
02NCC12 [25], FзС [3, 21 23], СlзС [22, 23, 24], ВrзС
[22, 23], 02NCH2 [7, 26], 02NCMe2 [27, 28], 02NCMe2CMe2 [27,
29], 02NCH(Me) and 02NСН(Еt) [16], (02N)2CH [7], (02N)зС [7,
30], (02N)2C(Me)C(N02)Me [27], (О2N)зСС(N02)2 [7], MeHN ,
MeDN , СDзНN and СDзDN [10, 31], Me2N and (CD3)2N [11,
31], MeO and СDзО [32 34], ЕtO [35, 36], пРепtO ,
PbCH20 and EtC(Me)20 [38], CH2==CHCH20 [37], iPrO [37],
H2C==CH [5, 14], MeCH==CH [39], EtCH==CH [38], Pb [3,5,
14, 4 3], Ph d5 [40, 44], XPb (Х = 2 , 3 and 4 Me [43, 45 50],
4 HO(0==)CCH2 [48], 4 N=CCH2 [45], 3 and 4 HOCH2 [48], 2 , 3 and
4 CICH2 [48], 3 and 4 BrCH2 [45, 48], 4 FзС [45], 3 алd 4 N=C [45, 47,
48, 50], 2 , 3 and 4 Н(0==)C [45, 47, 48, 51], 3 and 4 Me(0==)C [45, 48,
50], 3 nPr(0==)C, 2 , 3 and 4 HO(0==)C [45, 48, 52], 3 and 4 MeO(0==)C
[45, 47, 48, 50], 3 and 4 ЕtO(0==)с [45, 47, 50], 2 , 3 and 4 CI(0==)C
and 2 , 3 and 4 BrCH2(0==)C [45, 48], 2 , 3 and 4 H2N [45, 47 9, 56-----
58], 2 , 3 and 4 Me(0==)CNH [45], 4 Mc2N, 4 Et2N and 4 H2NNH [45],
9.5 Nitro
255
2 , 3 and 4 02N [45, 47, 48, 50, 59---64, 85], 2-, 3 апd 4 HO [3, 45, 47,
48, 53, 54], 3 and 4-МеО [45, 47, 48, 50], 2 and 4-ЕtO [55], 2 and 4
Ме(О===)СО [45], 2 MeOS [45], 2 , 3 and 4-F [43, 45, 48, 50, 65], 2 , 3-
and 4 Cl [43, 45, 47, 48, 50, 64, 66], Br [43, 45, 47, 48, 50, 66], 1 [43,
45, 47, 48]), X 2 MePh (Х = 3 CI [67], 5 C][68], 3 02N [63], 5 02N [63,
69], 3 H2N [70], 4 1--1O [71], 5-Ме(0==)С [45], 3, 5 (02N)2 [72, 73, 74]),
X-2 НОРh (Х = 3 02N [45, 63], 4 Н(0==)C, 4 , 5- and 6 BrCH2(0==)C
[45], 5 Me(0===)C, 5 CI), X 2 H2NPh (Х = 3 02N [45, 63], 5 CI [75,76],
5 Me, 5 MeO [45], 3,5 (N02)2 4,6 (NH2)2 [77, 78]), X 2 McOPb (Х = 5
Ме(О==)С [45]), X 2 CIPh (Х = 3 , 4 and 5 C] [85]), X-2 ВrРh (Х = 5-
Br [79]), X-3 I--IOРh (Х = 4 BrCH2(0==)C [45]), X-з МеоРh (Х = 4-Br
[80]), X 3 H2NPh (Х = 4 HO [71]), X 3 02NPh (Х = 4 HO(0==)CCH20
4 MeO(0===)CCH2 [63], 5-НО(О==)С [45], 5-CI(0==)C [45, 63], 4 H2N, 4
H2NNH, 5-0 2 N [45, 63, 81, 82], 4 HO, 4 BrCH2CH20, 4-F [45, 63, 83, 84,
85], 4 Cl [45, 66, 84, 85], 4-Br [45, 66, 85]), X 3 C1Ph (Х = 4 апd 5-Сl
[79, 85], 4 H2N [75, 76]), X-3 ВrРh (Х = 4 MeO [80]), Х 3- ОзSРh (Х
= 4-Сl [45]), X 4 HOPh (Х = 3 BrCH2(0==)C апd 3 Me(0==)C [45]), .
3,5 (02N)зРh dз [45, 81, 82], 2 (02N)2 Me4Ph [86], F5Ph [87], 4
Py [88], 4 Py N oxide do and d4 [89], 2 Тh .
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10
Normal Vibrations and
Absorption Regions of
Оху Compounds
10.1 R'.OXY COMPOUNDS
10.1.1 Hydroxy
Тhe ОН group provides three поrmаl vibrations: vOH, БОН and 'у ОН, of which
not оnlу the stretching vibration but also the out of plane deformation are good
group vibrations.
ОН stretching vibration
Тhe competition Ьсtwееп steric hindrance and inter and intra molecular hydrogcn
bridges makes it possible that, in the spectra of R OH compounds in the liquid
or solid state, 'Ье ОН stretching viЬrаtiоп appears in the extensive region 3275 ::!::
370 cm l. Тhis region is reduced 'о 3380 ::!:: 200 cт l if some high values iп the
spectra оС phenols and low values in thc spectra of carboxylic acids ате not taken
into account.
Sterically unhindered alcohols, including most of the primary alcohols but not
aromatic alcohols апd polyols, show this vOH. . .0 at 3370::!:: 50 cm l, usually еуеп
а! 3345 ::!:: 15 cm l, as а strong broad band. Тhe ring substituted aromatic primary
alcohols (benzyl alcohols) соует а wider region (ззоо::!:: 120 cm l), limited Ьу 3,5
(MeO)2PhCH20H (3420) оп 'Ье опе side and 2 IPhCH20H and 1,3 (HOCH2)2Ph
(3180 cm l) оп the other. Тhe little shoulder (3550 cm l) оп thc broad band
10.1 R' oxy Coтpouflds
259
(3380 cm l) in the spcctrum оС benzenemethanoI gives away 'Ье presencc of а
monomer.
Alicyclic ОН compounds are activc а! 3330 :!: 50 cт 1 апd sесопdаry alcohols,
being stcrically hiпdсrеd 'о а certain degrce, usually аЬоуе 3350 cm l (3370 :!:
30 cm 1). Cyclohcxanol and cyclopentanol absorb а! 3333 cm l, сусlоЬutапоl
а! 3304 cm ] and 'ВиСН(ОН»Х (Х = Мс and Et) пеаr (Ье upper limit: 3391
cm l.
Thc ОН stretching vibration оС 'Ье more stroпglу sterically hiпdеred tertiary
alcohols appcars а! highcr wavenumbers: 3470 :!: 1 10 cm l. 'П the fоllоwiпg
examples thc ОН strctching vibration shows more and more the character of а free
vOH, the band becomes sharper and the wavenumber increases: МезСОН dо (3365)
апd d9 (3380), ЕtзСОН (3405), ОсtзСОН (3410), РhзСОН апd сНехзСОН (3475),
Ph(Me)C(OH)C(OH)(Me)Ph (3495) and (Ph)2C(OH)C(OH)(Ph)2 (3577 cm l).
Polyols, if 'Ьеу are по! sterically hiпdеrеd, show low аЬsоrptiоп Ьапds (3280
:!: 100 cm I), particularly compounds with ап iпtепsе fоrmаtiоп of hуdrogеп
bridges such as ЕtС(СН20Н)з (3231), НОСН2СН(ОН)СН(ОН)СН20Н (3215) апd
3 HOCH2PbCH20H (3180 cm l). Likewise, а! the LW side опе finds the vOH...O
iп the spectra of hydroxylamines (RIR2N OH) and oximes (R==N OH) in the
region 3255 ::!::: 75 cm l and iп those оС silanols (RIR2RзSi 0Н) ath 3260:!: 40
cm l.
Phenols covcr thc widcst range: 3390 :!: 255 cm l. Тhe highest ОН strеtсhiпg
vibrations are found in 'Ье spectra of 2,6 disubstituted рhепоls, with 2,6 !Bu2PhOH
(3645 cm l) as ап example. ТЬе lowest values соmе from с==о subs!itu!ed
phenols (3190 :!: 55 cm l) [58], 2 nitropheno]s (3230 :!: 40 cm l) [41] and
2,4,6 trinitrophcnol with 3150 cm l [41]. Mos! of the other рhепоls were fоuпd
!о give this ОН stretching vibration in [Ье rеgiоп 3390 :!: 70 cm l, in which
the 2 substituted {4 substituted} phenols are responsibIe for 'Ье highes! {Iowest}
values:
vOH
2 X PhOH
3475 ::!::: 90
3 X PhOH [62]
3360 :!: 40
4 X PhOH [62] Naphtho1s
3310 :!: 90 3310:!: 90
Examples are: 2 Ph PhOH (3565), 2 MeOPbOH (3512), 2 MePhOH (3448), 3
MePhOH (3335), 4 iBuPhOH (3221), Naph I OH (3290), 2 , 3 and 4 !BиPbOH
(respectively 3535, 3360 and 3240 cm l) апd 2 Me Naph I OH (3390 cm I).
Compounds falJing outside the аЬоvе mепtiопеd rеgiопs are: 2 HOPhPh 2 OH
(3155), 3 HOPhOH (3184) and 4 cPentPhOH (3184 cm l).
ТЬс associated ОН. . .0 stretching vibration iп organic acids gives rise 'о а very
broad band with maximum absorption а! 3050 :!: 150 cт l (Sесtiоп 7.1.7).
In [Ьс absencc of intramolecu1ar hydrogen bridges, the broad Ьапd of the ОН
stretching vibration disappears in dilute soIution or in the уарош state and retums
260 NomlCl[ Vibтtiolls а//(/ AbsOI'[Jtioll Regiolls о/О.\у Compoll//(/S
as а slзаrp peak а! 361 О :l: 30 ст 1. In acids tl1c broad band docs по! disappcar
complctely and the absorption in 'Ьс ncigl1bourl100d of 3500 cm 1 shows part оС
thc frcc ОН.
The ОН in plane dсfоrтаtiоп
Primary a1cohols in the associatcd state exhibit а wcak 'о modcrate, often diffuse
band in 'Ье rcgion 1400:l: 40 cm l, attributed to the ОН...О in plane deformation.
Somctimes this region is extended 'о lower wavenumbcrs (1310 :l: 130 cm l)
because of tl1e coupling оС this vibration with thc methylene wag and twist. In this
case 'Ьс ОН in plane deformation is conceived as а mixcd vibration: Б(ОН + СН2)
[59 61]. In secondary a1cohols also this БОН (1380:l: 50 cm 1) is coupled to the
Бен. Tertiary a1cohols absorb in thc region 1370 :l: 40 cm l. In dilute solutions
'Ье ОН iп рlапе deformation shifts 'о lower wаvспumЬсrs and is difficult 'о detect
among the СН deforrnations.
ln 'Ье spectra of silanols 'Ье БОН appears as а weak 'о moderate band а! 1065
:l: 35 cm 1.
ТЬе moderate 'о strong absorption а! 1350 :l: 40 cm ' in the spectra of phenols
is аssigпеd 'о the БОН. . .0. The band with the strongest intensity in the region
1220 :l: 40 cm 1 is due to the vC O with а contribution of this он in plane
deformation [34, 55, 57]. Рhепоls give the free ОН in plane dcformation as а sharp
peak with moderate intensity in the region 1170 :l: 30 cm 1 [55].
The region 1395 :l: 55 cm 1 in the spectra of carboxylic acids is also assigned
as well 'о this ОН in plane deforrnation [56].
The он out of plane deformation
With the exception оС acids, 'Ье ОН out of plane deformation in thc associated
statc exhibits а broad, diffuse Ьапd in the extensive region 685 :l: 115 cm 1. 'П 'Ье
spectra of higher a1cohols (octadecanol upwards) and poly substitutcd phenols, in
which 'Ье он group contributes only in а small аmоuпt, the weak band, оп Wl1ich
other absorptions ме superimposed, is difficult 'о observe. Primary a1cohols absorb
а! 640 :l: 70, secondary а! 630 :l: 30 and tertiary a1cohols а! 620 :l: 30 cm 1.
The ОН out of planc dеfоrmаtiоп in 'Ье spectra of phcnols takes up the whole
region: 685 :l: 115 cm l. Carbonyl substituted phenols give high valucs: 750 :l:
50 cm 1, for example 2 MeC(==O)PhOH (800), 4 MeC(==0)PhOH (780) and
3 HC(==O)PhOH (710 cm I). The rcmaining phenols restrict thcmselves 'о the
rcgion 650 :l: 80 cm ' with а weak, broad band disturbed Ьу ring vibrations.
Carboxylic acids display this /,ОН...О iп (Ьс rапgс 905:l: 65 cm 1 as а weak
'о moderate band with the appearancc of а У.
ТЬс free он out of plane deformation is described as а torsion and absorbs а!
low wavenumbers: 300 :l: 80 cm 1 in thc spectra of a1cohols [ 11] and 330 :l:
80 cm 1 in 'Ье spectra of phenols [29, 30, 32].
10./ R' oxy CoтpOll/lds
261
ТаЫе 10.1 Absorplion rеgiопs (cm l) of 'Ье поrmаl viЬrаtiопs ofthe associated OH
ViЬrаtiоп Nоп aromatic Aromatic Sесопdаry апd Teniary Polyols
primary alcohols primary alcohols alicyclic alcohols
vOH 3370 :1:: 50 3300:1:: 120 3340 :1:: 60 3470:1:: 1]0 3280:1:: 100
бон ]400 :1:: 40 1400:1:: 40 1380 :1:: 50 1370:1:: 40 ]400:1:: 35
"У ОН 640 :1:: 70 660 :1:: 20 630 :1:: 30 620 :1:: 30 650 :1:: 70
Hydroxylamines Silапоls Phenols Carboxylic
апd oximes acids
vOH 3255 :1:: 75 3260 :1:: 40 3390 :1:: 255 3050 :1:: 150
бон ]400 :1:: 30 ]065 :1:: 35 1350 :1:: 40 1395:1:: 55
"У ОН 740 :1:: 60 670 :1:: 30 685:1::115 905 :1:: 65
R CH20H compounds (see Sесtiоп 3.2.1).
R CH2CH20H compounds (see Sесtiоп 3.5.4).
R CHOH R' compounds (see Section 5.3).
R OH compounds
R = cBu [1], cPent [2], cHex , cHept , cOct , tBu [3 5],
(СDз)зС [4, 5], ЕtзС , ОсtзС , сНехзС , FзС(Ме)2С [6),
(FЗС)2МеС [7], (FзС)зС [8), СlзС(FЗС)2С (9), F2С==С(СFз) (10),
4 HO(Me)2C Pb C(Me)2 [11], FзС (12], (Рh)зС (13, 14),
Рh(Мс)С(ОН) С(Ме)Рh , (Рh)2С(0Н) С(Рh)2 , Me2N [15, 16),
McCH==N [17], Me2C==N , Me(EtO)C==N , MeC(==O)NH ,
(Ме)зSi (18], PI12(HO)Si , РhзSi , 4 HO(Me)2Si Ph Si(Me)2 [19,
20], Pb [21 29], 2 , 3 and 4 XPb (Х = Ме [29 34], Е! and iPr [34], tBu
[26), НС(==О) [34-----36], МеС(==О) [34, 36], РЬС(==О), НО [25, 34,37,38],
H 2 N [34,36,39], 02N [34,40,41], F, CI, Br, 1 [30, 31,34, 36), 4 XPh (Х
= iBu, cPent, BrCH2C(==0) [34], N=C [34, 36], НО [28), 2 апd +
XPb (Х = EtC(==O), nPrC(==O) [34J), 3 and 4 XPb (Х = МеОС(==О)
[34], НОС(==О) [34, 36]), 2 XPh (Х = Ph, 2 HOPb, HONH(O==)C [54]),
Me2Ph [34, 42], МезРh [43], 2,6 tBu2Ph , CI2Ph [34, 42, 44],
СlзРh [44], CI4Ph [44, 45], CI5Ph [44, 46], 2,4,6 ВrзРh [47],
Br5Ph [46J, 2,4,6 IзРh [48], 2,3 (HO)2Pb [49], (02N)2Ph [34],
(02N)зРh [41], 2 H2N 5 MePh [50], 2 H2NA MePh апd 2 H2NA
CIPh [51], 2 H2N 4 02NPh [52J, Naph I-, Naph 2 апd 6 HO Naph
2 [53].
References
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31. С. Garrigou Lagrange. М. Chehata and J. Lascombe,J. СЫт. P/,yS., 63, 552 (1966).
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(1988).
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40. y'J(jshore, S.N.Sharma and c.P.O.Owivedi, /"dia" J. PI,yS., 48, 412 (1974).
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/0.1 R' oxy Coтpouпds
263
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АСIa, Par/ А, 39А, 677 (1983).
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50. R.к. Gocl, к.Р. Kan al and S.N. Sharma, /lIdiall J. Pure Арр/. Phys., 17,778 (1979).
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28] (] 980).
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10.1.2 Methoxy
ТЬе СНзО group yields 3N 6 = 12 поrmаl viЬrаtiопs, ofwhich nine Ьеlопg 10 the
methyl group. ТЬс rcmaining three Пlау Ье described зs: c o strеtсhiпg vibration,
c o deformation and McO torsion. Oftеп the МеО group, which is capable
of taking up diffcrent positions with respect to (Ье rest of the molecule, gives rise
(о extra bands, mainly in the I/sMe rеgiоп. Moreover, оvеrtопes апd соmЫпаtiоп
bands of (Ье deformations Пlау occur in ,Ье strеtсhiпg mode area, which obstructs
ап unambiguous assignment. Because of the поп еquivаlепсе of (Ье СН Ьопds, 'Ье
methyl vibrations сап also Ье described as iпdерепdепt СН viЬrаtiопs.
Methyl stretching vibrations
То аН appearanccs the МеО molecules display the l/аМе а! а wavenumber
lower than 3050 cm 1 (3000 :J: 50 cm t). А! the HW side of this rеgiоп
absorption is shown Ьу МеОС(==О)ОС(==О)ОМе (3049) and also Ьу esters in
which 'Ье halogen clearly asserts its iпfluепсе: FC(==O)OMe (3047 cm l) and
CIC(==O)OMe, CICH 2 C(==0)OMe, CI 2 CHC(==0)OMe, С1зСС(==0)ОМе апd
CIC(==O)C(==O)OMe, which аН absorb in (Ье пеighЬоurhооd of 3040 cm l. А!
'Ье LW side опе finds МеОСН==СНОМе (2955) апd Н2С==СНОМе (2959cm I).
There is а realistic chance of finding the l/ а Ме with weak (о moderate iпtепsitу iп
the region 2995 :J: 35 cm t.
264 Nо/'llШ/ Vibтliol1S al1d AbsOlpliol1 Regiol1s о{ Оху ComjJolll/(/s
Тl1e I/ Mc is \ocatcd in 'Ьс rcgion 2975 :1: 55 cm 1 so tl1at bo!h stretchings
oftcn coincidc. Compounds such as МеОС(==О)ОС(==О)ОМс and FC(==O)OMc
rc"eal this v Me near 3025 cт 1 and the metllyl estcrs of thc chlorinatcd acctic
acids in the neighbourllOod of 3020 СП1 I. Sclf cvidcntly опс 11as !о procccd with
caution in аssigпiпg thcsc s!rC!cI1ings iп unsaturated or аroП1аtic mе!Ьуl cthers and
esters because оС !hc ==сн stretcl1il1g vibra!ions being expectcd also in !!lС abovc
mcntioncd regions. In tl1C LW area mсthохуmеthапе dз and dl (2917 and 2922),
MeS(==O)OMc (2925) and Н2С==СНОМе (2927 cm l) are active. The remaining
studicd МеО СОП1роuпds absorb usuaHy in the rеgiоп 2975 :1: 40 cт ) with а weak
'о moderatc intcnsity.
The methyl symme!ric s!retching vibration in mcthyl esters is reported in 'Ьс
extensive ral1ge 2920:1: 80 cm J, but 2900:1: 60 cт 1 is also useful if the high
values in the spectra of КОС(==О)ОМе (2996) and FC(==O)OMe (2974 cm l)
are disregardcd. In thc region 2850 :1: 30 cт 1 опе fiпds 'Ьс vsMe of saturated,
unsaturated and aromatic methyl ethers. The lowcst values (::::::2820 cm J) have
Ьееп observed in the spectra of ЕЮМе d2, МеСН==СНОМе, MeOCH2CHzOMe,
cBuOMe and in those оС а few aromatic methyl ethcrs such as 2 CIPhOMc (2830),
РЬОМе (2834), 2 McOPy (2850) апd the isomcrs of (MeO)2PhC(==0)H and
(МеО)зРhС(==О)Н with 2850 :1: 10 cm J. ТЬе compounds in which the МеО
group is joil1ed 'О а halogenated С atom display this vsMe а! the HW side of the
above mentioned region.
Methyl deformations
Тhe regions оС the mcthyl dcformations overlap each other, so that !hese normal
viЬrа!iопs are по! always observed separately.
Тhe 8аМе is repor!ed in 'Ьс region 1460 :1: 25 cm ) with, а! 'Ье HW
sidc, МеОМе and MeS(==O)OMe with 1485 cт 1, Н2С==СНОМе with 1482
cm ) and methyl acetate with 1480 cm J. Тhe lowest wavenumbers arc due
to ОО(О==)ССН==СНС(==О)ОМе (1438) and НО(О==)ССН==СНС(==О)ОМе
(1440 cт 1). Disregarding thcse extreme va1ues, most оС thc МеО compounds
show this vaMe а! 1460 :1: 20 cm J.
Тhe 8 Me is active iп 'Ье region 1455 :1: 20 cm l. Тhe highest wavenumbers
соmе from Н2С==СНОМе (1471) and Ме2РОМс (1470 cт 1) and the lowest from
ОО(О==)ССН==СНС(==О)ОМе (1438) and НО(О==)ССН==СНС(==О)ОМе
(1439 cm 1). Methoxymethane absorbs а! 1459 cm J.
In some methoxy compounds the methyl symmetric deformation (1435 :1: 35
cm J) is scarccly or поt а! аН separated from its antisymmetric counterpart,
such as in the spcc!ra of Ме2Р(==0)ОМс (1470), 4 N=CPhOMe (1467), 3
N=CPhOMe (1462), cis MeOCH==CHOMe (1460) and FCH20Me (1453 cm J).
Low valucs originate from the spectra of H2NC(==S)OMe do and d2 (1400
and 1410), Me2P(==S)OMe (1417), CI 2 P(==S)OMe (1422) and МсООМе (1424
cm J). Тhe majority of thc investigated molccules were found 'о give this
/0.1 R' oxy Coтpollпds
265
symmctric deformation in а region (1445 :!: 15 cm l) relatively high compared
with that for the saturated hydrocarbons (1375 :!: 15 cm I). Nevertheless, some
investigators assign thc absorption near 1390 cm 1 iп di апd tri-mеthохуЬепz-
aldehydcs 'о thc Ь"Мс instcad of the Бен of the aldehyde fuпсtiоп [52,57].
Methyl rocking viЬrаtiопs and c o strctch
Мапу of the R OMe compounds shows the рМе in the rеgiоп 1195 :!: 45 cт l
with variabIe intensity, ехсер! МсОМе (1250 апd / /8/) and CI2NC(==O)OMe
(1071 cm I). High values оrigiпаtе from the spectra of МеОСН20Ме (1232),
cBuOMe (1228), Н 2 С==СНОМе (1219) and ХСН2СН20Ме (Х = CI, Br, 1) with
values near 1210 cm l. In the spectra of some RC(==O)OMe соmроuпds the рМе
is assigned а! or ncar the same wavenumber as 'Ьа! of 'Ье c(==o) o strеtсhiпg
viЬrаtiоп, which appears as а strong band iп the rеgiоп 1255 :!: 60 cm l. /п the
LW area опе finds MeHNC(==S)OMe (1150), 2 ТhOMe (1151), МеООМе (1156)
and Cl2HCCF20Me (1159 cm l). Most оС the R OMe molecules give lhis рМе,
\vhich is least coupled to the c o stretching vibration, iп 'Ье region 1180 :!: 20
cm l.
The p'Me/yC O is more coupled to the C O strеtсhiпg viЬrаtiоп апd
absorbs in 'Ье rcgion 1155 :1: 35 cm l. А few соmроuпds show both
methyl rocking vibrations а! 'Ье same wavenumber, such as Ме2Р(==О)ОМе
(1187), ClS(==O)OMe (1186), Me2POMe do and d6 (1183), lСН20Ме (1180),
CI2P(==S)OMe (1175) and MeS(==O)OMe (1173 cm l). Iп аdditiоп, the нw side
оС 'Ьс above mentioned region is limited Ьу BrCH20Me (1190), НзSiOМе (1185)
and FзСС(==О)ОМе (1178 cm I). Тhe lowest values соте fюm H2NC(==O)OMe
(1120), МеСН==СНОМе (1121), 2 BrPhOMe (1121), 4 N=CPhOMe (1122) апd
2 CIPhOMe (1129 cm l). Most of 'Ье R OMe compounds show this normal
vibration а! 1150 :1: 25 cm 1.
Тhe vibrational analysis of R OMe molecules reveals the vC Olp'Me iп the
region 975 :1: 125 cm 1, usually with moderate iпtепsitу. The majority оС the
invcstigated molecules wcre found to give this strеtсhiпg mode iп [Ье narrOwer
rеgiоп 980 :1: 80 cm l, exceptions being H2NC(==S)OMe (1100), MeSiH20Me
(/092), Ме2РОМс (1068) and СDзОМе (853), H2NC(==O)OMe (880) апd
Н 2 С==СНОМе (896 cm l). Тhe vsCOC in the spectrum of mеthохуmеthапе is
assigned а! 919 cm l and methoxyethane shows this yC O а! 1019 cm l.
Skeletal deformation
Тhe skeletal c o dcformation сап Ье fоuпd iп the ехtепsivе region 415 :!: /65
cm l. Тhis band rarely possesses moderate iпtепsitу, апd is usually very weak 10
weak. Тhe highest wavenumbers (460 :!: 120 cm l) are assigned iп the spectra
of saturated methyl ethers and the lowest iп those of esters (320 :!: 70), aromatic
methyl ethcrs (320 :1: 50) and mеthохуsilапеs (320 :!: 25 cm I).
266 Norl1la/ Vibт(iolls ат/ AbsOl1Jtioll Regiolls о[ О.\у COI1l[JOIl1/(/s
ТаЫе 10.2 Absorption regions (cm l) of tl1C поmзаl vilJrations of OMe
ViЬ"tiоп
Saturalcd Unsaturatcd АroпШic (ll1io)cstcrs S(==O) P bondcd Si bondcd
l/qMc 3000 :!: 25 2985 :!: 35 2985 :!: 20 3020 :!: 30 3015 :!: 25 3020 :!: 30 2975 :!: 15
l/аМс 2955 :!: 35 2945 :!: 20 2955:!: 20 2990 :!: 40 3000 :!: 25 2985 :!: 35 2940:!: 15
VsMc 2845 :!: 25 2850 :!: 30 2845:!: 15 2920 :!: 80 2940 :!: 25 2930 :!: 30 2835 :!: 15
б"мс 1465 :!: 20 1470 :!: 15 '465:!: 10 1460 :!: 25 1465 :!: 20 1460:!: ]5 1465 :!: 10
б мс t 455 :!: 20 1460:!:]5 1460:!: 15 1450 :!: 15 ]455 :!: ]0 1455 :!: ]5 ] 460 :!: 10
бsмс 1445:!: 15 1450:!: 10 1450:!: 20 1425 :!: 25 ]445 :!: 15 1445 :!: 25 1450:!: ]5
рМс 1195:!: 40 1190 :!: 30 1190:!: 45 1185 :!: 35 1195 :!: 25 1185 :!: 15 1185 :!: '5
p'McIVC O 1160 :!: 30 1 '45 :!: 25 1150:!: 30 ] 155 :!: 35 1165 :!: 25 1 ]65 :!: 25 1160 :!: 25
vC Olp'Mc 940 :!: 85 945 :!: 50 1О25:!: 30 975 :!: 125 990 :!: 20 1055 :!: 30 ]070:!: 25
бс о 460 :!: 120 430 :!: ] 00 320:!: 50 320 :!: 70 475 :!: 60 425 :!: 75 320 :!: 25
Мс \orsion 225 :!: 40 235:!: 15 225 :!: 65 220 :!: 50 190 :!: 40
МсО \orsion 160:!: 50 185 :!: 50 185 :!: ]5
R OMe compounds
R = R'CH2 (see Section 3.2.2).
R = Me [1 12], СDз [1, 11, 13], OCH2 [1], McC02 [14],
CICD2 [10, 15, 16], СDзСD2 [14], BrCH2CH(MeO) [17],
iPr [4, 18], Ме(СFз)СН [19], (CF3)2CH [20], cBu [21],
tBu [22], Me2(MeO)C [23], Me(McO)2C [24], CI2HCCF2 [25J,
H2C==CH [26----31], CH2==C==CH [32], H2C==C(Me) [33, 34],
MeCH==CH [35], MeOCH==CH [36, 37], Ph [38----41], Ph-d5 [39],
XPh (Х = 2 , 3 and 4 Me [50], 4 HOCH2CH2, 3 CICH2, 4 l-IOCH2 [42],
3 FзС, 2 , 3 and 4 H(0==)C [43, 44, 50], 2 , 3- and 4 Me(0==)C [50], 3 and
4-Сl(0==)С, 4 MeCH==CH, 2 , 3 and 4 N=C [45, 50], 2-, 3- and 4 H2N
[46,50],2- and 3 02N [50], 2 , 3 and 4 HO [50], 2 , 3 and 4 MeO [50], 2 , 3
and 4 HS, 2-, 3 and 4 F [38, 47, 48, 50], 2 , 3 and 4 C! [38,47, 50], 2 , 3 and
4 Br [38, 47, 50], 2- and 3 1), X 2 HOPh (Х = 3 , 4 and 5-Н(0==)С [49,
50]), X 2 MeOPh (Х = 3 Me [51], 3 апd 4 H(0==)C [52], 3 and 4-МеО
[50, 53]), X 2 H2NPh (Х = 4 Cl [54]), X-з-МсОРh (Х = 4 Н(0==)C
[52], 5 MeO [50, 53]), X 2 CIPh (Х = 4 H2N [54], 3 CI [55], 5-С! [47,
48], 6 CI [50]), X 3 FPh (Х = 4 F [56] ), 2,3 (МеО)2 4-НСО==)СРh ,
2,4-(МеО)2 5 Н(0==)СРh and 3,5 (МеО)2 2-НСО==)СРh [57], 2
Py [58], 2 Fu [59], 2 Тb [60].
R = R'C(==O) (see Scction 7.1.8).
R = H2NC(==S) , HDNC(==S) and D2NC(==S) [68], McHNC(==S)
[61], KOC(==S) [62], MeS(==O) [63], MeOS(==O) [6
67], CIS(==O) [64], MeS(==0)2 [69], McOS(==0)2 [67, 70],
FS(==0)2 , CIS(==0)2 [69, 71], 4 MePhS(==0)2 , Me2P [72, 73],
(C03)2P [72], F2P [74], MC2P(==0) [75, 76], (C03)2P(==O) [76],
Me(McO)P(==O) [75, 77, 78], (MeO)2P(==0) [75, 79], F2P(==0)
[80], C]2P(==0) [81 3], MC2P(==S) [75], Me(MeO)P(==S) [75],
10.1 R' oxy Coтpollllds
267
(MCO)2P(==S) [75,84, 85], C1(MeO)P(==S) [84], CI2P(==S) [86,87],
НзSi and DзSi [88, 89J, MeSiH2 and MeSiD2 [90], МезSi апd
(СDз)зSi [91], McO [92, 931, O==N [94].
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10.1 R' oxy Compouпds
269
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10.1,3 Ethoxy
Тhe ЕЮ group providcs 21 normal viЬrаtiопs. Еightееп are attributed (о ethyl
(Scction 3.5.1). ТЬе remaining three normal vibrations are: а c o strеtсhiпg
vibration, а c o dcformation and ап ЕtO torsion.
Methyl and methylene stretching vibrations
Тhe буе ethyl СН stretching viЬrаtiопs absorb Ьеtwееп 2995 апd 2855 cm 1 with
а moderate to strong intcnsity in ethyl ethers апd а weak 'о moderate iпtепsitу iп
ethyl esters. These norma! vibrations are usually arranged in order of dеsсепdiпg
\vаvепumЬеr:
УаМе Y Me у а СН 2 > vsMe VsCH2'
Methyl and mcthy!ene deformations
ТЬе methy! symmetric deformation gives rise (о а moderate to stroпg band iп the
rеgiоп 1385 :!:: 15 cт 1. The other three deformations absorb \veakJy to moderately
and often coincide. In the HW region опе finds the БСН2 iп the spectrum of
ethoxy ethane а! 1494 cm 1 [7] or 1490 cm l [10]. In uпsаturаtеd апd aromatic
ethers thc methylene scissors stays а! 1480 :!:: 10 cт 1. Тhe methyI апtisуmmеtriс
deformations are active betwecn 1480 and 1425 cm l. А low wаvепumЬеr ( 1425
270 NO/'l/т/ Vibтtiolls ащ/ Abs01'ptioll Regiolls о! О)..у Compolll/(/s
cm 1) is assigncd in thc spcctrum оС ctllOxyctllanc, but nlOst EtO compounds SllOW
tllC mcthyl апtiSУПШlсtriс dcformations а! 1455 :!: 25 cm l.
Mcthylcnc wagging and twisting vibrations
With а rangc of 1350 :!: 40 cm 1 апd а modcratc to strong intcnsity, tllC
methylenc \vag in R OE! compounds comes in thc region оС tl1C mcthyl symmetric
deformation. In this 'сх! we ассер! that thc БsМс {wCH 2 } possesscs thc highcst
{Iowcst} \vavenunзbcr, altllOugh thc litcraturc does по! agrce conccrl1ing this
assignmcnt.
ТЬс Пlctllylene t\vist is locatcd in thc region 1285 :!: 45 cm 1 with а weak to
moderate intcnsity. Wavenumbcrs in the ncighbourhood of 1325 cm 1 arc observcd
in Ihe spectra of ethyl benzoatc and 'Ьс cthyl esters of pyridinecarboxylic acids. Low
values Ьаус Ьесп traced in tlle spcctra of ЕtO(О==)ССН==СНС(==О)ОЕ! (1244
cт 1) and in those of а few ethyI ethers SUcll as MeSCH 2 0Et, 4 H(0==)CPhOEt
and 2 FPhOEt with \vavenumbers near 1260 cm 1.
Methyl rocking vibrations and се/со strctching vibrations
These four vibrations are couplcd in such а way as to make it difficult 'о dctcrmine
which vibration contributes in thc highcst dcgree 10 а distinct absorption. The
intensities of these vibrations arc mostly wcak or modcratc, rarely strong.
ТЬе highest absorption rеgiоп (1165 :!: 30 cm 1) is assigned 'о the рМс. Wavc-
numbers in the neighbourhood of 1195 cm l are found in the spectra of ЕtOЕ!
and tralls MeCH==CHOEt. In ethyl esters this vibration сап hide in the С(==О)О
stretching vibration \уысь appears in the region 1245 :!: 65 cm l.
ТЬе р'Ме is located in 'Ьс region 1120 :!: 40 cm l. Ethoxyethane shows these
rocks а! 1155 and 1120 cm 1 and ethyl acetate а! 1098 cm 1. In this region also
'Ье antisymmctric СОС strctching vibration in ethers is active, so that опе has 'о
proceed with caution in assigning these vibrations.
ТЬе region 1060 :!: 40 cm 1 is attributed to а skcletal stretching vibration with
а contribution of the c c and 'Ье c o bond. For most of the ethyl esters the
c o stretching vibration is assigned in this region. In ethyl ethers, however, the
c c stretching vibration dominates in this аЬsоrptiоп.
In the spectra оС ethyl esters, the stretching vibration in thc region 875 :!: 65
cm l is attributed mainly 'о thc c c bond. In the spcctra оС ethyl cthcrs this
vibration is often called the СОС symmetric stretch, with а contribution of thc
c c bond. ЕtOЕ! gives this у . СОС а! 850 cm l.
Methylene rocking vibration
ТЬе mcthylenc rock is activc with а wcak 'о moderate intensity in thc region 790
:!: 50 cm l, which narrows 'о 800 :!: 25 cm 1 if thc valucs from ,Ьс following
/0.1 R' oxy coтpoиl!d's
271
compounds arc по! takcn into account: 4 H(0==)CPhOEt (838), 4 BrPhOEt (830),
1, 4 (EtO)2Ph (748) and 2 Thc(==0)OEt (750 cm I).
Skcletal dcformations
Тhe skcleta1 o c c dcformation occurs а! 390 :f: 85 cm ! with а weak to
moderate intcnsity. Ethoxycthanc absorbs а! 450 cm J, mеthохуеthапе а! 470 cm 1
and cthylacetatc а! 378 cm J. ТЬс vcry cxtcnsivc rеgiоп (390:f: 140 cm l) for the
extcrnal c o c dсfоrmаtiоп is due (о the fact {Ьа! ethers (450 :f: 80) absorb а!
higher wavenumbers than esters (310:f: 60 cm l).
ТаЫе IО.з Absorption rеgiопs (cm l) of (Ье поrmаl viЬrаtiопs of
OE!
Vibration Saturated Uпsаturаtеd Aromatic Esters
lIа Ме 2985 :1: 1 О 2985 :f: 10 2985 :f: 10 2985 :f: 10
II Ме 2965 :1: 25 2975 :f: 10 2975 :f: 10 2975 :f: 15
lI а СН 2 2940:1: 10 2935 :f: 15 2935 :f: 10 2945 :f: 15
IIsMe 2910:1: 30 2905 :f: 15 2895 :f: 15 2910:f: 20
II s CH 2 2875 :f: 20 2875 :f: 15 2875 :f: 15 2885 :f: 25
с5СН, 1475 :f: 20 1480 :f: 10 1480 :f: 10 1475 :f: 15
c5aM 1465 :1: 15 1460 :1: 10 1470:f: 10 1460:f: 15
c5 Me 1445 :1: 20 1440 :f: 10 1445 :f: 15 1450:f: 15
c5 s Me 1385 :1: 15 1385 :f: 10 1385 :f: 10 1385 :f: 15
WCH2 1350 :1: 30 1335 :f: 25 1345 :f: 25 1360:f: 25
ТСН2 1285 :1: 25 1290 :1: 20 1280 :f: 20 1285 :f: 45
рМе 1165 :1: 30 1170:1: 25 1160:f: 15 1165:f: 30
р'Ме 1120 :1: 40 1120:f: 10 1110 :f: 20 ll15 :f: 35
IIC O/C C 1065 :1: 35 1080 :1: 20 1070 :f: 30 1060:f: 40
IIC C/C O 875 :1: 65 870 :f: 30 885 :f: 50 890 :f: 50
рС Н 2 805 :1: 20 800 :f: 35 790 :f: 50 800 :f: 25
c5C O C 470 :1: 60 420 :f: 50 420 :f: 50 310:f: 60
c50 C C 395 :1: 75 390 :1: 50 390 :f: 50 350 :f: 45
torsion Ме 230 :1: 30 235 :1: 15 235 :f: 25 245 :f: 35
torsion Е! 150 :1: 50 150 :f: 50 160 :f: 40
tоrsiоп ОЕ!
R OE! molecules
R = H and D [1 3], Me [3---8], СDз [4---6], Et [7 10], iPr [7],
CICH2CH2 , HC=CCH2 [11], MeSCH2 (12], H2C==CH [13 16],
MeCH==CH [17, 18], PЬ [19, 25], 2 and 4 XPb (Х = F, CI and
Br [2Q-.-.22, 25], 02N and Н(О==)С [23, 24] ), 4 MeC(==O)NНPb , з and
4 ЕtOРЬ [25], 1,3CI2Ph [25].
272 NomlU/ Vibratio"s аl/(/ AbsollJtio" Regio"s о! О.\у Com[Jo/l"ds
References
1. У. Mika\va, J .W. Brasch and R,j. Jakobsen, Spectrocllim. Acta, рш.t А, 27 А, 529 (1971).
2. J.R. Durig, W.E. Вису, C,j. Wшrеу and L.A. Carreira, J. P/,yS. ClICIII., 79, 988 (1975).
3. N.L. Allil1ger. М. Ra!lman aI1d J. H. Lii, J. Ат. C/ICIII. Soc., 112,8293 (1990).
4. Т. Кitaga\va, к- Ohl1o, Н. Sugata and Т. Miyaza\va, B//II. C/lem. Soc. JplI., 45, 969
(1972).
5. J .Р. Perchard, Spectrocllim. Acta, Part А, 26А. 707 (1970).
6. J.R. Durig and О.Д,с. Compton,J. Cllem. P/,yS., 69, 4713 (1978).
7. R.G. Snyder al1d G. Zerbi, Spectruc/lim. Acta, Part А, 23А, 391 (1967).
8. д'О.Н. Clague al1d Д, Danti, Spectrocllim. Acta, Part А, 24А, 439 (1968).
9. Н. \Vieser, W.G. Laidlaw, p,j. Кrueger al1d Н. Fuhrer, Spectrocllim. Acta, Par/ А, 24А,
1055 (12968).
10. Н. Wieser and p,j. Кrueger, Spec/rocllim. Ас/а, Part А, 26А, 1349 (1970).
11. S.W. Charles, ЕС. CuHen and N.L. Owel1, J. C/lCI/I. Soc.,Faraday Trans II 72, 351
(1976).
12. Н. Matsuura, Н. Murata and М. Sakakibara,J. Мо/. Str//ct., 96, 267 (1983).
13. J.R. Durig and D,j. Gerson,J. Мо/. S//"IIc/., 71,131 (1981).
14. М. Sakakibara, Е Inagaki, 1. Harada and Т. Shimanouc!li, B//II. C/lem. Soc. Jp/l., 49, 46
(1976).
15. N.L. O\ven and G.O. S0rensen, J. P/lYS. C/lem., 83, 1483 (1979).
16. N.L. О\уеп and N. Sheppard, SpeclI'ocllim. Ас/а, 22, 1101 (1966).
17. S.W. Charles, ЕС. СиНеп and N.L. O\ven,J. Мо/. Str//c/., 18, 183 (1973).
18. Е Marsault Herail. G.S. Chiglien, J.P. Dorie and M.L. Manin, Spec/rocllim. Ас/а, Part
А, 29А, 151 (1973).
19. J.H.S. Green, Spec/rocllim. Ас/а, 18,39 (1962).
20. Е.Е Моопеу, Spec/rocllim. Acta, 19, 877 (1963).
21. S.P. Sinha and C.L. Chalterjee, Spectrosc. Lell., 9,455 (1976).
22. R.C. Mahesh\vari and М.М. Shukla. /lIdia/l J. P//re Арр/. P/,yS., 13, 135 (1975).
23. К-М. Mathur, О.Р. Juyal and R.N. Singh,//ldia/l J. РlII'е Арр/. P/,yS., 9, 756 (1971).
24. Р. Venkoji, Spectrocllim. Acta, Part А, 42А, 1301 (1986).
25. G. Varsanyi, Assiglll1le/lts for Vibratio/la/ Spectra ofSeI'e/l H///ldred Be/lzelle Derivatives,
J.Wiley & Sons, New York (1974).
10.2 R' YLOXY COMPOUNDS
The R'C(==O)O group iп which R' = Н (formates), СI (chloroformates) or Ме
(acetates) provides for R' = Н and Сl {Ме} nine {eighteen} normal vibrations of
which six {fifteen} are studied with 'Ье C(==O)H group (see Section 7.1.1), 'Ье
C(==O)CI group (see Sесtiоп 7.1.3) {or 'Ьс C(==O)Mc group (see Scction
7.1.5)}.
10.2.1 Formylox
The СН strctching vibration of formatcs of the 'уре HC(==O)O R usually absorbs
а! 2935 ::1: 35 cm ! with а weak to moderateintensity. The most characteristic
10.2 R' -у/оху Coтpouпds
273
band of 'Ье formatcs ariscs from 'Ье с==о stretching viЬrаtiоп which absorbs
strongly in the region 1730 :1: 40 cm l. Тhe HW side of this region is limited
Ьу НС(==О)ОСН 2 СI (vapour 1770 [15], liquid 1740 cm 1 [9, 13]) and the LW
sidc Ьу НС(==О)ОМс (solid 1692 [8J, liquid 1754 cm l [2, 4, 6, 7, 10]). For
the remaining formatcs this rеgiоп narrows 'о 1740 :!: 20 cm l. Thе СН iп рlапе
deformation is а wcak to moderatc аЬsоrptiоп in the rапgе 1365 :!: 15 cт l with
the cxception оС HC(==O)OSiD] with 1331 cт l [19]. Thе C(==O) O strеtсhiпg
vibration appears strongly а! 1165 :1: 45 cт J with extreme values of 1207 апd
1210 cт l in the spectra оС HC(==O)OMe do and dз and 1120 cm l iп the
spectrum оС HC(==0)OCH2Cl. Most of IЬе HC(==O)O R соmроuпds show the
СН out-of plane deformation а! 1040 :1: 30 cm J, ехсер! НС(==О)ОSiНз-dо апd
-d з with respectively 1104 and 1095 cm J. Тhe band with moderate iпtепsitу iп the
region 720 :1: 50 cm l is due 10 the с==о in plane dеfоrmаtiоп, which is 'о some
degree couplcd to the бен. Тhe external skeletal C O R in plane dеfоrmаtiоп
is assigned in Ihe region 320 :1: 90 cm l, with 325 cm l for НС(==О)ОМе. Some
vibrational analysis of formates reveals the out of plane skeleta1 deformation or
torsion а! 290 :1: 70 cm l and the OC(==O)H torsion а! lower wаvепumЬеrs:
105:1: 40 cm l.
ТаЫе 10.4 Absorption regions (cm l) of (Ье поnnаl viЬrаtiопs of
OC(==O)H
Vibration Region ViЬrаtiоп Region
уСН 2935 :1: 35 6С==0 720 :1: 50
уС==О 1730:1: 40 6C 0 320 :!: 90
бсн 1365 :1: 15 torsion 290 :!: 70
yC(==o) o 1165 :1: 45 torsion 105:!: 40
,СН 1040 :1: 30
R OC(==O)H compounds
R = Me [1 10], CO] [7 10], Et [9, 11], HC=CCH2 [9, 12],
CIН2C [9, 13 16], СID2С [9, 13, 15], tBu [9, 17], H2C==CH [18],
H]Si and D]Si [19].
10.2.2 Chloroformyloxy (chlorocarbonyloxy)
Six normal vibrations оС chloroformyloxy зrе treated with the chloroformyl group
(see Section 7.1.3). Тhe c(==o) o strelching viЬrаtiоп gives rise 'о а stroпg band
in the region 1160 :1: 45 cm l. Durig and Griffin [22] аssigпеd the band а! 1202
cт l in 'Ьс spectrum of МеОС(==О)СI 'о this stretching viЬrаtiоп and that а! 1159
cт l to а mcthyl rock, whereas Nyquist [21] preferred the сопtrаry. Thе lo\vest
valuc comes from CICH20C(==0)CI (1117 cm l). Тhe ехtеrпаl skeletal C O R
274 Normal Vibтl;o"s aJl(1 AbsOIpl;o" Reg;o"s о[ О.\у Com[Jo/llllls
in plane dcfornlation absorbs wcakly а! 275 :1: 25 cm 1 Шld tllC OC(===O)CI
torsion near 70 ст I .
ТаЫе 10.5 Absorption regions (сш l) of I!1е normal vibrations of
OC(==O)CI
Vibration Region Vibration Region
уС===О 1780:1: 20 8C CI 365 :1: 50
yC(===O) O 1160:1: 45 8C 0 275 :1: 25
yC C1 790 :1: 60 torsion 160:1: 20
I с==о 675 :1: 15 torsion ;::::70
R OC(==O)CI compounds
R = Mc [2 22], СDз [22], Et [11], nPr , iPr , nBu and iBu [38],
H2C==CHCH2 , HC=CCH2 [21], PhCH2 , CICH2 , CICHD and
clCD2 [14, 23], Ph .
10,2.3 Acetyloxy (acetoxy)
Methyl vibrations
In acetates the methyl stretching vibrations give rise [о vcry wcak absorptions.
The antisymmetric deformations, however, absorb with moderate iпtепsitу and
the methyl symmetric deformation with moderate [о strong intensity. ТЬе Me C
stretching vibration is coupled 'о the methyl rock.
Тhe с===о stretching vibration
With 'Ье exception of МеС(==О)ОСI (1818 cm l) the с===о stretcJling vibration
in R OC(==O)Me compounds occurs а! 1750 :1: 20 cm l. As examples,
MeC(==0)OCH2CI absorbs а! 1770 cm l, MeC(==O)OPh а! 1765 cm l (the
formula isomer РЬС(===О)ОМе а! 1724 cm l) and МеС(===0)ОСН2СН===СН2
а! 1743 cm l.
Тhe c(==o) o vibrations
Тhe c(===o) o stretching vibration absorbs strongly in the region 1235 :1: 30
cm l with high wavenumbers fOT МеС(===О)ОСDз (1265) and МеС(===О)ОSiНз
(1257) and low values for МеС(===О)ОРЬ (1205) and МеС(==0)ОСН===СН2 (1217
cm I). Тhe skelctal C O R in plane deformation is active in 'Ье region 275 :1:
45 cm l.
/0.2 R' yloxy CoтpOll1lds
275
ТаЫс 10.6 Absorplion regions (cm J) of the normal vibrations of
OC(==O)Mc
Vibration Rcgion Vibration Region
vaMe 3010 :1: 30 р'Ме 975 :1: 45
v Mc 2970 :1: 30 vC C 860 :1: 50
vsMe 2910:1: 40 ЬС==О 620 :1: 30
vC==O 1750:1: 20 ,с==о 600 :1: 20
ЬаМе 1445 :1: 20 bC C O 415:1: 50
b Me 1435:1: 15 Бс о 275 :1: 45
(5.,Ме 1370 :1: 10 torsion 160:1: 50
vC(==O) O 1235 :1: 30 torsion
рМе 1050 :1: 30 lorsion
R OC(==O)Me compounds
R = Me [2, 4, 6, 24----27], СDз [2, 5, 24, 28], Et [29 31],
H2C==CHCH2 [32], CICH2 (14, 33, 34], CICD2 [14, 34],
H2C===CH [35], Pb [36, 39], Ph d5 [36], 4 FPh , 2 and 4
MeOPb [39], 2 and 4 02NPh [39], CI [37], НзSi апd DзSi [19].
References
1. А. Hadni. J. Deschamps and M. L. Josien, C.R. Acad. Sci., 242, 1014 (1956).
2. J.K. Wilmshurst,J. Мо/. Spec/rosc., 1, 201 (1957).
3. Н. Susi and J.R. Scherer, Spec/rocl1im. Ас/а, Par/ А, 25А, 1243 (1969).
4. Р. Matzke, О. Chacon and С. Andrade, J. Мо/. S/rиc/., 9, 255 (1971).
5. J. Derouault. J. Le Calve and M. T. Forel, Spec/roc/lim. Ас/а, Par/ А, 28А, 359 (1972).
6. R.M. Moravie and J. Corset,J. Мо/. S/rиc/.. 30,113 (1976).
7. Н. Susi and Т. Zell, Spec/rocl1im. Ас/а, 19, 1933 (1963).
8. W.c. Harris, О.А. Сое and W.O. George, Spec/roc/lim. Ас/а, Par/ А, 32А. 1 (1976).
9. M.G. Dah1qvist and К. Euranto, Spectroc/lim. Ас/а, Part А, 34А, 863 (1978).
10. Е.В. Marmar, С. Pouchan, А. Dargelos and М. Chaillet, J. Мо/. Strиc/., 57, 189 (1979).
11. S.W. Charles, G.I.L. Jones, N.L. О\уеп, S.J. Cyvin and B.N. Cyvin,J. Мо/. S/rllct.. 16,
225 (1973).
12. G.I.L. Jones, D.G. Lister and N.L. Owen, Tralls. Faraday Soc., 71, 1330 (1975).
13. M.G. Dahlqvist, Spec/roc/lim. Ас/а, Par/ А, 36А, 37 (1980).
14. F. Daeyaen, Thesis, UIA, An!\уетр, 1988.
15. F. Daeyaen and B.J. Уап der Veken, J. Мо/. S/rllc/., 213, 97 (1989).
16. М. Rasanen, Н. Kunttu, J. Murto and М. Dahlqvist. J. Мо/. S/rиc/., 159,65 (1987).
17. У. Umemura, J. Corset and R.M. Moravie.J. Мо/. S/rиct.,52, 175 (1979).
18. W. Pyckhout, С. A1senoy, H.J. Heise, B.J. Уап der Veken, Р. Coppens and М. Traetteberg.
J. Мо/. Strllc/., 147,85 (1986).
19. A.G. Robiette and J.c. Thompson, Spec/roc/lim. Acta, 21, 2023 (1965).
20. J.C. Evans and J. Overend, Spec/rocl1im. Acta, 19, 701 (1963).
21. R.A. Nyquist, Spec/roc/lim. Acta, Par/ А, 28А, 285 (1972).
22. J.R. Durig and M.G. Griffin, J. Мо/. Spec/rosc., 64, 252 (1977).
23. F. Daeyaen and B.J. Уап der Veken,J. Мо/. S/rиct., 198,239 (1989).
276 Norlllal Vib,'alio"s a"d Abs01plio" Regio"s о[ Оху COlllpO/l/l(/S
24. W.O. George, Т.Е. Houston and W.c. Harris, Speclroc!Jil1l. АсШ, Parl А, 30А, 1035
(1974).
25. Н. Hollenstein and Н.Н. Giinthard,J. Мо/. Speclrosc., 84, 457 (1980).
26. R. Fausto and J,j.C. Teixcira Dias, J. Мо/. Slrllcl., 144, 215 (1986).
27. D. Steele and А Muller, J. P//ys. С//еl1l., 95, 6163 (1991).
28. В. Nolin and R.N. Jones, Call. J. С/IeII1., 34,1382 (1956).
29. М.А Raso, М.У. Garcia and J. Morcillo, J. Мо/. Slrucl., 115,449 (1984).
30. У. Mido, Н. Sllioтi, Н. Matsuura, М.А. Raso, М.У. Garcia and J. Morcillo, J. Мо/.
Slrllcl., 176,253 (1988).
31. Т.-К На, С. Раl and P.N. Ghosh, Speclroc!Jil1l. ACla, Parl А, 48А, 1083 (1992).
32. В. Singh, R. Prasad and R.M.P. Jais\val, Рюс. IlIdoall Acad. Sci. (С//еl1l. Sci.), 89, 201
(1980).
33. S.W. Charles, G.l.L. Jones, N.L. Owen and L.A West, J. Мо/. SlruCI., 32, 111 (1976).
34. F. Daeyaert, Н.О. Desseyn and B.J. Уап der Veken, Speclroc!Jil1l. ACla, Parl А, 44А,
1165 (1988).
35. W.R. Fairheller and J.E. Katon, J. Мо/. Slrucl., 1, 239 (1967).
36. У. Кiт, Н. Noma and К Machida, Speclroc!Jil1l. ACla, Parl А, 42А, 891 (1986).
37. J.c. Evans, G.Y.S. Lo and Y.L. Liang, Speclrocl!il1l. Acla, 21,973 (1965).
38. Н.А Оту, Speclroc!Jil1l. ACla, 16, 1488 (1960).
39. G. Vаrs;шуi,Аssiglll1lеlllsfоr Vibraliolla/ Speclra ofSevell Hlllldred Bellzelle Derivalives,
J.Wiley & Sons, New York (1974).
11
Normal Vibrations and
Absorption Regions of
Sulfur Compounds
11,1 ТНIO COMPOUNDS
11.1.1 MethyltlIio
Тhe MeS group yields twelve normal vibrations, оС which пiпе Ьеlопg to (Ье
methyl group. ТЬе rеmаiпiпg three mау Ье described as: C S stretching vibration,
C S deformation and MeS torsion. Since the СН bonds of the methyl group
take up different positions with respect to 'Ье C S bond and the methyl group
strictly does по! possess С Зv symmetry, the methyl vibrations have to Ье described
in terms of individual СН vibrations. For сопvепiепсе, however, the usual terms
antisymmetric and symmetric are used.
Methyl stretching vibrations
Тhe УаМе appears weakly (о moderately iп the rеgiоп 3005 :1: 25 cт ] with the
highest value (3030 cm ]) for N=CSMe апd EtSSMe, folIowed Ьу CIC(==O)SMe
with 3025 and HC=CSMe with 3017 cm l. Iп the LW rапgе MeSMe (2982) апd
MeHgSMe (2984 cm ]) show absorption.
The region of 'Ье Y Me (2980 :1: 45 cm ]) partly overlaps that of the УаМе апd
often both methyl stretchings occur а! the same wavenumber. ТЬе highest values
are those due to CIC(==O)SMe (3025), N=CSMe (3022), O==NSMe (3012)
and HC=CSMe (3012 cm ]). Low wavenumbers are fоuпd iп 'Ье spectra of
278 Nomra/ Vib/-atio"s ти/ AbsOlptio" Regio"s о[ 5///[1/1' Com[1o//l/(/s
H2NC(==S)SMc (2940) and McSMc (2960 cm 1) but most R SMc compounds
sho\v tl1is //;Мс а! 2980:1: 20 cm l.
TllC vsMc absorbs nlOdcrately to strongly in the region 2925 :1: 20 cm l. А
fe\v examplcs arc: HC=CSMe do апd dl (2944), CIC(==O)SMc (2941), HSMe
(2930), H2NC(==S)SMe (2910), McHNc(==S)SMe (2910) and MeSMc (2917 and
2904 cm 1 [13]).
Mcthyl dcformations
Тhc antisymmctric dсfоrшаtiопs БаМе and Б;Ме arc assigned in thc respcctivc
rcgions 1445 :1: 25 and 1430 :1: 30 сш l, so that thcre is а realistic chance of
finding both dcformations а! the same wavenumbcr. The БsМе in McS сошроuпds
occurs \vith moderatc iпtепsitу а! ::::::120 cm 1 lower wavenumbers (1320 :1: 20
cm l) 'Ьап 'Ье БsМе in МеО соmроuпds (Sссtiоп 10.1.2).
Methyl rocking vibrations
In delimiting the absorption region оС the рМе (995 :1: 40 сm 1) (Ьс high value 1065
cm l for MeSH has not Ьееп taken into ассоuпt. In the HW region, absorption
is sho\vn Ьу such compounds as MeSCH2CH2SMe (1035), McSMe (1032) and
MeOCH2SMe (1008 сш l). Thc LW side of the above mentioned region is Iimited
Ьу 955 сш 1 from the spectra of MeSSMc, EtSSMe, tBuSSMe and MeHgSMe.
The р'Ме is assigned а! 940 :1: 40 сш l with 976 сш l (coincident with рМе)
for CIC(==O)SMe and 950 and 906 cm l for MeSMe. Both rocking vibrations
absorb а! ::::::200 cm l lower wаvепuшЬеrs than (Ьс corresponding rocks in МсО
compounds.
Тhe C S stretching vibration
Тhe C S stretching vibration in R SMe compounds gives rise 'о а \усзk 'о
шоdеrаtе, rarely strong band in the region 725 :1: 50 сш l. Тhe highest values
havc Ьссп obscrved in 'Ьс spectra оС McOCH2CH2SMc (773), McS(CH2)IISMc
(п = 3 5) (::::::770) and McSMc (742) as vaCSc. Thc ga//c//e conformcr of EtSMc
absorbs а! 676 cm l. Тhc rcmaining observcd C S stretching modes absorb at 720
:1: 30 cт 1. Тhe compounds tBuSSMe, MeSSMe, MeHgSMe and N=CCH2SMe
зrс active in thc ncighbourhood of 693 cm 1. МеthуIthiошсthапе shows 'Ьс vsCSC
а! 694 cm 1.
Skeletal dеfоrшаtiоп
Vibrational studies suggest that the skeletal C S deformation occurs а! 270 :1:
70 cт 1 as а wcak Ьапd. In the spectra of McC(==S)SMc this band is found а!
338 сш l, iп 'Ьа! of MeSMe а! 284, McSSMc а! 274 and MC2PSMc а! 207 cm l.
/J./ ТJ/io CO/1/poullds 279
ТаЫе 11.1 Absorption rеgiопs (ст 1) of 'Ье normal viЬrаtiопs of SMe
Vibration Saturated Unsaturated Esters Disulfides N апd Р Si апd Hg
Сl bonded aromatic Ьопdеd Ьопdеd
vaMe 2990:!:: 10 3005:!:: 15 3005 :!:: 25 3010:!:: 20 3003 :!:: 10 2990:!:: 10
lJ, Me 2980 :!:: 20 2985 :!:: 30 2980 :!:: 45 2985:!:: 10 2995 :!: 15 2982 :!: 10
v..Me 2920 :!:: 15 2930:!: 15 2925 :!: 20 2915:!: 10 2920 :!: 15 2920:!: 10
баМе 1440:!:: 15 1450:!:: 20 1430:!: 10 1432:!: 10 1435:!: 10 1435 :!: 10
б Ме 1420:!:: 20 1440:!: 20 1425:!:: 10 1425:!: 15 1423:!: 10 1430:!: 10
б..Ме 1320:!:: 20 1320:!:: 10 1310:!: 10 13]0:!: 10 1315:!: ]5 1315:!: 10
рМе 1000:!:: 35 995 :!:: 30 967:!: 10 970:!: 15 977 :!: 10 975 :!: 20
р'Ме 940 :!:: 35 960:!: 10 945 :!: 35 950:!: 10 960 :!: 20 965:!: 10
vC S 725 :!:: 50 715:!:: 25 715:!:: 20 715:!: 25 720 :!: 20 700 :i: 10
БС s 250 :!:: 40 290 :!:: 35 270 :!:: 70 280 :i: 50 240 :!: 40
torsion Ме 195 :!:: 35 150 :!: 25 155:!: 20
torsion SMe 145 :!:: 35 100:!: 30
R SMc molecules
R = R'CH2 (see Sесtiоп 3.3.2).
R = H [1 5], Me [()"",13], CI [53], CH2==CH [14,
15], CH2==C(SMe) [16], HC=C and oc=c [17 19], N=C [20],
Ph [21 26], Ph d5 [23, 24], 4 XPh (Х = Н(О==)С, НО(О==)С, MeS
[26], Сl and Br [26, 27]), 2 Pyт [28], Н(o==)c [29], CI(O==)C
[30 32], Me(O==)C [33], H2N(0==)C [34], Me(S==)C [38],
MeS(S==)C [38], H2N(S==)C and D2N(S==)C [34---36],
MeHN(S==)C [37], MeS [39---45], EtS [44, 46], tBuS [43, 47],
F(O==)CS [48], O==N [49, 50], Me2P [51], CI2P(==0) [52],
MeH2Si [54], MC2HSi [55], MeHg [56].
References
1. J. Wagner, Z. P/,yS. CI,em., АЬ/. В, 408, 36 (1938).
2. H.W. Thompson and N.P. Skепеlt, Tra//S. Faraday Soc., 36, 812 (1940).
3. Н. Siebert, Z. Allorg. AlIg. C/leпr., 271, 65 (1952).
4. I.W. Мау and E.L. Расе, Spec/roc/lim. ACfa, Par/ А, 24А, 1605 (1968).
5. A.J. Bames, Н.Е. Hallam and J.D.R. Howells, J. C/lem. Soc Faraday Tralls. 2,68,737
(1972).
6. J.P. McCullough, W.N. Hubbard, ЕА. Fro\v, I.А. Hossenlopp and О. Wаddingtоп, J.
Ат. Cllem. Soc., 79, 561 (1957).
7. J .R. Allkins and Р. Hendra, Spec/rocltim. Ас/а, 22, 2075 (1966).
8. J.M. Freeman and Т. Henshall,J. Мо/. S/ТlIC/., 1, 31 (1967).
9. S.O. Frankiss, J. Мо/. SfТllC/., 3,89 (1969).
10. N.L. Owen and R.E. Hester, Spec/rocltim. Ас/а, Par/ А, 25А. 345 (1969).
11. О. Oeiseler and О. Hanschmann,J. Мо/. S/r"cf., 8, 293 (1971).
12. М. Tranquille, Р. Labarbe, М. Fouassier and M. T. Forel, J. Мо/. SIr"Cf., 8, 273 (1971).
13. I.W. Levin, R.A.R. Pearce and R.C. Spiker, Spec/roc/lim. Ас/а, Par/ А, 31А, 41 (1975).
14. J. Fabian. Н. Кrober and R. Mayer, Spec/roc/lim. Ас/а, Par/ А, 24А. 727 (1968).
15. S. Samdal, Н.М. Seip and Т. Torgrimsen, J. Мо/. S/r"c/., 57, 105 (1979).
280 Norllla/ Vibтlio"s ат/ AbsOl'[Jlio" Rcgio"s о[ SII/[III' COIII[JOIIIl(/S
16. Р. Jandal. Н.М. Scip and Т. Torgrimsen,J. Mol. S/ruc/., 32, 369 (1976).
17. H.J. Boonstra and L.C. Riпzепш, Recl. Trav. Сiliт. Pays Bas, 79, 962 (1960).
18. А.а. Moritz, Spec/rocilim. Асш, Рат/ А, 23А, 167 (1967).
19. О.Н. Chrislensen and О. deI1 Engelsen, Speclrocilim. Ас/а, Рат/ А, 26А, 1747 (1970).
20. N.S. Нат and J.B. Willis, Spec/rocilil1l. Асш, 16,279 (1960).
21. J.H.S. Green, Spec/rocilil1l. Ас/а. 18,39 (1962).
22. J.H.S. Green, Spec//'Ocilim. Асш, Рат/ А, 24А, 1627 (1968).
23. М. Bouquet, а. Chassaing, J. Corset, J. Favrot and J. Limouzi, Speclrocilim. Ас/а, Рт'/
А, 37А, 727 (1981).
24. W.J. Balfour, KS. Chandrasekhar and S.P. Куса, Spec/rocilim. Ас/а, Par/ А, 42А, 39
(1986).
25. а. Paliani and S. Santini, J. Ramall Spectrosc., 19, 161 (1988).
26. а. Varasnyi, AssigllIIIelllsfor Vibratiollal Spec/ra ofSevell Halldred 8e//zelle Derivalives,
J.Wiley & Sons, New York (1974).
27. J.H.S. Green, O.J. Harrison, W. Kynaston and O.W. Scott, Spectrocilil1l. Ас/а, Parl А,
26А, 1515 (1970).
28. а. МШе, М. аиiliапо, J. Кister, J. Chouteau and J. Metzger, Spec/rocilil1l. Ас/а, Рат/
А, 36А, 713 (1980). .
29. G.1.L. Jones, О.а. Lister, N.L. Owen, M.C.L. Gerry and Р. Pa1mieri, J. Mol. Spec/rosc.,
60, 348 (1976).
30. Т. Miyazawa and K.S. Pitzer, J. C/Jel1l. P/JYs., 30, 1076 (1959).
31. J.c. Evans and J. Overend, Spec/rocilil1l. Ас/а, 19,701 (1963).
32. R.A. Nyquist, J. Mol. S/rlIc/., 1, 1 (1967).
33. А. Smolders, а. Maes and Т. Zeegers Huyskens,J. Mol. S/rllc/.,172, 23 (1988).
34. L. Zhengyan, R. Mattes, Н. Sсhпбсkеl, М. Thiinemann, Е. Hunling, U. Нбпkе and С.
Mendel, J. Mol. S/rlICI., 117, 117 (1984).
35. KR.G. Oevi, O.N. Salhyanarayana and S. Manogaran, Spec/roc!Jil1l. ACla, Parl А, 37А,
3l (1981).
36. R. Matles, L. Zhengyan, М. Thiinemann and Н. Sсhпбсkеl, J. Mol. S/ruc/., 99, 119
(1983).
37. K.R.G. Oevi, O.N. Sathyanarayana and S. Manogaran, Spec/roc!Jil1l. Ас/а, Рат/ А, 37А,
633 (1981).
38. к- Herzog, Е. Steger, Р. Rosmus, S. Scheithauer and R. Mayer, J. Mol. S/rucl., 3, 339
(1969).
39. Н. Gerding and R. Westrik, Recl. Trav. C/rim. Pays Bas, 61, 412 (1942).
40. I.F. Trotter and H.W. Тhompson, J. C/rem. Soc., 481 (1946).
41. O.W. Scott, H.L. Finke, М.Е. Gross, а.В. Guthrie and Н.М. Huffman, J. Ат. C/rem.
Soc., 72, 2424 (1950).
42. S.G. Frankiss, J. Mol. S/rllc/., 3, 89 (1969).
43. Н. Sugeta, Spec/roc/lim. Ас/а, Рат/ А, 31А, 1729 (1975).
44. W, Zhao and S. Кriтm, J. Mol. S/rlIc/., 224, 7 (1990).
45. М. Meyer, J. Mol. S/rllcl., 273, 99 (1992).
46. к-а. А11иm, J.A. Creighton, J.H.S. Green, G.J. Minkoff and L.J.S. Price, Spec/roc!Jil1l.
Ас/а, Рат/ А, 24А, 927 (1968).
47. Н. Sugeta, А. ао and Т. Miyazawa, 81111. C/rel1l. Soc. JPIl., 46, 3407 (1973).
48. С.О. ОеlIа УМоуа, Spec/roc/Jim. Ас/а, Рат/ А, 47А, 1619 (1991).
49. О.Н. Christensen, N. Rastrup Andersen, О. Jones, Р. ЮаЬое and E.R. Lippincott,
Speclroclril1l. Ас/а, Рат/ А, 24А, 1581 (1968).
50. О.М. Byler and Н. Susi, J. Mol. S/ruc/., 77, 25 (1981).
51. J.R. Ourig, O.F. Smith, О.А. Barron, R.J. Harlan and Н.У. Phan, J. Ral1lall Spec/rosc.,
23, 107 (1992).
/ /./ ТЫо Compoипds
281
52. R.A. Nyquist. Spec/rocl1im. Ас/а, Par/ А, 27А. 697 (1971).
53. F. Winther, А. Guarnieri and О.Р. Nielsen, Spec/roc/rim. Ас/а, Par/ А, ЗIА, 689 (1975).
54. К. Taga. К. Ohno and Н. Murata, J. Мо/. S/rrtc/.,67, 199 (1980).
55. К. Taga,J. Мо/. S/rrtc/., 82, 1 (1982).
56. R.A. Nyquist and J.R. Мапп, Spec/roc/rim. Ас/а, Par/ А, 28А, 511 (1972).
11.1.2 Ethylthio
Just Jike OEt, the SEt frаgmепt displays 21 fundamental viЬrаtiопs. Еightееп
vibrations belong 10 the elhyl group (Sссtiоп 3.5.1). То these viЬrаtiопs are added
а C s strеtсhiпg viЬrаtiоп, а C S deformation and ап EtS torsion.
Methyl and mcthylene strelching viЬrаtiопs
Usually the five СН stretching viЬrаtiопs are assigпеd between 2995 and 2850
cm 1 with а moderale intensily. The absorption а! 2875 cm 1 in the speclrum of
EtSCN is assigned 'о Ihe symmetric stretching viЬrаtiоп [27 29) and aIso 'о ап
overtone [30,31] (see Section 10.1.2).
Methyl and melhylene deformations
ТЬе antisymmetric methyl deformalions give rise 10 а medium Ьапd between 1480
and 1440 cm 1 and the methylene scissors absorbs Ьеtwееп 1445 and 1415 cm l,
as for example in the spectrum of еlhуlthiоеthапе (Б.Ме 1480 апd 1460 Б Ме,
1455 and 1445 and БСН2 1441 and 1425 cm l). Тhe lowest wavenumber for the
methylene scissors is found in the speclrum of MeSSEt and EtSSEt: 1418 cm l.
ТЬе region of 'Ье melhyl symmelric deformation (1380 :f: 10 cm l) agrees with
that of ,Ье Mc(CH2)1I fragmcnts (Sесtiопs 3.5.1 апd 3.5.5).
Меthуlепе wagging апd twisting vibralions
ТЬе mеlhуlепе wagging vibralion exhibils а rnoderate to strong band iп Ihe rеgiоп
1280::1:: 30 cm l, usually еуеп а! 1275 ::!: 10 cm l, Ihal is ::::::80 cm 1 lower Ihan
in ОЕ! compounds. ТЬе methylene twisl absorbs scarcely 25 сrп 1 lower thап Ihe
wag. Ethylthioethane shows the wag al1282 апd 1271 cт 1, EISCN а! 1273 cm 1
and MeSEt at 1264 cm l, and the twist аl respectively 1261 апd 1246, 1244 апd
1249 cm 1.
Methyl rocks and c c strelching viЬrаliоп
ТЬе methyl rocks are reported between 1100 and 1010 cm 1 with а weak to
modcratc intensily. Ethanethiol absorbs near 1100 and 1048 cm 1 апd СDз SЕt
near 1040 (traпs) or 1014 cm 1 (gallclle). The c c stretching viЬrаtiоп is active
in 'Ьс range 975::1:: 25 cm 1 wilh ап intensily vаrуiпg between \уезk апd slrong. As
contrasted wilh the OEt compounds, in which the methyl rocks are strongly coupled
282 Norlll01 Vibrot;o/ls о//(/ AbsOIpt;o/l Reg;o/ls о{ S//I{III' COlll{JOIllU/S
to tllc c c and 'Ьс c o stretcllil1g vibratiol1, tllcSC rocks arc по! couplcd 'о Ihc
vC S and hardly 'о 111C //c c.
Mcthylenc rocking vibration
ТЬе methylenc rock in R SEt compounds is assigncd а! rclatively low wavc
numbcrs (765 :!:: 35 cm l) with а \veak 'о moderatc intcnsity. ТЬе 11ighest value
comcs from EtSEt (798 and 762) and the lowcst from HSEt (tr: 782; g: 735 сm I ).
ТЬе rcmaining compounds show this рСН2 а! 775 :!:: 25 cm l. This vibralion is
somc\vhat coupled 'о 'Ьс //C S and sensilive to сопt'оrmаtiоп.
Thc C S strctching vibration
Тhe C S stretching vibration occurs а! 670 :!:: 35 cт 1 with а wcak 'о moderate
intensity, 'Ьа! is 50 cm l lowcr than the Me S strctching vibration, but agrecs
with 'Ье vsC S C (680 :!:: 45 cm l) in R CH2SMe compOUl1ds (Section 3.3.2)
[39]. Ethylthioethane sho\vs both C S stretching vibrations а! 696 and 638 cт 1,
EtSSEt а! 670 and 640 cm l and EtSCN а! 686 cm l. Тhis vibration is sensitivc 10
'Ье conforrnational state of the molecule. Compounds such as iPrSEt and tBuSEt
absorb а! 695 cm 1 in 'Ьс tro/ls conformation and а! 670 cm l in the gOllc//e
conformation.
Skeletal deformations
Тhe highcst dcformation is considered as а S C C deformation occurring а! 350
:!:: 40 cт 1. lп ethylthioethane the two S C C deformations absorb а! 395 and
336 cm 1. Тhe lo\vest deformation is (Ьс external R S C skelctal dcformation
(235 :!:: 70 cm l). High wavcnumbers are due 'о EtSEt (305 and 294) and lо\у
wаvепumЬеrs to EtSCN (165) and MeSEI (t/.: 215; g: 270 cm I). In тапу R SEt
compounds this extcrnal skeletal deformation is located а! 265 :!:: 35 ст 1 .
ТаЫе 11.2 Absorption regions (cm l) of the поmlаl vibrations of SEt
Vibration Region Vibration Region
vaMe 2980 :!:: 15 рМе 1075 :!:: 30
v Me 2965 :!:: 10 р'Ме 1035 :!:: 25
V a C H 2 2940 :!:: 20 vC C 975 :!:: 25
vsMe 2920 :!:: 25 Р СН 2 765 :!:: 35
V s CH 2 2880 :!:: 30 vC S 670 :!:: 35
БаМе 1465 :!:: 15 Бs с с 350 :!:: 40
Б'Ме 1450 :!:: 10 Б S С 235 :!:: 70
Бен, 1430:!:: 15 torsion Ме 245 :!:: 35
БsМ; 1380 :!:: 10 torsion Е! 185 :!:: 30
WCH2 1280 :!:: 30 torsion SEt 75 :!:: 30
ТСН2 1250 :!:: 20
11.1 ТМо Coтpoullds
283
R SEt molcculcs
R = H [ЦUJ, o [5J, Mc [ I7], СDз [11, 12J, Et [7 12, 18---22J,
nPr [211, CICH2CI-12 [22J, PhCH2 [23], MeOCH2 [24J, iPr [10,
25, 261, tBu [10, 26], N=c [27 3IJ, Ph [32, 33J, MeS [3 37J,
EtS [10, 35 38J.
References
1. N. Sheppard,J. С//ст. P//ys., 17,79 (1949).
2. A.J. Barnes, Н.Е. Наllаm and J.D.R. Howells, J. C/rcm. 50c.,Faraday " 68, 737
(1972).
3. О. Smith, J.P. Devlin and D.W. Scott, J. Мо/. 5peclrosc., 25, 174 (1968).
4. J.R. Durig, W.E. Bucy, C.J. Wurrey and L.A. Carreira, J. P//ys. C/rem., 79, 988 (1975).
5. Н. Wolff and J. Szydlowsky, Call. J. CI/em., 63,1708 (1985).
6. D.W. Scott, H.L. Finke, J.P. McCullough, М.Е. Gross, К.О. Williamson, G. Wаddiпgtоп
and Н.М. Huffman, J. Ат. C/rcm. 50С., 73, 261 (1951).
7. D.W. Scott and M.Z. El Sabban, J. Мо/. 5peclrosc., 30,317 (1969).
8. R. Fausto, J.J.c. Teixeira Dias and P.R. Carcy, J. Мо/. 51"'CI., 159, 137 (1987).
9. W.O. George, J.H.S. Green and D.J. Harrison, 5pcclroc/riт. Acla, Parl А, 24А, 367
(1968).
10. О.\У. Scott and J.P. McCullough,J. Ат. С//ст. 50С., 80, 3554 (1958).
11. М. Ohsaku, У. Shiro and Н. Murata, 8//1/. C/rem. 50С. Jp//., 46, 1399 (1973).
12. N. Nogami, Н. Sugeta and Т. Miyazawa, 8//1/. C/rclll. 50С. Jp//., 48, 3573 (1975).
13. М. Hayashi, Т. Sllimanouchi and S. Mizushima, J. С//С1ll. P/rys., 26, 608 (1957).
14. М. Ohsaku, У. Shiro and Н. Murata, 8//1/. C/rcm. 50С. Jp//., 45,954 (1972).
15. J.R. Durig, О.А.с. Compton and M.R. Jalilian, J. P/rys. Clrcm., 83, 511 (1979).
16. М. Sakakibara, Н. Matsuura, 1. Harada апd Т. Shimапоuсhi, 8//1/. С//ет. 50С. Jp//., 50,
111 (1977).
17. J.R. Durig, M.S. Rollins and Н.У. Phan, J. Мо/. 51"'CI., 263, 95 (1991).
18. D.W. Scott, H.L. Finke, W.N. Hubbard. J.P. McCullough. GД Olivier, М.Е. Gross,
С. Katz. К.О. WilIiamson, G. Waddington and Н.М. Huffman, J. Ат. С//С1ll. 50С., 74,
4656 (1952).
19. М. Ohsaku, У. Shiro and Н. Murata, 8//1/. C/relll. 50С. Jp//., 45,956 (1972).
20. R.S. Cataliotti, G. Paliani and S. Santini, Са//. J. P/rys., 64, 100 (1986).
21. М. Otha, У. Ogawa, Н. Matsuura, 1. Harada and Т. Shimanouchi, 8//1/. С//ст. 50С. Jp//.,
50, 380 (1977).
22. S.D. Christesen. J. Raтa// 5peclrosc., 22, 459 (1991).
23. К. Doerffel and В. Adlcr, lViss. Z. Tcc/r. Hoc/rsc//. С//ет. Lerтa.Mcrseb//rg, 10, 7 (1968).
24. Н. Matsuura, Н. Murata and М. Sakakibara,J. Мо/. 51"'CI., 96, 267 (1983).
25. М. Ohsaku, Н. Murata and У. Shiro, 5pcclroc//im. ACla, Parl А, 33А, 467 (1977).
26. М. Sakakibara, 1. Harada, Н. Matsuura and Т. Shiшапоuсhi, J. Мо/. 5Ir//cl., 49, 29
(1978).
27. R.P. Нirschmann, R.N. Кniseley and У.А. Fassel, 5peclroc//illl. Acla, 20, 809 (1964).
28. G.A. Crowder, J. Мо/. 5Ir//cl., 7, 147 (1971).
29. О.Н. Ellestad and Т. Torgrimscn, J. Мо/. 51"'CI., 12.79 (1972).
30. J.R. Durig, J.F. Sullivan and H.L. Heusel, J. P/rys. C/relll., 88. 374 (1984).
31. G.O. Braathen and А. Gatial, 5peclroc/rilll. Acla, Рап А, 42А, 615 (] 986).
32. J.H.S. Green, 5pcclroc/rim. ACla, 18,39 (J9б2).
33. G. Varsanyi, Assig//mc///s [о, Vibralio//a/5peclra of5evc// Ншrdrс<J 8e//ze//e Derivalives,
J.Wiley & Sons, Ne\v York (1974).
284 NO/'/Ila/ Vibratiolls alld Absorptioll Regiolls о[ 5///[/11' Compo/ll/(/s
34. KG. Аl1ит, J.A. Crcigllton. J.H.S. Grccn, G,j. Minkoff and L,j.S. Pril1cc, 5pcctrocl!im.
Acra. Part А, 24А, 927 (1968).
35. Н. Sugeta, А. Go and Т. Miyazawa.8///I. С/и!т. 50С. Jpll., 46, 3407 (1.973).
36. Н. Sugeta, 5pcctrocl!im. Acta, Pa/'l А, 31А, 1729 (1975).
37. W. Zhao and S. Кrimm, J. Мо/. 5tr//ct., 224, 7 (1990).
38. D.W. Scolt, H.L. Finke, J.P. McCul1ougll, М.Е. Gross, R.E. Pcnnington зпd G.
Waddington, J. Ат. CllCIIl. 50С., 74, 2478 (1952).
39. М. Ohsaku, 8///1. C/lem. 50С. Jpll., 48, 707 (1975).
11.2 METHYLSULFINYL
Тhc S(==O)Me frаgшепt, just likc 'Ьс C(==O)Me group, accounts for
fifteen поrrnаl vibrations, of which nine belong to the Ме group. Тhe rcmaining
six are describcd as follows: vS==O, 6S==0, ')'S==O, vC S, 6C S and
MeS(==O) torsion. In the C s configuration thcse поrшаl vibrations are divided
in 9а' and 6а" species of vibration:
а': v Me, vsMe, 6 Me, 6 s Me, vS==O, р'Ме, vC S, 6S==0, 6C S ;
а": vaMe, 6 а Ме, рМе, ')'S==O and two torsions.
In 'Ье spectrum of MeS(==O)Me the 24 поrmаl vibrations arc dividcd among 13а'
and 11а" types of vibration (Table 11.3).
ТаЫе 11.3 Normal vibrations and assignments of
McS(==O)Mc in thc Iiquid statc [2]
Vibration (а') cт 1 Vibration (3") cm l
vaMe 2998 vs==o 1058
vaMe 2998 рМс 1022
v Mc 2998 рМс 954
v Mc 2998 р'Мс 932
vsMc 2914 р'Мс 897
v.,Mc 2914 vaCSC 699
6а МС 1438 v,CSC 669
6а МС 1420 6s==0 382
6 Mc 1420 ')'S==O 332
6'Ме 1407 6C S C 309
6;Ме 1310 torsion Мс 248
6 s Mc 1295 torsion Мс 214
In dеliшitiпg the absorption regions оС (Ьс S(==O)Me fragmcnt, only а few
iпtеrрrсtаtiопs of R S(==O)Mc spectra are available, so that the limits are only
indicativc and far frош rерrеsепtаtivе.
J 1.2 Metl!ylsulfillyl
285
Mcthyl strctching vibrations and deformations
Thc strctching vibrations and the deformations give rise 'о weak or moderate
absorptions. Often both antisymmetric modes coincide. The methyl symmetric
deformation is shifted 'о lowcr values (1305 :1: 15 cm 1) as compared with those
for satиrated hydrocarbons, for cxample in the spectra of PhS(==O)Me (1295),
ClS(==O)Me (1297), 4 McPhS(==O)Me (1300) and MeOS(==O)Me (1302 cm 1).
ТЬс S==O strctching vibration
Тhe vS==O absorbs strongly iп 'Ье region 1095 :1: 50 cm 1. The highest wave
numbers are found in thc spectra оС CIS(==O)Me (1145) and MeOS(==O)Me (1130
cm l). Тhe narrower region 1060:1: 15 cm 1 is useful for mапу simple sulfoxides
[7]. Тhe S==O stretching viЬrаtiоп is sensitive to dissolution [9, 11] and more 'Ьan
опе band in the above mentioned rеgiоп сап Ье attributed to diffеrепt сопfоrmеrs
[7]. The wavenumber оС the vS==O is easily derived from the епvirопmепt. If
for instance MeOS(==O)OMe absorbs а! 1208 and MeS(==O)Me а! 1058 cт 1, а
compound such as MeOS(==O)Me is expected 'о absorb а! yl1208 х yll058 = 1133
cm l. In а similar way 'Ье vS==O of CIS(==O)Me (1145 cm l) is ca1culated from
those of MeS(==O)Me (1058) and C1S(==0)C! (1240 cm I).
Mcthyl rocking vibrations
Thc methyl rocks give rise to weak or moderate Ьапds Ьеtwееп 1025 апd 895
Cffi l. Both limits соте from 'Ье spectrum of sulfiпуlЫsmеthапе (Table 11.3).
CIS(==O)Me shows these rocks а! 948 and 932 cm 1.
ТЬе C S strctching viЬrаtiоп
In the spcctra of the tested compounds the vC S, which iп пеаrlу symmetrical
compounds is assigned as VaCSC and vsCSc, occurs а! 680 :1: 20 cт l with а
weak to moderatc iпtепsitу.
Тhe S==O deformations
Кresze et al. [9] rcport that the S==O in plane dеfоrmаtiоп оС 4 XPhS(==0)Me
compounds (Х = Ме, МеО, Cl, OzN) occurs а! 530 :1: 10 cm l. As the 8S==0
in PhS(==O)Me absorbs а! 497 cffi l and in MeS(==O)Me а! 382 cm 1, the
absorption region of the S==O in plane dеfоrmаtiоп is 460:1: 80 cm l. Тhe S==O
out of plane deformation is located in the rеgiоп 355:1: 25 cm l, with 360:1: 10
cт 1 for 4 XPhS(==0)Me compounds [9].
Skelctal C S defonnalion
The C S skeletal deformation exhibits а very weak Ьапd а! 300:1: 20 cm 1 iп
286 Norтal Vib/'at;o"s a"d AbsOIpt;o/l Reg;ollS u! SlIlfll1' CoтpOIlI/ds
infrarcd spcclra, somclimcs visibIc only in 111C Ramal1 spcctra, such as ill 1110SC of
PllS(==O)Mc (320R), 4 McPIIS(==0)Mc (282R) and 4 McOPllS(==0)Mc (285R).
Tallle 11.4 АЬsоrpliоп rсgiопs (cm l) of 111C поrтаl
viЬrаtiопs of 5(==0)Mc
Vibralion Rcgion Vibration Rcgion
vaMc 3005 :!: 20 р'Мс 930 :!: 35
v;'Mc 2995 :!: 15 vC S 680 :!: 20
vsMc 2925 :!: 25 155==0 460 :!: 80
Бамс 1425 :!: 15 ,S==O 355 :!: 25
Б;'Мс 1415 :!: 15 БС S 300 :!: 20
Бsмс 1305 :!: 15 lorsion 190 :!: 80
vS==O 1095 :!: 50 lоrsiоп 100 :!: 60
рМс 985 :!: 40
R S(==O)Me molcculcs
R = Me [Н5], Et , iPr and IBu [7J, McScH2 , Ph [8, 9], Ph
d5 [8], 4 MePh [7, 9], 4 XPh (Х = МеО, CI, 02N) [9], MeO [10],
CI [10].
References
1. W.O. Horrocks Jr. апd ЕА. Соttоп. Speclrocllim. Acta. 17, 134 (1961).
2. M. T. Forcl апd М. Tranquillc, Speclrocllim. АСIa, Part А. 26А, 1023 (1970).
3. G. Gciselcr апd G. Напsсhтапп,J. Мо/. Slrtlct., 8, 293 (1971).
4. G. Gcisclcr and G. Hanschmann, J. Мо/. Slrtlct., 11, 283 (1972).
5. М. Тrапqui1lс. Р. Labarbe, М. Fouassicr апd M. Т. Forcl, J. Мо/. Strtlct., 8, 273 (1971).
6. S. Bianco, R.S. Calaliotti, S.Chicli, F. Gucrrini, С. Gaburri, G. Раliапi, А. Pcraio, М.
Scamosci and С. Taralza, Speclrocllim. Acta, Parl А, 42А, 855 (1986).
7. М. Oki. 1. Oka and К. Sakaguchi, 81111. C/lem. Soc. Jp"" 42, 2944 (1969).
8. М. Bouquct, G. Chassaing, J. Corsct, J. Favrol апd J. Limouzi, Spectroc/lim. Acta. Parl
А, 37А, 727 (1981).
9. G. Кrcszc, Е. Roplc апd В. Schradcr, Spectroc/lim. АСIa, 21. 1633 (1965).
10. G.E. Вiпdсr and А. Schmidt, Speclroc/lim. АСIa, Parl А, 33А, 815 (1977).
11. Т. Caims, G. Еgliпtоп and О.Т. GiЬsоп, Spectroc/lim. ACla, 20, 31 (1964).
11.3 SULFONYL COMPOUNDS
11.3,1 Methylsulfonyl
Тhc S(==0)2Me fragmenl possesscs 3N 6 = 18 normal vibrations of which nine
arc mcthyI vibralions and ,Ьс rcmaining опеs belong 10 thc S(==0)2C skclclon.
In Ihe C s configuralion the distribulion is as foIlows:
11.3 SII/foпy/ Coтpollllds
287
а': v Mc, ,/,Ме, Ь:'Мс, Б,Мс, v.,SOz, р'Ме, I/C S, bSO z , wSOz, БС S ;
а": vlIMc, ыlс,, 1/IIS02, рМс, TS02, pS02 апd two tоrsiопs.
ТаЫе 11.5 Normal vibrations апd аssigпmепts of
MCS(==0)2 Mc
Vibration cт 1 ViЬrаtiоп cт 1
vlIMc 3027 рМе 1011
vlIMc 3024 рМс 987
v Mc 3015 р'Мс 947
v Mc 3015 р'Мс 934
v,Me 2935 l/QC S C 763
vsMc 2935 I/sC S C 700
БlIмс 1439 БS0 2 50]
Бамс 1427 WS02 457
Б Мс 1427 7S02 383
Б Мс 1408 pS02 326
Б.,мс 1335 БС S С 300
Бsмс ]314 torsion Ме 271
V ll S02 1298 torsion Мс
V.,S02 1135
Mcthyl stretching vibrations and deformations
ТЬе methyl strctching vibrations are observed Ьеtwееп 3050 апd 2920 cm l апd
'Ьс deformations betwcen 1460 and 1300 cm l. Both antisymmetric modes оftеп
coincide. The methyl symmetric deformation, iп most cases occurring а! 1325 :f:
15 cm l, is oftcn obscured Ьу the strong band of the S02 strеtсhiпg viЬrаtiоп.
Тhc S02 strctching viЬrаtiопs
Тhe most characteristic absorptions оС (Ье S02Me group are the SOz stretching
vibrations. With ,Ьс exception of MCS020Na (1247 cm 1), the алtisуmmеtriс mode
appcars strongly in the rеgiоп 1330 :f: 60 cm 1. The highest value (1390 cm l) is
furnishcd Ьу MeS02F and MeS02Br, followed Ьу 1366 cm 1 from MeS02CI. Low
values сотс from 4 H2NNHPhS02Me (1270), EtS02Me (1274) and PhS02 Me
(1285 cm l). Тhe rеmаiлiпg molecules show this strong Ьапd а! 1330:!: 30 cm l.
Sulfur dioxide absorbs near 1361 cm l.
The symmetric counterpart absorbs also strongly iл (Ье region 1180 :f: 45 cm l,
with high wavenumbers in the spectra of MeS02F (1223), MeS020Na (1190) апd
НС=ССН(Ме)S02Ме (1181 cm l) and low wаvепumЬеrs in those of EtS01Me
(1132), MCSS02Me (1134), H2C==CHS02Me (I 135) апd MeS02Me (1 I35 cm I).
288 Norl11a/ Vibтtio/ls а//(/ Absorptio/l RegiOlls о[ SIl/[II1' COl11pOIl1IC/S
Mos! оС the R S(==0)2Me compounds givc tllc 1/ 5 S02 in !hc l1arrow rcgion 11 БО
:1: 20 cm l. Sulfur dioxide stretches symmctrically а! 1151 cт 1.
Methyl rocking vibrations
For 24 aromatic methylsulfoncs Momose et а/. [25] assign thc mcthyl rocks in
the rcgions 965 :1: 15 and 955 :1: 10 cm 1 and thc C S strctching vibration а!
770 :1: 20 сm 1. Mcrian [24] supposcs that thc rcgion 970 :1: 5 сm I mау Ье
reservcd for а methyl roсkiпg vibration. Often both rocks are assigncd а! thc same
wavenumber. ТЬеу are active \vith а \veak (о moderate intensity in the rcgions 985
:1: 35 and 940 :1: 40 cm l. ТЬе former region narrOWS 'о 970 :1: 20 cm 1 if the
values оС 1011 cm l in the spec!rum оС sulfonylbismethane and 1017 cm l in that
of HC=CH(Me)S02Me are disrcgardcd.
ТЬе C S stretching vibration
Thc C S stretching vibration appears moderately 'о s!rongly in 'Ьс region 745
:1: 45 cm l. ТЬе HW side is limitcd Ьу СОзNНS02Ме and СDзNDS02Ме with
790 cт 1 and Ьу MeS020Na and H2C==CHS02Me with 788 cm 1. ТЬе lowest
values are obscrvcd in the spectra of MCS02Me (vsCSC 700), MeOS02Me (721),
пРrОS02Ме (724), cICH2CH20S02Mc (729), FS0 2 Mc (730), ЕЮS02Ме (733)
and BrS02Me (733 cm 1). The majority of the invcstigated molecules were found
'о give this stretching mode а! 760 :1: 25 cm l.
ТЬе S02 deformations
ТЬе S02 scissors сап readily Ье detected in 'Ье rcgion 535 :1: 40 cm l, mainly Ьу
the moderate (о strong intensity. Sulfur dioxide 'snips' а! 519 cm l.
ТЬе S02 wagging vibration appears wcakly (о modcrately а! 485 :1: 50 cm 1
but the vibration in this region is sometimes reported as а rock [10].
If for аН investigated molecules it is accepted that (Ье rock absorbs а! а lower
wavenumber than (Ье twist, the region 405:1: 65 cm 1 is considercd for the twisting
vibration and the region 320 :1: 40 cm 1 for the rocking vibration. In (Ье spcctrum
of C1CH 2 S0 2 Me the absorptions а! 507, 452, 374 and 309 cm l are assigned
respectively 'о !he S02 deformation, wag, twist and rock [12].
Ske1etal C S deformation
ТЬе skclctal C S deformation сап Ье found as а weak 'о moderate absorption
in the region 295 :1: 40 cm 1. ТЬе C S N bcnd in MeNHS02Me is assigned а!
331 cm 1 [16] and the C S Cl bend in ClS0 2 Me а! 256 cm 1 [23].
JJ.З Sи/Joпy/ Сотроuпш 289
ТаЫе 11.6 Absorption rcgions (cm l) of (Ьс normal
vibrations of S02Mc
Vibration Region Vibration Region
УаМс 3030 :1: 20 р'Ме 940 :1: 40
Y Mc 3025 :1: 25 vc S 745 :1: 45
у.,Мс 2940 :1: 20 OS02 535 :1: 40
Оа МС 1430:1: 30 WS02 485 :1: 50
O Mc 1415:1: IS 7S02 405 :1: 65
OsMc 1325 :1: 25 pS02 320 :1: 40
V a S02 13 30 :1: 60 oC S 295 :1: 40
vsSOz 1180 :1: 45 torsion
рМс 985 :1: 35 torsion
R S(==0)2Me moleculcs
R = Me [1 10], СОЗ [9], Et [11, 70], CICH2 апd BrCH2 [12],
HC=CCH(Me) , H2C==CH [2], Pb [13, 69, 70], Ph ds [13], 4
XPh (Х = Ме, МеО, CI апd 02N [14], НО(О==)С, Н 2 NNН), H2N апd
D2N [15J, MeHN [16, 17], MeHN dl , dз and .d4 [16],iPrHN ,
tBuHN , Me2N , Et2N and iPr2N (17], PhNH do, dl , ds апd
d6 [18], 3 XPhNH (Х = Ме, CI, 02N) [19], 4 XPhNH (Х = Ме,
МеС(==О), N=C, 02N, МеО, Сl апd MeSOz) [19], MeO апd ЕtO [20],
nPrO , CICH2CH20 , NaO [50], MeS , F [10,21, 22], Cl [10,
21,22, 23], Br [21].
11.3.2 Fluorosulfonyl
In the С . symmetry thc nine norrnal vibrations of the S02F fragment are divided
iпtо 5а' + 4а" types of vibration:
а': V s S02, vS F, oS02, WS02, oF S ;
а": V a S02, pS02, 7S02 and torsion.
ТЬе literature does not always agree in assigпiпg 0502 > WS02 > 7S02 > pS02
with decreasing wavcnumbers.
ТЬе S02 stretching vibrations
ТЬе S02 antisymmetric stretching viЬrаtiоп in R 5(==0)2F compounds absorbs
strongly in the rcgion 1445 :1: 60 cm l with high values for R = F (1502), FO
(1501), F2NO (1492) and ею (1481 cm l) апd а low value (1385 cm l) for R
= 3 H2NPh and 4 H2NPh. ТЬе rcmaining molecules restrict themselves 'о 1440 :1:
40 cm ], with 1415 :1: 10 cm l for 'Ье aromatic sulfonyI fluorides.
The S02 symmetric stretching viЬrаtiоп appears strопglу iп the rеgiоп 1230 :1:
40 cm ]. If the highest values for R = F (1269), FzNO (1254), FO (1248), СЮ
290 NO/'llla/ \libтtiol/s а//(/ AIJSOlptioll Rcgiol/s о/ SIl//II1' Compoll1/ds
(1248) and НО (1243 cm l) arc по! takcn into account tllc rcgion narrows 'о 1215
:!: 25 сnз l.
Thc F S strctching vibration
The /IS F posscsscs а nзоdсrаtе intensity and occurs in tllC rcgion 825 :!: 75 cm l,
of \Vllich thc uppcr linзit is taken Ьу HOSOzF (896), FS02F (887), CICH 2 S0 2 F
(882) and BrCHzS02F (853 сnз I).
The S02 dcforrnations
The S02 scissors in R S02F compounds is located in thc region 555 :!: 70 cm 1,
\vith high values for R = F (625), 4 ClS02Ph (620), 4-сl(0==)СРh (617) and 4
HO(O==)CPh (608 сnз l) and low values for R = Br (489), СI (505), Ме (528) and
Me2N (531 сnз l), so that the rеnзаiпiпg compounds absorb а! 570 :!: 35 сnз l.
Тhc S02 wagging viЬrаtiоп nзаkеs its appearancc, separatcd frоnз thc scissors,
in the rcgion 510 :!: 60 сnз l, ехсер! for F2NOS02F, in which the scissors
vibration рroЬаЫу coincides with the wag. The spectrum оС 3 OcNPhS02F givcs
the highest value (567 сnз I). Тhe lowest wаvепunзЬеrs are found in ,Ье spectra
:>f BrS02F (458), MC2NS02F (461), CIS02F (480) and CICHzS02F (486 cm I).
The rеnзаiпiпg observed \vags fit into the region 525 :!: 35 cm l.
With the exception оС the low wаvепunзЬеr (310 сnз l) in the spectrum of
BrS02F, the S02 twisting vibration is located in the region 470 :!: 70 сnз l. For
R = Me2N, ОН or Сl the twist is assigncd а! respcctively 406, 409 or 430 cm 1
and for R = F thc twist appears а! 539 сnз l. Most of the sulfonyl ftuorides givc
this twist а! 480 :!: 35 cm l.
Тhe S02 rocking vibration has Ьесп observed in the rcgion 375 :!: 85 cm l with
low values for R = Br (290), СI (300) and BrCH2 (304 сnз l). The remaining
R S02F compounds absorb а! 390:!: 70 сnз l.
Skeletal F S deforrnation
Only а fe\v values for this deformation are kпоwп, so that the bF S рroЬаЫу
absorbs near 300 :!: 30 сm 1 .
ТаЫе 11,7 Absorption rcgions (cт 1) of thc normal
vibrations of S02F
Vibration Rcgion Vibration Rcgion
V a S02 1445 :!: 60 TS02 470 :!: 70
V s S02 1230:!: 40 pS02 375 :!: 85
vF S 825 :!: 75 bF S 300 :!: 30
bS02 555 :!: 70 torsion
WS02 510:!: 60
1 J.з Sи/fo"y/ Coтpoипds
291
R S(==0)2F molcculcs
R = Mc [](), 21, 22], clcH2 and BrcH2 [26), PhCHz , 2 XPh (Х
= 02 N , CI50 2 ), 3 XPh (Х = Мс(О==)С, НО(О==)С, CI[O==)c, H 2 N,
O==C==N, CIS02), 4 XPb (Х = Ме, НО(О==)С, CI(O==)C, H 2 N, CISO z ),
MC2N [27J, HO [29 32J, McO [31), F2NO [28, 31], FO [31,37],
СIO [31J, F [32 36], CI [32,35, 38], Br [39,40].
11.3.3 Chlorosulfonyl
Tlle S02 strctching vibrations
Thc V a S02 gives rise to а strопg Ьапd in the rеgiоп 1385 :!: 35 cm 1. Тhe R'050 2 CI
compounds (R' == Н, alkyl, aryl) take 'Ье upper Iimit with 1410 :!: 10 cm J.
Bcnzenesulfonyl chloridcs absorb а! 1390:!: 15 cm l [43,44J.
With the exccption of FзС5О2Сl (1237 cm l) the V s S02 appears stroпglу iп the
region 1180:1: 30 cm l, usually еуеп а! 1175 :!: 25 cm ) ехсер! for НО50 2 СI
(1209), (СD з )zN50 2 Сl (1207) and 4 MePhOSOzcl (1205 cm l). For Ьеnzепе
sulfonyl chlorides thc region narrows to 1185 :!: 15 cm l [43,44J.
The 502 deformations
The region 570 :1: 60 cm ) is attributed 'о [Ье S02 scissors Ьи' aIso 'о the CI S
stretching vibration, which is stroпglу coupled 'о this S02 iп рlапе dеfоrmаtiоп.
ТЬс upper limit is takcn Ьу FS02c1 with 625 cm l; CIS02cH2S02cI shows both
deforrnations а! 610 and 528 cm 1 and CIS02c02S02c1 а! 609 апd 510 cm l.
The rcmaining molccu1es display this S02 scissors а! 560 :!: 30 cm l.
ТIзе S02 wagging vibration is active in the rеgiоп 510:!: 40 cm l, formed Ьу
methanedisulfonylchloride (546 and 494) апd mеthапеdisulfопуlchlоridе d2 (533
and 473 cm l).
ТIзе 502 twisting vibration absorbs in the region 410:!: 80 cm l, with 490 cm 1
for McSO,Cl and 357 and 333 cm l for CISO,CO,SO,CI.
ТIзе S02 rocking viЬrаtiоп occurs а! 300 з о c l, \vith 290 cпl l for
mеthапсsu 1 fony Ichloride.
ТЬе CI 5 stretching viЬrаtiоп and deformation
Iп R 502Cl compounds 'Ье Cl S strеtсhiпg viЬrаtiоп is coupled to [Ье S02
dcformation. Birchall and Gillespie [32] assign the absorption пеаr 625 cm l in
the spectrum of FS02CI 'о the vCI S апd that at 427 cm l to 'Ье БS02 with а
contribution of уСI 5. According to Pfeiffer [35] or Craig and Futamura [38],
the band а! 427 cm l is due to the vCl S апd that а! 625 cm l 10 the Б5 0 2
and the vCI 5. Hanai et а/. [23] assign the Ьапd а! 373 cm I in (Ье spectrum
of MeSO,CI to the CI 5 stretch and that а! 533 cm l to the 502 dеfоrmаtiоп
as well a 'о the CI S strctching vibration. Тhe rеgiоп 395 :!: 35 cm l тау Ье
292 NomlO/ Vibт(io//s a//d Abs01]J(io// Regio//s о[ SIII[ш' Coтpoll//ds
reservcd for the cl S strctcll, althougll this vibration sccms 'о Ьс active also in
the rcgion оС tlle 6S0 2 (57О:!:: 60 cm I).
The vibrational analysis in 'Ьс Iitcrature rcveals only а fcw wavcnumbcrs for tllC
CI S skeletal dcformation.
ТnЫе 11.8 Absorption rcgions (cm l) of thc normnl
vibrations of S02C1
Vibration Region ViЬrntiоп Rcgion
V.S02 1385 :!:: 35 vCI S 395 :!:: 35
V s S02 1180:!:: 30 pS02 300 :!:: 30
6S0 2 570 :!:: 60 6C1 S 235 :!:: 45
WS02 510:!:: 40 torsion
7S02 410 :!:: 80
R S(==0)2Cl moleculcs
R = Me [10, 21 23], СDз [23], Et [48], iPr , CICH2 and
BrCH2 [26], nBu , Сl(СН2)З , ClS02CH2 and CIS02CD2 [41],
PhCH2 [44], 4 02NPhCH2 , FзС , Ph [42----44], 2 , 3 and 4
XPh (Х = Ме and 02N [44], FS0 2 ), 4 XPh (Х = F, Cl, Br, МеО
and Me2N [44]), 2,5 C12Ph , 2,4 (02N)2Ph [44], F5Ph , 2 Tb ,
Me2N [27, 45], (СDЗ)2N [45], O==C==N , HO [20, 29, 30],
MeO [20, 46, 47], ЕtO , nPrO , nBuO and PhO [47, 48J,
CICH20 , 4 MePbO and 4 CIPhO [47], F [32,35, 38], Cl [35,
49].
11.3.4 R' oxysulfonyl
ТЬе spectra of esters оС sulfonic acids are dominated Ьу three absorptions with а
moderate to strong intensity, due to both S02 stretching vibrations and а S O
stretch.
ТЬе S02 stretching vibrations
Ехсер! for MeS020Na, which absorbs а! 1247 ст " the S02 antisymmetric
stretching viЬrаtiоп Iics within the large rеgiоп 1415 :!:: 85 cm l. ТЬе highest
values of 1500, 1492, 1481, 1480 and 1465 cт l are attributed in the spectra
of derivatives оС fIuorosulfuric acid, respectively FS020F, FS020NF2, FS0 2 0CI,
FS0 2 0H and FS0 2 0Me (see Section 11.3.2). ТЬе lowest wavenumbers соте from
EtSS020Mc (1331), EtSS020Et (1332), MCSS020Et (1337) and MeSS020Me
(1338 cm l). Usually the esters of organic sulfonic acids absorb а! 1385 :!:: 35
cm l.
ТЬе S02 symmetric stretching vibration is obscrvcd in the region 1195 :!:: 60
cm l. Опсе more the highcst values соте from FS020NF2 (1254), FS020F
J 1.3 Su/foпyl Compollпds
293
(1248), FS020C1 (1248) and FS0 2 0H (1243 cm l) апd the lowest are from
EtSS020Mc (1135), EtSS020Et (1137), MeSS020Et (I138) апd Ме55020Ме
(J 141 сm 1). Most of 'Ьс csters of sulfonic acids show this V,S02 а! 1200 :!: 35
cm l.
The O S strctching vibration
With the схсерtiоп of FS0 2 0H (955) апd cIS020H (916 Cffi I), the O S
stretching vibration is assigned at 795 :!: 35 cffi l. As examples, Ме5020Ме
absorbs at 817 cm 1 and MeOS020Me gives rise 'о а vaOSO а! 828 cт 1 апd а
vsOSO at 760 cm 1.
Тhe S02 dcformations
Usually the S02 deformations absorb with а weak to moderate iпtепsitу. The 502
scissors (565 ::!: 45 cm l) absorbs near 610 cm l iп the spectra of FЗCS020R'
compounds and ncar 552 cm ' in those of MeS020R' compounds (R' = Ме, Et).
А second S02 dеfоrmаtiоп, оftеп assigned as а wаggiпg vibration, is fоuпd in а
neighbouring rеgiоп (535 ::!: 35 cm l) but clearly separated fют the scissors. The
literature docs not agrce in аssigпiпg the аЬsоrptiопs iп the regions 425 :!: 85 апd
345 ::!: 55 cm l, which in this work are attributed to the S02 twistiпg апd the 502
rocking vibration.
ТаЫе 11.9 Absorption rcgions (cm l) of the normal
vibrations of S020R'
Vibration Region Vibration Region
V a S02 1415 :!: 85 TS02 425 :!: 85
V s S02 1195 :!: 60 pS02 345 :!: 55
vO S 795 :!: 35 60 S 250
6S0 2 565 :!: 45 tоrsiоп
<.VS02 535 :!: 35
Et
FзС
4 MePh
4 02NPh
MeO
McS
EtS
R S(==0)20 R' molecules
R R'
Mc Me [20], Et [20], пРr , CICH2CH2 , HC=CCН(Me) ,
Na [50],
Me [20], Et [20],
H [51], Me , Et ,
Me [65], Et , СFЗСН2 , CICH2cH2 ,
Me
Me [52,53],
Me and Et [54],
Me and Et [54],
294 Norma/ Vi"тtio"s a"d л "sOI'ptio" Regio"s о[ SU/[Ш. Compoul/(/s
F H [29 32], Mc [31J, F2N [28, 31], F [31, 37], CI [3IJ,
cl H [20, 29, 30], Me [20, 46, 47], Et , nPr , nBu and
Pll [47, 48], CICH2 , 4 McPII and 4 CIPll [47].
11.3.5 Aminosulfonyl (sulfопаnзidо)
The S(==0)2NH2 frаgnзспt in рrinзаrу sulfonamidcs givcs 15 поrnзаl vibrations.
Six vibrations are inllcrent 'о tllC NH2 group (see Section 9.1): vaNH2, vsNH2,
6NH2, pNH2, wNH2 and torsion. Tlle rcmainiJ1g niJ1e vibrations belong 'о
thc S02 N skcleton: V a S02, V s S02, 6S02, WS02, rS02, pS02, vN S,
6N S and torsion.
The S02 stretching vibrations
The S02 antisymmctric strctching viЬrаtiоп in primary sulfonamidcs is strongly
active in the region 1335 :1: 25 cm J, extreme valucs being 1358 сnз 1 for
MeHNS02NH2 and 1310 aJ1d 1315 cm 1 for СDЗS02NН2 and MCS02NH2
respectivcly. Bcnzenesulfonamidcs absorb аl 1325 :1: 15 cm 1 [59]. The S02
symmetric stretching vibration is observed in the region 1150:1: 15 cm t.
The N S stretching vibration
ТЬе N S strеtсhiпg vibration exllibits а moderate band in thc rcgion 905 :1: 30
cm J. Mcthancsulfonamide absorbs аl 881 cm ) and H 2 NS0 2 NH 2 givcs rise to а
vaN S N at 931 and а vsN S N аl 904 cm l.
The S02 deformations
AJthough the rcgion of the S02 scissors (570 :1: 60 СП1 J) and that of the S02
\vagging vibration (520:1: 40 cm l) partly overlap, the two viЬrаtiопs are observed
separately.
ТаЫе 11.10 Absorption rсgiопs (cm J) of thc normal
vibrations of S02NH2
Vibration Rсgiоп ViЬrаtiоп Rсgiоп
v" NH 2 3355 :1: 35 6S0 2 570 :1: 60
v s NH 2 3250 :1: 20 WS02 520 :1: 40
6 NH 2 1565 :1: 15 rS02 445 :1: 45
V a S02 1335 :1: 25 rNH2 355 :1: 65
p NH 2 1160 :1: 30 pS02
V.,S02 1150 :1: 15 6 S
vN S 905 :1: 30 tоrsiоп
wNH2 690 :1: 40
J J.3 Sи/follY/ compo/llJds
295
R S(==0)2NH2 compounds
R = Mc and СDз [15J, Pb [43, 58, 65], Ph d5 [43], 2 XPb (Х =
Мс, Мс(О==)С, H2N, 02N), 4 XPh (Х = Ме [65], НО(О==)С, H2 N
[65], 02N, СI ), 2 Th [60, 62], H2N [55, 56], MeHN , Me2N and
(СDЗ)2N [57].
11.3.6 R' aminosulronyl
The NH vibrations
The NH strctching vibration in secondary sulfопаmidеs is observed iп the region
3270 :1: 65 cm 1, mostly а! 3265 :1: 45 cm l. Laurепсе е/ а/. [61] fоuпd 3265 ::J:
10 cm l for thirty N (3 and 4 Х рhепуl)suЬstitutеd mеthапеsulfопаmidеs for the
dimer and 3390 :1: 1 О сm 1 for the monomer iп dilute CC14 solution. Arcoria е/
а/. [60] assigncd the vNH а! 3240 :1: 35 cm 1 iп the spectra of thirty N substituted
2 thiophcnesulfonamides.
The NH in plane deformation exhibits а moderate аЬsоrptiоп Ьапd iп the rеgiоп
1395 :1: 25 cm l, usually а! 1395 :1: 15 cm l, а rеgiоп also proposed Ьу Kalova
е/ а/. [19] for а serics of thirty secondary sulfопаmidеs.
The ,NH or NH wagging vibration is а broad аЬsоrрtiоп with low intensity in
the region 650 :1: 50 сm 1, and is sometimes difficult 'о detect аmопg the iпtепsе
aromatic СН out of plane deforrnations.
Thc S02 vibrations
Thc S02 antisymmetric strеtсhiпg vibration appears iп the region 1330 ::J: 30 cт 1
and the symmetric counterpart in the rеgiоп 1160 ::J: 30 cm l, both with high
intensity. In the spcctra of а series оС thirty 3 and 4 X PhNH502Me compounds
'Ье V a S02 is assigncd а! 1335:1: 10 cm l and the V s S02 а! 1160:1: 10 cm l [61J,
and in 2 ThS02NHR' compounds а! 1340:1: 15 апd 1145:1: 15 cm l [60]. Kalova
е/ а/. [19] found 1340 :1: 20 and 1160:1: 20 cm l for the series of sесопdаry
sulfonamides.
The S02 scissors is аssigпеd in the rеgiоп 560 :1: 40 cт 1 апd 'Ье S02 \vаggiпg
vibration near 500 :1: 55 cm 1, both with medium iпtепsitу апd clearly separated.
А compound such as PhS02NHPh absorbs а! the HW side with 580 апd 554 cm 1
for these dcformations and МеS02NНСDз а! the LW side with 522 апd 446 CПl I,
followed Ьу MeS02NHMe with 523 and 457 cт 1.
The S02 twisting vibration is assigned iп the area 440 :1: 40 cт l апd [Ье 502
rock in the neighbourhood of 350 cт 1 оп the basis of the scarce data available.
The N S vibrations
ТЬе N S stretching vibration provides а weak 'о moderate Ьапd in [Ье rапgе 905
:1: 70 cm 1 . In the spectra of the N substituted 2 thiорhепеsulfопаmidеs, Arcoria е/
296 Norllla/ Vib,'atio//s a//d AbsOIptio// Regio//s о! SII/fш' COlllpo/тds
а/. [60] assigncd Ihe vN S in tllC rcgion 900 :1: 65 cm l, Wllicll narrows 10 925 :1:
40 cm ! wilhoul thc low value of 835 cm l from tllC spcctrum of 2 TI1S02NHMc,
а wavenumber also applicablc for tl1C samc vibration in MCS02NHMc. TllC majority
of Ihe il1vcstigatcd sccondary sulfonamides wcre found 10 give Ihis strclching
vibralion аl 910:1: 35 cm l.
Thc C N S dсfоrПШliоп absorbs ncar 280 cm t.
ТаЫе 11.11 Absorption rcgions (cm l) of (Ье поrmа\
vibrations of R S02NH R'
Vibration Rcgion Vibration Rcgion
vNH 3270 :1: 65 8s0 2 560 :1: 40
8NH 1395 :1: 25 WS02 500 :1: 55
V a S02 1330 :1: 30 7S02 440 :1: 40
V s S02 1160 :1: 30 pS02 ::::::350
vN S 905 :1: 70 8C N S ::::::280
I'NH 650 :1: 50 torsion
R
Me
R S(==0)2 NH R' molecules
4 02NPhCH2
FзС
Ph do and d5
4 MePh
2 02NPh
4 02NPh
2 H2N 4 CIPh
R'
Me [16, 17], СDз [16], iPr and IBu , [17], Ph-
do and d5 [18], H2N , 4 XPh (Х = Ме, МеС(==О),
N=C, 02N, МсО, MeS(==0)2, CI) [19], 3 XPh (Х = Ме,
02N, СI ) [19]
Me
2,6 Et2Ph
Me [17], Ph [43]
Me [17, 19,65]
Ph and 3 XPh (Х = Ме, 02N, МеО, Cl) and 4
XPh (Х = Ме, МсС(==О), N=C. 02N, МеО, CI) [19]
Ph and 3 XPh (Х = 02N, CI) and 4-ХРh (Х = 02N,
Мео, Cl) [19]
N=CCH2CH2
11.3.7 Sulfonyl
The R S02 R' compounds in which R and R' represenl а saturaled or
unsaluraled carbon alom, generally namcd sulfones, have Ьесп considered. The
mClhylsulfones wilh Ihe formula MeS02 R' bclong also 10 Ihe melhylsulfonyl
group (see Scclion 11.3.1).
11.3 Su/foIlY/ Coтpouпds
297
Thc S02 strctching vibrations
Ехсср! for (CCI3)2S(==0)2 (1382) and (СВrЗ)2S(==0)2 (1374 cm t) the S02 апti
symmctric strctching vibration appears strongly in the rеgiоп 1315 :!: 45 cm 1.
Thc highest wavcnumbcrs arc those due to 4 cIPhS02cF2cH(F)cl (1360) and 3
02N 4 FPhS02Ph 3 N02 4 F (1354 cm t) апd the lowest have Ьееп traced in the
spcctra of MCS02PhNHNH2 (1270) and MCS02Et (1274 for V.S02 апd 1302 for
LLlcH2 [11], but bcttcr thc rcversc ?). Thc rеmаiпiпg sulfопеs display the V.S02
а! 1305 :!: 25 cm J, thc samc rеgiоп as that found Ьу Flett [59] for 15 sulfопеs.
Schreiber [58] has examined 16 sulfoncs and located the V.S02 iп the range 1325
:!: 25 cm J.
The S02 symmetric stretching vibration is observed а! 1150:!: 30 cm l, а rеgiоп
in good agreement with that proposcd Ьу Schreiber (1140 :!: 20 cm l) or Ьу Flett
(1I55:!: 10 cm J). For а numbcr of RS0 2 R' соmроuпds iп ccI 4 sоlutiоп, Butcher
et а/. [48] found а correlation bctween the two vibrations: v, == 0.679 V. + 244.
The S02 deformations
With the exception of the extreme values 625 and 606 cm 1 for respectively 5 02N
2 PyS02 2 Py 5 N02 and 2 PyS02 2 Py 5 N02 [66], the S02 scissors gives rise
'о а moderate band in the region 540 :!: 60 cm J. High values оrigiпаtе also fюm
the spectra of 4 СIРhS02СF2СН(F)Сl (598), 2 PyS02 2 Py (594) and 2 PyS02Ph
(592 cm 1). The 10west wavenumbcrs are assigned in the spectra of СDЗSО2СDз
(488) and MCS02Me (500 cm J). Most оС the sulfопes have their аЬsоrptiопs iп
the region 550 :!: 40 cm J.
The S02 wagging vibration is active in the rеgiоп 500 :!: 70 cт 1 with
high values for 5 02N 2 PyS02 2 Py 5 N02 (570), 2 PyS02 2 Py 5 N02 (569), 2
PyS02 2 Py (568), 2 PyS02Ph (566), PhS0 2 Ph (563) and 4 СIРhS02СF2СН(F)Сl
(561 cm J) and low wavenumbers for СDзSО2СDз (426) апd пНехS02пНех (441
cm l). Disregarding thcse extreme values, most of the sulfопеs absorb а! 505 :!:
45 cm J.
Ignoring without rejecting the low values of 312 cm ) iп the spectrum of
PhS0 2 Ph and 307 cm J in that of 2 PyS02 2 Py 5 N02, the S02 twistiпg vibration
is reported in the range 420 :!: 75 cm J. The twепtу availabIe values for the S02
rock are locatcd in the region 345 :!: 55 cm t.
ТаЫе 11.12 Absorption regions (cm l) of 'Ьс normal
vibrations of R S02 R'
Vibration Region Vibration Rcgion
V.S02 1315 :!: 45 LLlS02 500 :!: 70
V,S02 1150 :!: 30 7S02 420 :!: 75
БS0 2 540 :!: 60 pS02 345 :!: 55
298 Norma/ Vibratio//s тll/ Abso/1Jtio// Regio//s о[ SII/[Ш' СоmРОШIl/S
Thc data are collcclcd frош tl1C spectra of 111C followiI1g R S(==0)2 R'
compounds.
R=
R
Ph
4 MePh
4 CIPh
4 BrPh
4 H2NPh
2 Py
R' == СDз [9], Et , nPr , iPr , nBu , sBu , iВu and
пНех [2], ССlз and СВrз [68], H2C==CH [2, 70,
71], Pll [43, 58, 64, 66, 70], Ph d5 [43], 4 McPh , 4
McO(O==)CPll , 3 and 4 H2Pll , 4 HOPh , 4 FPh , 4-
CIPh , 3 02N 4 FPh , 2,5 Вr2 4-НОРh , 2 Py [66, 67],
5 02N 2 Py [66]
R'
MeO(0==)CCH2 , HO(0==)CCH2CH2 , CICH 2 and BrCH2
[63], H2C==CH , 4 CIPll , 2 H2NPll , 2 Py [67]
CICH2 and BrCH2 [63], N=CCH2
CICH2 and BrCH2 [63], CI(F)CHCF2
CICH2 and BrCH2 [63]
Me(CH2)15
2 Py 5 N02 [66].
References
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12
N ormal Vibrations and
Absorption Regions of
Ring Structures
12.1 CYCLOPROPYL
According to the D зl , structure, cyclopropane has only 14 поrmаl viЬrаtiопs [1 5].
Substitution of а hydrogen Ьу Х gives rise to а cPr Х molecule with 21 поrmаl
vibrations (12а' + 9 а"), belonging to the С, group, for which the рlапе of 'Ье
molecule is по! the symmetry plane:
а': v a CH 2 , VsCH2, vCH, БСН 2 , БСН, ТСН2, vR, БsR, ""СН2, рСН2, yC X and
Б С Х;
а": v a CH 2 , v s CH 2 , БСН2, тСН 2 , ""сн 2 , 7 (w)CH, БаR, рСН2 and 7 C X.
in which vR rcpresents the cyclopropyl ring Ьrеаthiпg, БаR the апtisуmmеtriс ring
deforrnation and БsR the symmetric ring dеfоrmаtiоп. Тhe mеthуlепе vibrations
зrе iп рhаsе (а') or out of phase (а"). Substitution оС yC X (а') Ьу а tоrsiоп (а")
gives the 21 vibrations of the cPr fragment.
Methylene vibrations
Тhe five СН stretching vibrations absorb а! wavenumbers higher thап 3000 cm 1,
the region in which the absorptions of the sp2 hybridized СН Ьопds are active.
Because of coincident wavenumbers, usually the spectrum reveals only two bands,
а typical pattern for the three membered ring.
ТЬе two methylene deformations, which absorb iп а region (1475 1410 cm 1) in
which the sрЗ hуЬridizеd methylene groups also зrе active, appear clearly separated.
302 Norma/ Vib/.atiolls alld AbsOlplioll Regiolls о[ Rillg SlmCll/res
MoSI of 111C invcstigalcd moIeculcs SllOW the 6СН in 111C rcgiol1 1345 :i: 50 cт 1.
Although thc two metllylel1c t\visling vibralions absorb in ncigllbouring rcgions
(1175 :i: 20 and 1130 :i: 40 cт 1), coil1ciding wavcl1t1mbcrs arc thc exccption
rathcr Ihan а rulc. Both mcthylcnc \vаggiпg vibrations and IIIC СН wag occurring
bet\vcen 1105 and 975 cт 1 are more or less couplcd. Bccause it is not always
obvious Wllicll vibration makcs the grcatcsl contribulion to а distincl absorplion,
Ihese \vags arc assigncd as WCH2/WCH or wCH/wCH2. 'С it is acccptcd that Ihe
СН2 rock absorbs а! lo\vcr wavcnumbcrs tl13n thc ring dcformations, Ihc regions
830 :i: 40 and 765 :i: 50 cm 1 are uscful for bOlll rocking vibralions.
Ring vibrations
ТЬе ring breathing, absorbing at 1200 :i: 20 cm l, is а good group vibration for
cyclopropyl compounds. ТЬе intensity is only modcrate in the infrared but strong
in the Ramап. Although much vibrational analysis revcals the antisymmetric ring
deforrnation а! 930 :i: 55 cm 1, sometimes а СН2 rock is assigned in this rcgion,
and the ring vibralion is located in the region of thc rock (830 :i: 40 cm I). The
symmetric ring deformation absorbs in the rcgion 860 :i: 45 cm l.
ТаЫе 12.1 Absorption rcgions of (Ьс normal viЬrаtiопs of
cPr
ViЬrаtiоп Rсgiоп Vibration Rcgion
V a CH 2 3090 :i: 25 WCH2/CH 1075 :i: 30
V a CH 2 3075 :i: 25 WCH2/CH 1040 :i: 30
V s CH 2 3040 :i: 40 wCH/ CH 2 1010 :i: 35
V s CH 2 3020 :i: 20 6a R 930 :i: 55
vCH 3015 :i: 45 6.,R 860 :i: 45
6СН, 1455 :i: 20 Р СН 2 830 :i: 40
6СН; 1425 :i: 15 РС Н 2 765 :i: 50
6СН 1330 :i: 90 cxt.sk.dcf.
vR 1200:!: 20 cxt.sk.dcf.
ТСН2 1175:!: 20 torsion
ТСН2 1130:!: 40
R cPr molecules
R = D [6], Me [7], Et [8], cPrCH2 [9, 10], N=CCH2 [11], HOCH2
[12, 13], CICH2 [11, 1 17], BrCH2 [11, 17, 18], ICH2 [11,
17], HO(Me)CH [12], iPr [8], cPr [19], H2C==C(cPr) [20],
HC=C and DC=C [21], cPrC=C [22, 23J, N=C [2 30],
C==N [31], H(O==)C [32], F(O==)C [33], CI(O==)C [5, 25,
34, 35], Br(O==)C [5, 25], Me(O==)C [36, 37], HO(O==)C [38
40], 02C [5, 39], MeO(O==)C [36], cPr(O==)C [20, 41],
Ph(O==)C [42], 4 XPb(0==)C (Х = F, CI, Br) [43], H2N(0==)C [38],
J 2.3 Aziridi1lY/
303
H2N [44, 45], D2N [44, 46], 02N [78], O==C==N [47),
S==C==N [47 9], CI [5, 48, 50], Br [5,25,48,51, 52), ' [5.
48], FзSi [53J, (cPr)2HSi [54].
12.2 OXIRANYL
Oxiranc (cthenc oxidc) Ьсlопgs 10 Ihe роiпt group С2" апd the 15 поrmаl vibrations
are dividcd among 5аl + 3а2 + 3ы + 4Ь2 species of viЬrаtiоп [55 59J.The охirапуl
(сС2НЗО) fragmcnt gives risc 10 3N 6 = 15 normal viЬrаtiопs, of which 12 are
collectcd in ТаЫе 12.2.
The СН stretching vibrations absorb Ьеtwсеп 3070 апd 2970 cm l, but the
position of Ihe vCH is uпссrtаiп. Nyquist et а/. [63] апd ТоЫп [60] assigп the
region 1410 ::!: 35 cm l rather 10 the СН 2 twisting viЬrаtiоп and the region 1175
:i: 35 cm l 'о the СН dеfоrmаtiоп.
ТаЫе 12.2 Absorption rcgions (cm 1) of [Ье попnаl
vibrations of Ox
Vibration Rеgiоп Vibration Rеgiоп
V a CH 2 3055 ::!: 15 wCH 1075 :i: 35
vCH 3005 :i: 30 БаR 920 :i: 45
V s CH 2 2990 :i: 20 БsR 845 :i: 35
БСН2 1465 ::!: 35 рСН2 775 :i: 25
Бен 1410 ::!: 35 cxt.sk.def.
vR 1255:1: 10 cxt.sk.dcf.
ТСН2 1175 :1: 35 torsion
"" СН 2 1130 ::!: 10
Ксу: vR: ring brcathing: БаR: riпg anlisymmclric iп'рlаDС
deformation; c5 s R: ring symmclric in.planc dcformalion.
R Ox moleculcs
R = Me [5, 6Q.....62], Et [8, 62], Me(CH2)п (11 = 7, 8, 11, 13, 15)
[62], FCH2 [17, 63, 64], CICH2 [16,17, 63], BrCH2 [17, 18,63),
ICH2 [17, 63], jPr , iBu , tBu [62], Ox [66], H2C==CH [65],
Ph , 2,4 CI2Ph .
12.3 AZIRIDINYL
Aziridine belongs 10 the point group С . and the 18 поrmal viЬrаtiопs зrе divided
iпtо 10 а' + 8 а" specics of vibration [67 72]. In N.substituted R Az c?mpounds,
the Az fragmcnt (cC2H4N ) possesses 18 поrmal viЬrаtiопs, of \vhlch 15 зrе
collected in ТаЫе 12.3.
304 No/'lllU/ Vibro/io"s Оlll/ AbsOIp/io" Regio"s о[ Ri"g S//'IIclllres
Тhe in phasc (а') and оut оf рlзаsс (a/l) СН 2 апtiSУП1mсtric and symmctric
stretching vibrations coincidc but thc СН2 dcformatiol1s arc obscrvcd scparately.
The ring breathing (а') occurs а! 1235 :!: 50 cm 1 and а! 1212 СП1 l in aziridinc,
althougll Spcll [77] assigned this vibration in the region 1285 :!: 75 СП1 l.
ТаЫе 12.3 Absorption rcgions (cm 1) of the normal
viЬrаtiопs of Лz
ViЬrаtiоп Rсgiоп Vibration Rcgion
V a CH 2 3080 :!: 20 WCH2 1115 :!: 30
V a CH 2 3080 :!: 20 WC H 2 1065 :!: 40
V s CH 2 3000 :!: 25 БаR 905 :!: 20
V s CH 2 3000 :!: 25 БsR 850 :!: 30
БСН2 1470:!: 15 рС Н 2 815 :!: 25
БСН2 1445 :!: 20 Р СН 2 765 :!: 35
vR 1235 :!: 50 ext.sk.dcf.
ТС Н 2 1210:!: 50 ext.sk.dcf.
ТСН2 1145 :!: 40 tоrsiоп
R Az П101ссulеs
R = Me [5], Az [75], AzC(==o) [73], H2NC(==0) and
02NC(==0) [74], AzS(==o) [70], Cl and Br [69,76].
References
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305
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58. J.E. Bcrtic and О.А Othcn, Сап. J. CI,eIII., 51,1155 (1973).
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306 N01'flla/ Vib,'u1iolls ulld Absorp1io1l Rcgiolls о[ Rillg S1mc1111'cs
61. P.L. Polavarapu, L. НссЬ! and L.D. Baron, J. P//ys. С//ст., 97, ] 793 (1993).
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65. У.Е Kalasinsky and S. Pcchsiri, J. Rama/l Spcc/rosc., 9, 120 (1980).
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127,337 (1988).
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77. H.L. Spell, A/la/. С//ст., 39, 185 (1965).
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12.4 PHENYL
Benzene, bclonging 'о the роiпt group D61" hзs 20 normal vibrations, of which fош
are infrared active. After substitution of an Н зtоm Ьу ап Х atom, the symmctry is
lowered from Dбt. to С2" and the number оС normal vibrations increases to 30, bcing
СН, СХ and ring vibrations. Ву ап uncoupling, 'Ьс vibrations 6 up to and including
10 and 16 up to and including 20 of benzene are redoubled. This uncoupling does
not take place in 1,3,5 trisubstituted benzenes with idcntical substituents. А further
lоwеriпg of the symmetry fюm С2" 'о С , leads to а distribution of the normal
vibrations in 21а' and 9з" types. ТаЫе 12.4 shows the поrmзl vibr3tions of benzene
and X substituted bcnzene derivatives, corresponding to the Wilson notation [8].
ТаЫе 12.4 Normal vibrations of benzene and substitutcd bcnzcnes
Bcnzene Х substitutcd bcnzcncs
О61. С2" а1 а2 Ь1 Ь2
С , а' а" а" а'
vCH 2, 7, 13, 20 vCH,vCX 2, 7а, 13, 20а 7Ь, 20Ь
vPh 1,8, 14, 19 1, 8а, 19а 8Ь, 14, 19Ь
Бсн 3, 9, 15, 18 Бсн, Бсх 9а, 18а 3, 9Ь, 15, 18Ь
БРh 6,12 6а, 12 6Ь
,СН 5,10,11,17 ,СН, ,СХ 10а, 17а 5, 10Ь, 11, 17Ь
,РЬ 4,16 16а 4,16Ь
12.4 Pheпy/
307
Evcry ncw substitucnt Icads (о three СХ vibrations апd diminishes (Ье пumЬеr of
СН vibrations Ьу thrcc, but there is some ambiguity iп deducing which number of
СН vibration, according to Wilson, is replaced Ьу а СХ viЬrаtiоп апd the literature
docs по! agrcc conccrning this probIem. Iп mопоsuЬstitutеd Ьепzeпes six modes
of vibration arc substitucnt scnsitivc, which mеапs 'Ьа! their wavenumbers shift
sigпifiсапtlу with mass or inductive or mesomcric cffccts of (Ье suЬstituепt. Тhe
remaining 24 сап Ьс considcrcd good group viЬrаtiопs. Тhc strеtсhiпg апd Ьепdiпg
of the substituent bond поt опlу give rise 'о а Pb X strеtсhiпg viЬrаtiоп, а Pb X
in plane and а Ph Х оut оf рlапс dеfоrmаtiоп, but also iпfluепсе the аЬsоrptiоп
frсquспсу of а ring strctch, ап iп рlапс апd ап оut оf рlапе riпg dеfоrmаtiоп. Тhese
ring vibrations are couplcd with thc Pb Х viЬrаtiопs iп such а way as to make it
difficult to dctermine which wаvепumЬеr Ьеlопgs (о а Pb X vibration апd which
wavenumber to а ring vibration. For this rеаsоп, the tabIes shоwiпg аЬsоrptiоп
regions do по! always agrec completely with 'Ье assigпmепts iп 'Ье literature:
interchange сап occur betwecn some suЬstituепt sепsitivе modes. For disubstituted
benzenes 10 от 11, апd for trisubstituted Ьеnzeпеs 14 or 15 suЬstituепt seпsitivе
viЬrаtiопs are taken into account.
The СН and СХ stretching vibrations (2, 20а, 20Ь, 13, 7а, 7Ь)
The СН stretching vibrations absorb weakly to moderately Ьеtwееп 3120 апd
3000 cm l. ТЬе highest values near 3120 cm 1 are observed iп [Ье spectra
оС benzcnc substituted with СF з , F, 02N апd C=N; examples зrе 2 апd 4
02NРhСFз, 2,4 (02N)2PhF, 2 Сl(0==)СРhСFз, 2 N=СРhСFз, 4 MeOPhC=N
and 2,5 Me2PhC=N. In this ncighbourhood also оvеrtопеs or соmЫпаtiопs of
ring strctching vibrations сап occur. Low values (пеаr 3000 cт 1) are assigned
in the spcctra of (substituted) аlkylЬепzепеs such as Ph nBu, 4 H2NPhEt, +
MePhCH 2 CI and 4 MePbCH2BT. UsuaIly the СН stretching viЬrаtiопs зrе active
Ьеtwееп 3110 and 3010 cт 1.
'П monosubstituted bcnzenes the highest suЬstituепt sепsitivе rnode аррезrs in
the region 1175 :1: 115 cт 1, in this text caIled the C X stretching vibration
(iп vibrational analysis оftеп 13 or 7а). Ассоrdiпg 'о Varsапуi апd Szбkе [1], (Ье
absorption in the rеgiоп 1195 :1: 90 cm 1 is for the most part due (о а C X
stretching vibration in benzencs substituted with а light atom (atornic rnзss < 25)
апd that in the rcgion 1090 :1: 30 cm 1 to а ring stretch iп Ьепzепеs substituted
with а heavy atom (atomic mass > 25). The Ph c strеtсhiпg viЬrаtiоп iп aJl.:yl
Ьепzепеs appears weakly in ,Ье neighbourhood of 1210 cm l. Тhis Ьапd shifts 'о
higher wavenumbers in benzenes substituted with atoms with ап unshared pair of
electrons пех! to the ring (activators) such as пitrogеп (:::::1280) апd oxygen (:::::1250
cm 1). Bcnzenes with multiple bonds пехt to the riпg (deactivators) such as N 0 2
and N==C==O (1107), С(==О)ОН, C(==0)NH2 and С0 2 (:::::1150) and С=СН
and C=N ( 1190 cт 1) absorb а! lower wаvепumЬеrs. lп Ьепzепes substituted
with а Р atom this substituent sensitive mode occurs пеar 1100 cm l, with ап
308 Norllla/ Vibratiolls а/l(/ Absorptioll Regiolls о! Rillg Stmctllres
S atom near 1090 and \vith ап As atom near 1080 cm l. In l1alogcnatcd bcnzel1cs
the wavenumbcr drops from 1083 cт 1 in cll10robcnzenc, via 1070 in bromo
benzene, to 1060 cm ! in iodobcnzene. Тhc intensity of tllis Pb X strctching
vibration increases with tllC polarity of the Х atom. In di- and tri-substitutcd
benzenes thc same cffccts are applicable within the appropriate absorption regions.
For substituents in thc 1,3 position, опс of ,Ьс Pb Х strctching vibrations absorbs
а! lower wavcnumbers (lIIeta effcct) [1].
Ring strctching vibrations (8а, 8Ь, 19а, 19Ь, 14, 1)
Тhe bcnzene ring possesses six ring strctching vibrations, of which the four with
'Ье highest wavenumbers (8а, 8Ь, 19а and 19Ь, occurring respcctively near 1600,
1580, 1490 and 1440 cm l) are good group vibrations. With Ьсауу substituents
thc bands tend 'о shift to somewhat lower wavcnumbers. Тhe greater the numbcr
оС substitucnts оп the ring, the broader the absorption regions wil1 Ье.
In thc absence of ring conjugation, the band а! 1580 cm l is usual1y weaker
than that а! 1600 cm t. In mапу cascs, such as alkyl substitution, the 1580 cm l
absorption is only а shoulder оп the 1600 cт l band. When the ring is substituted
а! the 1,4 position with identical substituents, both vibrations are infrared inactive.
In the case of с==о substitution the band near 1490 cm l сап Ье very weak. The
fifth ring stretching vibration (vPh 14 or Kekule vibration) is active ncar 1315 :1: 65
cm l, а region which overlaps strongly that of the сн in plane deformation (бен
3). If further data are по! available, ,Ье highest {lowcst} wavenumber is assigned
to the ring stretching vibration (vPh 14) {сн in plane deformation (бен 3)}. In
phenols this ring stretching vibration is coupled to the он in plane deformation
Ьу which the region extends to 1390 cт l [2]. ТЬе sixth ring stretching vibration
or ring breathing mode (vPh 1) appears as а weak band near 1000 cm l in mопо
,1,3 di and 1,3,5 tri substituted benzenes. In the otherwise substituted benzenes,
however, this vibration is substituent-sensitive and difficult to distinguish from the
ring in plane deformation (БРh 12). In this text the ring breathing is assigned а! а
higher wavenumber than thc ring in plane deformation.
The сн and СХ in plane dcformation (3, 9а, 9Ь, 15, 18а and 18Ь)
Supposing that аН thc сн in plane deformations absorb а! lower wavenumbers than
the ring stretching vibration vPh 14, the сн in plane deformation with the highest
wavenumber (бен 3) mау Ьс assigned а! 1265 :1: 65 cm l. Togethcr with the othcr
сн in plane deformations this providcs а supplementary indicator for 'Ье presence
of а benzcne ring.
Particularly in di and tri substituted bcnzenes the substituent sensitive РЬ Х
in plane dct.ormations are of minor importance as а diagnostic tool. ТЬе heaviest
substituents give rise to thc lowcst wavenumbcrs.
12.4 PJ/eпy/
309
The СН and СХ out of plane dcformations (5, 17а, 17b, 10а, 10Ь and 11)
The СН out of plane dcformations arc obscrved between 1000 апd 720 cm l,
but 2 H(0==)CPhC(==0)H (1002), 2 02NPhC(==0)H (1002) and 2 02NPhN02
(1005) overstcp this uppcr limit. Generally the СН out-of plane deformations with
the highcst wavcnumbcrs have а weaker intensity than those аЬsоrЫпg а! lower
wavcnumbers. Thc spcctral position of the weaker СН оut оf рlапе dеfоrmаtiоп
near 900 cm l ОП this 'сх! namcd /CH 17Ь) corrclates wcll with the electron
dопаtiпg or elcctron attracting properties of the substituent (see ТаЫе 12.5). The
stronger СН in phase oиt of planc dcformation band осcurriпg in the region 770 :1:
50 cm l (, СН 11 or umbrella modc) also tcnds 'о shift 'О lower {higher} wave
пumЬеrs with increasing electron donating {attracting} power of the suЬstituепt,
but seems 'о Ье more sensitive to mcchanical interaction effects. The lowest wave
пumЬеrs for this иmbrella mode are foиnd in the spectra of Ьепzепеs substituted
with а saturated carbon or ап hcavy atom such as halogen, sulfur or phosphorus
[2, 3, 5, 7].
ТаЫе 12.5 Absorption wavenumber (сm 1) of , СН 17Ь апd , СН 11 in mопоsuЬstitutеd
Ьепzепеs
SuЬstituепt , СН 17Ь , СН II Substituent , СН 17Ь ,СН 11
C(==O)F 938 797 СН== СН 2 909 775
С(==О)СI 937 777 СН==СНМе 909 735
С(==О)ОМе 936 808 NHC(==O)Me 906 755
С(==О)ОН 935 812 N==C==S 905 749
N02 934 793 tBu 905 765
S(==0)2 Me 932 750 пРr 905 743
S(==0)2 C1 930 752 Е! 904 746
S(==0)2 NH 2 928 754 N==C==O 904 751
С(==О)Ме 927 760 1 904 730
C=N 926 758 Br 903 735
C(==0) NH 2 925 807 СI 902 740
CF] 924 770 iPr 902 761
S(==0)2 Ph 921 758 С Н 2 С1 900 768
С(==О)Н 920 746 CH2N==C==S 899 733
С02' 919 819 Ме 896 728
S(==O)Me 919 748 F 896 753
С=СН 918 757 SH 895 727
CH==C(C=N)2 918 764 SMe 893 738
CCl] 917 788 ОС(==О)Ме 892 750
CHCI2 916 780 ОЕ! 884 755
CH2Br 915 758 ОН 883 757
S(==O)Ph 915 754 ОМе 882 754
СН20Н 912 735 N H 2 880 753
С(Ме)== СН 2 912 770 NHMe 870 754
CH2NH2 910 736 NMe2 864 758
310 Norma/ Vib,'atio/lS а//(I AbsOIptio/l Rcgio/ls о! Ri/lg Stтctlll'CS
Тlle wcak substituent scnsitive Ph Х out of plane dcformations absorb а! thc
LW sidc of [Ьс Pll X in plane dсfоrnшtiопs. TllCY arc of liШс praclical use il1
clucidating thc molccular structurc.
Ring dсfоrmаtiопs
Thrcc or more ring dеfоrmаtiопs are substituent scnsitive and thcir utility for
idспtifiсаtiоп purposes is very limited. They arc strongly couplcd 'о the Ph X
strctcl1ing vibration and ап intcrchange witll the latter is по! cxcluded. Тlзе ring
out of plane deforrnation occurring near 695 cт l (, Ph 4), оп 'Ье contrary, merits
bcing caIled а good group vibration. It is, together with the lowcst СИ out of plane
deformation, of great imроrtапсе in distinguishing different typcs of aromatic ring
substitution.
Types of aromatic ring substitution (region 97 650 cm )
The out of plane СН deforrnation near 770 cm ! (, СИ 11) and thc out of plane
ring deformation absorbing near 690 cт ) (, Ph 4) forrn а pair of strong bands
characteristic оС monosubstituted Ьепzепе derivatives [7]. The spectral position оС
, СИ 17Ь and , СИ 11 in а numbcr of monosubstituted benzenes is shown in ТаЫе
12.5.
In the case of 1,2 disubstitution only опе strong absorption in the region 755 ::1:
35 cт 1 is observed, and is due [о the , СН. The out of plane ring deformation
, Ph 4 gives rise to а weak shoulder оп the , СН band or coincides with it, or is
еуеп inactive for identical substituents. colthup [3] calculatcd the СН out of plane
deformations near 940 and 755 cт ! with the 900 cт ! phenyl band (,СИ 17Ь)
wavenumbers of benzenes substituted with the same substitucnts as оп the 1 and
2 роsitiопs (see ТаЫе 12.5).
,СИ near 940 = 0.5 (ст! + СТ2) + 36 cm !
, СН пезr 755 = 0.5 (СТI + СТ2) 149 cт )
in which ст! = , СН 17Ь wavenumber оС Ьеnzепе substituted with the same group
as оп the l position and СТ2 = , СИ 17Ь wavenumber оС benzene substituted with
the same group as оп the 2 position.
Тlзе 1,3 substitution pattern resembIes that of monosubstitution, with the СИ
out of plane deformation near 770 cт ! and the out of plane ring deformation
(, Ph 4) in the neighbourhood of 685 cт ) oftcn absorbing with equal intensity.
According to the formula of Colthup [3]:
! СН near 860 = 0.9 (ст) + стз) 757 cm I
, СИ near 770 = 0.5 (СТI + стз) 120 cm )
12.4 Pheпy/
311
in which (11 {(13} = , СН 17Ь wavenumber of benzene substituted with (Ье same
group as оп the 1 {з} роsitiоп (see ТаЫе 12.5).
ТЬе strong св out of plane deformation, occurring а! 840 :1: 50 cт l, is
typical for а 1 ,4 disubstitution. This band is situated а! а greater distапсе from
'Ье weak ring out of pIane deformation (, Ph 4), which is еуеп iпfrаrеd iпаctivе
with identical substituents. The Jower СН out of plane dеformаtiоп absorbs iп the
same neighbourhood (820 :1: 45 cm 1) Ьи! is much weaker or iпfrаrеd iпасtivе.
According to the formula of Colthup et а/. [4] (Ье "( СН пеаr 840 cm 1 сап Ье
predicted from the , СН 11 wаvепuтЬеrs of both suЬstituепts:
, СН near 840 = 0.6 «(11 + (14) 75 cт 1
in which (11 {(14} = , СН 11 wаvепumЬеr of Ьепzепе substituted with 'Ье same
groиp as оп position 1 {4} (see ТаЫе 12.5).
For 1,2,3 trisubstitution the strong СН оut оf рlапе dеfоrmаtiоп апd 'Ье ring
out of plane deformation (, РЬ 4) are respectively observed а! 790 :1: 40 and 710
::1: 30 cm 1.
,СИ пеат 790 = 0.6 «(11 + (13) 303 cm 1 [3]
in which (11 {(13} = , СН 17Ь wavenumber of Ьепzепе substituted with the same
group as оп position 1 {3}.
In the case of 1,2,4 trisubstitution, two medium to strопg I СН bands are
observed а! 890 ::1: 50 and 815 :1: 45 cт 1 respectively. The I РЬ 4 appears as
а medium band а! 700 ::1: 40 cт l.
, СН near 890 = 0.7 «(12 + (14) 393 cm 1 [3]
in which (12 {(14} = , СН 17Ь wavenumber of Ьепzепе substituted with 'Ье same
group as оп position 2 {4}.
, СИ пезr 815 = 0.6 «(11 + (14) 75 cm 1 [4]
iп which (11 {(14} = , СН 11 wavenumber of Ьепzепе substituted with (Ье same
group as оп position 1 {4}.
1,3,5 trisubstituted benzenes give rise to simple spectra if (Ье three suЬstitиепts
ате по! (оо different. 1dentical substitиents reduce the пumЬеr of поrmаl viЬrаtiопs
(о 20. UsиaIly а medium , СИ band is observed а! 835 :1: 25 cт 1 and another а!
860 ::1: 30 cm 1 accompanied Ьу а weaker Ьапd а! 890 :1: 50 cm 1. The lзs! t\vo
coincide if the three substitиents are identicaI or near idепtiса1 'о give опе band iп
(Ье region 885 ::1: 55 Cт l. Colthиp [3] caIculated the position of this I СН with
(Ье formиla:
, СИ = 0.7 «(11 + (13 + (15) 1040 cт l
312 NO/'1lla/ Vibra/io"s a"d AbsOlP/io" Regio"s о[ Ri"g S/1'IIc/llres
in which 0'1, О'з and 0'5 respeclively are tlle ')' СН 17Ь wavenumbers of benzenes
substituted with 111e saI1le group as оп position 1, 3 or 5.
SumI1lation bands (region 2000----1650 cI1l I)
Тlle infrared speclra оС substituted benzenes show а раНеrn оС weak bands that
tend 10 Ье characleristic for Ihe 'уре оС subslitution. Тhese bands are produced
Ьу overtones and combinations of the СН wаggiпg I1l0des. In с==о subslituted
benzenes, ho\vever, Ihese bands are dislurbed. According 'о Young е/ а/. [6] these
Iypical patterns are il1ustraled in Figure 12.1.
': I ;::-J ';J:...i..
.. ;... !. ; I .., ' .
. ..1... ,:' . .
., Ф'I "I ' +
I ::I
1,2,3 tri
1,2.4 tri
1,3,5 tri
.i.
I
. .' ,.:..
2000 1800
Figure 12.1
12.4 Pheпyl
313
12.4.1 Monosubstituted benzene derivatives
ТаЫе 12.6 Absorption regions (сm 1 ) of the normal viЬrаtiопs of mопоsuЬstitutеd Ьепzепеs
ViЬrаtiоп Wilson Мопо light Мопо ЬеауУ
IICH сн strctching vibration 20а 3085 :1: 20 3085 :1: 20
IICH сн strclching viЬrаtiоп 20Ь 3070 :1: 20 3075 :1: 15
IICH сн strctching vibration 2 3060 :1: 20 3055 :1: 15
IICH сн strctching viЬrаtiоп 13 3040 :1: 20 3040 :1: 20
,/сн сн strctching vibration 7ь 3020 :1: 20 3020 :1: 20
IIPh Phcnyl ring strctching vibration 8а 1605:1: 15 1590 :1: 20
IIPh Phcnyl ring stretching viЬrаtiоп 8Ь 1585:1: 15 1575:1: 15
IIPh Phenyl ring strctching vibration 19а 1485 :1: 25 1475:1: 15
IIPh Phenyl ring strеtсhiпg viЬrаtiоп 19Ь 1450 :1: 20 1435:1: 15
IIPh Рhспуl ring slrctching vibration 14 1335:1: 35 1310:1: 25
бсн СН in-planc dеfоrmаtiоп 3 1295 :1: 25 1275 :1: 25
IICX Phcnyl X strсtсhiпg vibration 7а (х) 1195:1: 90 1090 :1: 30
бсн сн iп рlапе deformation 9а 1175:1: 20 1180:1: 15
бсн сн in planc dcformation 9Ь 1150 :1: 20 1165 :1: 10
бсн СН in plane dcformation 15 1070 :1: 20 1065:1: 15
бсн сн in planc dcformation 18а 1020 :1: 20 1025:1: 10
IICH РЬспуl ring stretching viЬrаliоп 1 1000 :1: 10 'ООО :1: 05
')'СН сн out-of-planc dcformation 5 980 :1: 20 980:1: 15
')'СН сн out of-planc dcformation 17а 960 :1: 25 965:1: 10
')'СН СН out-of planc dеfоrmаtiоп 17b 900 :1: 35 915:1: 20
')'СН СН out-of planc dсfоrmаtiоп 10а 840 :1: 25 835 :1: 20
J'CH СН out-of planc dcformation '1 775 :1: 45 745 :1: 25
Ph Phcny1 ring iп-рlапс dcformation 12 (х) 750 :1: 80 700 :1: 50
J'Ph Phcnyl ring out-of-planc dcfonn. 4 695:1: 15 685:1: 15
Ph Phenyl ring in-plane defonnation 6Ь 625:1: 15 605:1: 15
;SPh Phcnyl ring out-of plane defonn. 16Ь (х) 510:1: 90 475 :1: 55
Ph PI1enyl ring iп рlапс dcformation 6а (х) 420 :1: 115 355 :1: 90
'у Ph Phenyl ring out of plane dcform. 16а 405 :1: 25 405:1: 15
бсх Phcnyl X in-plane dеfоrmаtiоп 18Ь (х) 300 :1: 110 250 :!: 60
')'СХ Рhспуl Х оut оf рlапе dcform. 10Ь (Х) 205 :1: 70 170:1: 30
Мопо light = benzcncs substituled with а light atom (atomic mass < 25).
Мопо hcavy = bcnzcnes substituted with а heavy atom (atomic тш > 25).
(х) = substiluent scnsitive vibration.
х Ph compounds
Х = Me [9 11], Et [2, 9], nPr , nBu апd iВи [2], PbCH2CH2 [12,
85], CICH2CH2 [85], N=CCH2 [2, 13], H2NCH2 [2, 13],
SCNCH2 [2], HOCH2 [2], HSCH2 [14], N==C==SCH2 [15],
PhCH2SCH2 (16], CICH2 [2, 10], BrCH2 [13, 42], iPr апd
sBu [2], H2NCH2(Ph)HC and HOCH2(Pb)HC [17], CI2HC (10],
tBu [2], СlзС (10, 81, 82], FзС [27, 80], H2C==CH [18, 19,
24], PhCH==CH [29 31], (N=C)2C==CH [32], H2C==C(Me) [з3J,
Ph [29, 34], HC=C [2, 48, 49], N=C [20, 23, 35, 36],
CIC=C and BrC=C [84], Н(o==)c [22, 37], F(O==)C [26],
CI(O==)C [26, 38], Me(O==)C [26, 39, 40], HO(O==)C [25, 26,
41, 43], MeO(O==)C [2, 26, 44], H2N(O==)C [26, 45], 02C [25,
314 Nomla[ Vib/'atio"s a"d Absorptio" Rcgiolls о[ Ri"g Strис(ш'сs
46], H2N(S==)C [86], ЕtO(о==)с [26], H2N [47], McHN [2,
50, 83], Me2N [2, 50, 51, 83], Et2N [51], Me(O==)CHN [52],
02N [11, 43, 53, 54], O==C==N [55], S==C==N [56], CN [79],
HO [9, 57, 58], MeO [59, 60], ЕtO [9, 21], Me(O==)CO [2,
61], PhO [9], F [34, 36, 62----65], HS [21], MeS [66, 67],
PhS [28, 68], Me(O==)S [69], Ph(O==)S [28, 68], Me(0==)2S [69],
Ph(0==)2S [68], CI(0==)2S [2, 70], H2N(0==)2S [2, 70],
R2N(0==)2S (R = Ме, Et, nPr) [71], H2P [2, 72], (Ph)2P [73],
НзSi [74], Cl [64,70,75, 76], Br [77, 78], I [2,65,78].
12.4.2 Disubstituted benzene derivatives
ТаЫе 12.7 Absorption regions (cт 1) of the normal vibrations of 1,2 disubstituted
benzenes
ViЬraliоп
1,2 di hcavy
vCH
vCH
vCH
vCH
vPh
vPh
vPh
vPh
vPh
Бсн
vCX
vCX'
Бсн
Бсн
Бсн
-усн
-усн
-усн
vPh
1'сн
БРь
l' РЬ
БРь
РЬ
1'РЬ
ОРЬ
Бсх
6сс;,
-усх'
(х)
(х)
1,2.di lighl
3085 :f:: 35
3070 :f:: 30
3050 :f:: 30
3030 :f:: 30
1605 :f:: 20
1585 :f:: 20
1495 :f:: 30
1455 :f:: 25
1315 :f:: 40
1275 :f:: 25
1245 :f:: 55
1170 :f:: 80
1150 :f:: 20
1110:!:: 35
1030 :f:: 30
975 :f:: 30
940 :f:: 30
880 :f:: 40
810:!:: 80
755 :f:: 35
730 :f:: 80
705 :f:: 35
560 :f:: 90
525 :f:: 65
440 :f:: 30
380 :f:: 180
370 :f:: 70
270 :f:: 90
230 :f:: 70
180:!:: 60
1,Ыight hсаvу
3090 :f:: 20
3070 :f:: 20
3050 :f:: 20
3035 :!:: 35
1600 :!:: 20
1575 :f:: 15
1475 :f:: 25
1435 :f:: 25
1300 :!:: 40
1270 :f:: 30
1220 :f:: 80
1085 :f:: 55
1150:!:: 20
1125 :f:: 20
1030 :f:: 20
980:!:: 15
935 :!:: 25
880 :f:: 40
770 :f:: 70
755 :!:: 35
715 :!:: 85
700 :f:: 40
500:!:: 150
515 :!:: 75
430 :f:: 40
380 :!:: 180
360:!:: 100
270 :f:: 90
210:!:: 70
170:!:: 70
3090 :!:: 30
3065 :f:: 25
3050 :!:: 20
3035 :f:: 35
1590 :f:: 25
1570 :f:: 15
1470 :f:: 25
1440:!:: 20
1280:!:: 20
1255 :f:: 25
1105 :!:: 25
1050 :f:: 50
1160 :f:: 10
1125 :f:: 20
1030 :!:: 30
980:!:: 10
945 :f:: 15
860 :f:: 20
720 :!:: 30
755:!:: 15
685 :f:: 45
695 :f:: 35
450 :f:: 100
500 :f:: 60
420 :f:: 30
350 :f:: 150
270 :f:: 70
215 :!:: 35
170 :f:: 50
135 :f:: 35
(х)
(х)
(х)
(х)
(Х)
(Х)
(Х)
(х)
(х)
di light = bcnzcncs substitutcd with two lighl atoms (atomic mass < 25).
lighl hcavy = bcnzcncs substitutcd with а lighl and а Ьсауу alom.
di-hcavy = bcnzcncs substitutcd wilh two Ьсауу atoms (atomic mass > 25 О).
*: strong clcctron withdrawing groups such as N02, с(==о)он, C(==O)NH2, N==C==O givc Ihc
cffcct of а Ьсауу substitucnt.
(х) = X scnsitivc vibralion.
J 2.4 Pheпy/
315
The compounds include:
2 MePhX', where Х' = Ме [93], Et [2], С(==О)Н [22], С(==О)Ме [2],
С(==О)ОН [25, 97J, С02' [25J, НС==СН2 [87, 88], C=N [23], NH2 [50], N02
[94],01-1 [96], F and 1 [93], Br and СI [93, 168];
2 E\PhX', where Х' = Е\ [2], NH2 [2], ОН [2J;
2 FзСРhХ', where Х' = С(==О)Н [89], С(==О)СI [100], C=N [101], F, СI and
Br [27);
2 02NPhX', where Х' = C(==O)OI-l [2], NH2 [2], N02 [95, 102], ОН [103],
OEt [104], F [94, 105], СI [94,95, 105, 106J, Br [94,106],1 [94, 105);
2 HOPbX', where Х' = СН201-1 [107], С(==О)I-I [108, 109], С(==О)Ме [110],
С(==О)Е! [110], С(==О)ОМе апd С(==О)ОЕ\ [108], ОН [111, 112], F, а, Br апd
1 [96];
2 McOPhX', where Х' = С(==О)Н [113, 114], С(==О)Ме [2], NН2 [115], ОМе
[2], F [60], СI [60, 116, 117], Br [60,116,117];
2 FPhX', where Х' = CH2Br, С(==О)Н [22], С(==О)ОН [25], С02' [25],
НС==СН2 [87], C=N [23], NH2 [118], ОЕ\ [119], F [93, 12().....123J, а and Br
[93, 124, 125], 1 [93];
2 CIPhX', where Х' = СН 2 СI [170], С(==О)Н [22], С(==О)ОН [25, 97], С02'
[25], НС==СН2 [87], C=N [23], NH2 [126], ОЕ! [116], Сl [93, 95], Br and 1
[93];
2 BrPhX', where Х' = С(==О)Н [22], С(==О)ОН [25], С02' [25], НС==СН2
[87], C=N [23], OEt [116], Br [93, 127, 128],1 [93];
2 IPhX', where Х' = 1 [93];
2 HO(0==)CPhX', where Х' = С(==О)ОН [97, 129], NH2 [97], NНMe and
NMe2 [130];
2 H(0==)CPhX', where Х' = OEt [131], NH2 [132];
2 HC=CPhX', where Х' = С=СН [133];
2 N=CPhX', where Х' = CH2Br [169], C=N [134].
ТаЫе 12.8 Absorp\ion regions (cm l) of thc normal vibrations of 1,3 disubstituted
bcnzcncs
Vibration 1,3.di.Jight 1.3-light hcavy l,з.di.hсзvу
усн 3090 :!: 30 3090 :!: 20 3095 :!: 25
усн 3075 :!: 25 3075 :!: 25 3065 :!: 15
усн 3050 :!: 30 3050 :!: 20 3055 :!: 15
усн 3030 :!: 30 зозо :!: зо 30З5 :!: 25
vPh 1605 :!: 20 1595 :!: 20 1590 :!: 25
vPh 1585 :!: 20 1575 :!: 20 1570 :!: 20
vPh \485 :!: 25 \480 :!: 20 \475 :!: 25
vPh 1440 :!: 30 1440 :!: 30 1420 :!: 20
vPh 1305 :!: 35 1295 :!: 25 1285:!: 15
Бсн 1280:!: 35 1270 :!: зо 1255:!: 15
УСХ (Х) 12ЗО :!: 80 1185:!: 80 1105 :!: зо
Бсн 1170 :!: 30 1160:!: 20 1170:!: 10
(соntiтюl)
316 Norl1la/ Vib,'atiolls alld AbsOlptioll Regiolls о/ Rillg Stmclllres
ТаЫе 12.8 (colllillllell)
Vibration 1,3-di light 1,3 light hcavy 1.3-di hcavy
Бсн 1115 :f: 45 1115:1: 45 1100 :f: 30
Бсн 1070:!: 30 1070 :1: 30 1065 :f: 20
vPh 1000 :1: 10 1000 :1: 10 1000 :f: 10
,сн 960 :1: 30 960 :1: 30 965 :f: 15
,сн 900 :1: 50 900 :1: 50 910 :f: 40
,сн 860 :1: 50 860 :1: 50 855 :f: 40
vCX' (х) 840:!: 120 805 :f: 95 760 :f: 50
J CH 770 :1: 45 770 :f: 40 770 :f: 30
Ph (Х) 720 :1: 80 715:1: 85 685 :f: 55
,Ph 685 :1: 25 685 :1: 25 680 :f: 20
JPh (Х) 530 :1: 90 510:!: 110 480 :f: 80
Ph (Х) 480 :1: 90 440:1: 130 330 :f: 100
JPh 440 :1: 35 440 :1: 35 430 :f: 20
Ph (х) 430 :1: 90 390 :f: 130 300 :f: 100
Бсх (х) 390 :1: 100 370 :1: 120 265 :f: 105
Бсх' (х) 290 :1: 100 230 :f: 90 170:!: 60
,СХ (Х) 235 :f: 55 235 :f: 55 200 :1: 20
,СХ' (х) 180:!: 60 170 :f: 50 145 :f: 45
Notcs as in ТаЫс 12.7.
Compounds include:
3 MePbX, where (Х = Ме [92], Е! [2], С(==О)Н [22], С(==О)ОН [25, 98],
СО2' [25], СН==СН 2 [87, 88], C=N [23], NH2 [50], N02 [94], ОН [96], ОМе
[2, 135], F and 1 [92], Сl and Br [92, 168];
3 E\PhX', where Х' = Е\ [2], ОН [2];
3 FзСРhХ', where Х' = СFз [136], С(==О)Н [89], C(==O)CI [100], C=N [101],
NН 2 [137], F, Сl and Br [27];
3 02NPhX', where Х' = С(==О)Н [2], С(==О)ОН [43], СН==СН 2 [87], N0 2
[95, 102], ОН [103], F [94, 105], Сl [94,95, 105, 106], Br [105, 106], 1 [94, 105];
3 HOPhX', where Х' = СН 2 ОН [107], С(==О)Н [2], С(==О)ОН [2, 98], ОН
[111], F, Cl, Br and 1 [96];
3 MeOPhX', where (Х' = С(==О)Н [113, 114], С(==О)Ме [2], С(==О)ОН [98],
C=N [138], NH 2 [115], МеО [2], F [60, 117], СI and Br [60];
3 FPhX', where (Х' = С(==О)Н [22], С(==О)ОН [25], СО2' [25], СН==СН2
[87J, C=N [23], NH2 [118, 139], F [92, 120], Сl and Br [92, 124, 125],1 [92];
3 C]PhX', where Х' = С(==О)Н [22], С(==О)ОН [25,98], С02' [25], СН==СН 2
[87], C=N [23], NH2 [126], Сl [92, 95], Br and 1 [92];
3 BrPhX', where Х' = nPr [140], С(==О)Н [22], С(==О)Ме [2], С(==О)ОН
[25], СО2' [25], СН==СН2 [87], C=N [23], Br [92, 127], 1 [92];
3 IPhX', where Х' = 1 [92];
3 HO(0==)CPhX', where (Х' = С(==О)ОН [98, 129], NH2 [98];
3 HC=CPhX', where Х' = С=СН [133];
J 2.4 Pheпy/
317
3 N=CPhX', whcre х' = C=N [134], NH 2 [141];
3 H2NPhX', whcre Х' = С(==О)Н [132], С(==О)Ме [2], S(==0)20H апd
S(==0)20Na [142].
ViЬrаtiоп
ТаЫе 12.9 Absorption rcgions (cm l) of thc normal vibrations of 1,4-disubstituted
bcnzcncs
(Х)
(Х)
1,4-di-light 1 ,4-ljght heavy 1,4-di-heavy
3090 :J: 30 3090 :I: 25 3095 :I: 25
3075 :I: 30 3070х '5 3080 :I: 20
3055 :J: 35 3050 :J: 20 3070 :J: 20
3045 :J: 40 3025 :J: 20 3050 :J: 30
'61О :J: 20 1600 :J: 20 1590 :J: 40
1585 :J: 30 1580 :J: 25 1585 :J: 40
1500 :J: 30 1495 :J: 25 1495 :J: 35
1430 :J: 45 1415:!: 35 1405 :J: 30
1325 :J: 45 1320 :J: 40 1305 :J: 25
1280:!: 45 1270 :J: 45 1265 :J: 40
1245 :J: 50 1210:!: 90 1085 :J: 25
1160х90 1075 :J: 45 1055 :J: 35
1165 :J: 25 1170:!: 20 1175:!: 15
1105 :J: 25 1110 :J: 30 1120 :J: 20
1015:J: 20 101O:J: 15 101O:J: 15
970 :J: 30 965 :J: 25 960 :J: 10
940 :J: 35 940 :J: 30 940 :J: 20
840 :J: 50 830 :J: 40 825 :J: 35
825 :J: 45 825 :J: 35 825 :J: 25
790 :J: 70 780 :J: 80 745 :J: 65
705 :J: 30 700 :J: 35 700 :J: 25
660 :J: 120 640 :I: 140 510:!: 110
635 :J: 25 625:!: 15 620:!: 15
540 :J: 80 505 :J: 65 480 :J: 30
455 :J: 80 365 :J: 150 270:!: 115
400 :J: 20 400 :J: 20 395:!: 15
370 :J: 100 365 :J: 85 310 :J: 60
290 :J: 140 245 :J: 105 220 :J: 80
260:!: 120 250:!: 110 230 :!: 90
195 :J: 90 155:!: 70 115 :!: 30
усн
усн
усн
усн
уРЬ
уРЬ
УРЬ
уРЬ
УРЬ
бсн
УСХ
уСХ'
бсн
бсн
бсн
,сн
,сн
,сн
,сн
уРЬ
1'РЬ
ЬРЬ
БРh
')' РЬ
ЬРЬ
l' Ph
Ьсх
Ьсх'
,СХ
,СХ'
(Х)
(Х)
(Х)
(Х)
(х)
(Х)
(х)
(Х)
Notes as in ТаЫе 12.7.
Compounds include:
4 MePbX', where Х' = Ме [90], Е! [2], С(==О)Н [22], С(==О)Ме [2],
С(==О)ОН [25, 99], СО2' [25], СН==СН2 [88], C=N [23, 143], N02 [94], ОН
[96, 144], ОМе [135], SH [91], F and 1 [90], СI and Br [90,168];
4 EtPhX', where х' = Е! [2], ОН [2];
4 tBuPhX', where Х' = tBu [145];
4 FзСРhХ', where Х' = С(==О)Н [89], С(==О)СI [100], C=N [101], N H 2
[146], F, Сl and Br [27];
318 Nomlal Vibratiol/s аl/(/ Absorptiol/ Regiol/s о! Ril/g St/'llсtш'еs
4 02NPllX', where х' = С(==О)ОН [2, 43], NH2 [147], N0 2 [95, 102J, ОН
[103], ОЕ! [104], F [94,105], СI [95, 105], Br [105,106],1 [94,105];
4 HOPhX', \vhere Х' = СН20Н [107], С(==О)Н [2], С(==О)Ме [2], С(==О)ОН
[2,99), C=N [148), NH2 [149), ОН [58, 111], F, CI, Br and 1 [96];
4 MeOPhX', \vhere Х' = СН20Н [150], С(==О)Н [113, 114], С(==О)Ме [2],
С(==О)ОН [99], C=N [138], NH2 [115], F [60, 151, 152, 153], Сl and Br [60,
116, 117, 152, 153], 1 [153];
4 FPhX', where Х' = СН20Н [154], СН2С1 [155], С(==О)Н [22], C(==O)Et
[156], С(==О)СН2СН2СI [157], С(==О)СН 2 СI [158], С(==О)ОН [25), С02'
[25], C=N [23], NH2 [118), SH [91], F [90, 120), Сl and Br [90, 124, 125),
1 [90];
4 CIPhX', where Х' = CH2C=N [150), CH2CI [170), С(==О)Н [22, 159],
С(==О)Ме [2, 160], С(==О)Е! [156], С(==О)СН2СН2СI [157J, С(==О)ОН [25,
99), СО2' [25], C=N [23, 161], NH2 [126, 162], NHC(==O)Me [163], OEt [2,
116], SH and SMe [91], Сl [90, 95], Br and 1 [90];
4 BrPhX', where Х' = С(==О)Н [22], С(==О)Ме [2], С(==О)Е! (156),
С(==О)СН2СН2СI [157], С(==О)ОН [25], COi [25], C=N [23], NH 2 (164),
NHC(==O)Me [52], ОЕ! [2, 116], SH and SMe [91], Br [90, 127], 1 [90J;
4 IPhX', where Х' = С(==О)ОН [25], С02' [25], SH [91), 1 [90];
4 HO(0==)CPbX', where Х' = С(==О)Н [131), С(==О)ОН [99, 129], NH2 [2,
99), NMe2 [165];
4 H(0==)CPhX', where Х' = NH2 [132], NMe2 [165], ОЕ! [131J;
4 HC=CPhX', where Х' = С=СН [133, 167];
4 N=CPhX', where Х' = CH2Br (169), C=N [134, 166], С(==О)Н [131], NH 2
[141, 148), NMe2 [161, 165];
4 H2NPhX', where х' = С(==О)Ме [2], NH2 [165], NHC(==O)Me [52],
S(==0)20H and S(==0)20Na [142].
12.4.3 Тrisubstituted benzene derivatives
Vibration
ТаЫе 12.10 АЬsоrptiоп rcgions (сrп l) of the normal vibrations of 1,2,3 trisubstituted
Ьспzспсs
tri hcavy
tri ligllt
di light, Ьеауу
light, di hcavy
vCH
vCH
vCH
vPh
vPh
vPh
vPh
vPh
Бсн
vCX
(Х)
3085 ::1:: 25
3055 ::1:: 25
3025 ::1:: 25
1610::1:: 25
1575 ::1:: 45
1505 ::1:: 45
1455 ::1:: 35
1290::1:: 40
1265 ::1:: 40
1255::1:: 55
3085 ::1:: 15
3055 ::1:: 25
3020 ::1:: 20
1600::1:: 20
1575 ::1:: 15
1480::1:: 30
1440 ::1:: 30
1285 ::1:: 35
1260 ::1:: 40
1245 ::1:: 55
3085 ::1:: 15
3060 ::1:: 20
3035 ::1:: 25
1600::1:: 30
1570 ::1:: 20
1475 ::1:: 35
1430 ::1:: 30
1280::1:: 30
1260 ::1:: 40
1235 ::1:: 55
3075 ::1:: 25
3055 ::1:: 15
3035 ::1:: 25
1585 ::1:: 20
1555 ::1:: 15
1440 ::1:: 20
1415 ::1:: 25
1280 ::1:: 20
1265 ::1:: 25
1180::1::20
J 2.4 Pheпy/
319
ТаЫе 12.10 (co/lti/ll/cd)
Vibration tri light di light, Ьеауу light. di heavy tri hc_vy
vCX' (Х) 1160::1: 60 1160::1: 60 1080::1: 50 1030::1: 30
БСН 1155::1: 35 1165::1:25 1155::1: 25 1155 :!: 25
Бсн 1085 ::1: 35 1085 ::1: 35 1085 :!: 35 1075 :!: 25
vCX" (Х) 955 ::1: 65 930 ::1: 90 840 :!: 90 770 :!: 40
,СН 970 ::1: 25 970 ::1: 25 970 :!: 25 970 ::1: 20
,СН 890 ::1: 30 890 ::1: 30 890 :!: 30 890 :!: 20
,СН 790 ::1: 40 790 ::1: 40 775 :!: 25 770 :!: 20
vPh (Х) 780 ::1: 50 770 ::1: 60 755 :!: 55 715 :!: 35
,Ph 715::1: 25 710::1: 20 700 :!: 20 700 :!: 20
БРh (Х) 650 ::1: 70 630 ::1: 50 630 ::1: 50 470 :!: 50
,РЬ (Х) 520 ::1: 60 520 ::1: 60 545 ::1: 45 520 ::1: 20
БРh (Х) 505 ::1: 95 495 ::1: 95 485 :!: 105 445 :!: 65
,РЬ (Х) 480 ::1: 70 470 ::1: 50 500 :!: 50 480 :!: 40
БРh (Х) 435 ::1: 65 430 ::1: 60 390 ::1: 50 330 ::1: 50
БСХ (Х) 405 ::1: 75 405 :!: 75 405 :!: 75 370 :!: 50
Бсх' (Х) 330 ::1: 60 310 :!: 60 260 :!: 70 210 :!: 50
,СХ (Х) 285 ::1: 55 285 :!: 55 245 :!: 35 235 :!: 25
Бсх" (Х) 270 ::1: 50 250 ::1: 50 220 :!: 60 180 :!: 50
,СХ' (Х) 210::1: 50 210 ::1: 50 180:!: 40 180:!: 40
,СХ" (Х) 140 ::1: 40 140 :!: 40 120 :!: 40 90:!: 30
Iighl = bcnzcncs subslitulcd wilh lighl _Iom (_Iomic m_ss < 25).
Ьсауу = Ьспzспсs subslilulcd wilh Ьс_уу 'Iom (.Iomic mass > 25 .).
. Slrong clcclron wilhdrawing groups such .s N02, С(==О)ОН, C(==O)NH2. N==C==O Ь.уе the
effcct оС . Ьсауу substilucnl.
Compounds include:
Me Pb 2X' 3 X" (Х', Х" = Ме, Ме [2, 171,209], Ме, C=N [232], Ме, NН 2
[200,221], Ме, ОН [173], Ме, F [2, 171], Ме, Br [207, 254], C=N, Сl [184],
NH2, Ме [2, 244], NH2, CI [199,247], ОН, Ме [2, 173], ОМе, ОМе [182,255],
F, Ме [2, 171], F, CI [2], CI, Ме [2, 171], Br, Ме [207,254]);
Н(0==)C Pb 2X' 3 X" (Х', Х" = ОН, ОН [248], ОН, ОМе [2,188], ОМе,
ОМе [223], F, F [253]);
N=C Ph 2 X' 3 X" (Х', Х" = F, F [202]);
H2N Ph 2 X' 3 X" (Х', Х" = Ме, NН2 [181], Ме, CI [199,236], Cl, СI [177,
230]);
02N Ph 2 X' 3 X" (Х', Х" = Ме, NН2 [192], Ме, N02 [205], Ме, Сl [210,
239], CI, СI [102, 233]);
HO Pb 2 X' 3 X" (Х', Х" = ОН, ОН [2, 174], ОМе, ОМе [196]);
MeO Pb 2 X' 3 X" (Х', Х" = ОН, ОМе [2], ОМе, ОМе [2], CI, Сl [179]);
F Ph 2 X' 3 X" (Х', Х" = Ме, СI [171, 212], C=N, F [202], C=N, С[ [141,
229], NH2, F);
320 Nor11la/ Vibratiolls а//(/ AIJsorptioll Regiolls о[ Rillg St/'llctllres
Cl Ph 2 X' 3 X" (Х', Х" = Ме, Сl [2, 171J, CH2C1, СI [242,256], С(==О)Н,
Сl [219], C(==O)Cl, Cl, C=N, Cl, NHz, Сl [177, 187,210,230], ОН, Сl [2, 173],
ОМе, Сl [2], F, Сl [2, 171], Сl, Сl [171, 191,203], Сl, Br [203], Br, С! [203,
226]).
ТаЫе 12.11 Absorption rcgions (cm l) of 'Ьс normal vibrations of 1,2,4 trisubstituted
bcnzcncs
Vibration tri light di light, heavy light, di hcavy tri hcavy
усн 3085 :!:: 40 3085 :!:: 35 3085 :!:: 25 3085 :!:: 25
усн 3065 :!:: 35 3065 :!:: 25 3065 :!:: 25 3065 :!:: 25
усн 3030 :!:: 30 3030 :!:: 30 3030 :!:: 30 3030 :!:: 30
уРЬ 1615 :!:: 30 1615 :!:: 25 1585 :!:: 25 1570 :!:: 15
уРЬ 1575 :!:: 30 1575 :!:: 25 1575 :!:: 25 1555 :!:: 15
уРЬ 1480 :!:: 50 1490:!:: 40 1475 :!:: 35 1450 :!:: 20
уРЬ 1440 :!:: 50 1440 :!:: 50 1410:!:: 50 1370 :!:: 20
уРЬ 1295 :!:: 35 1295 :!:: 35 1280 :!:: 30 1275 :!:: 25
Бсн 1255 :!:: 40 1255 :!:: 35 1250:!:: 30 1240 :!:: 25
уСХ (х) 1250:!:: 60 1240:!:: 60 1220 :!:: 80 1095 :!:: 25
уСХ' (Х) 1160:!:: 80 1120 :!:: 95 1060 :!:: 50 1025 :!:: 25
Бсн 1150 :!:: 35 1140:!:: 25 1140:!::25 1140 :!:: 20
Бсн 1075 :!:: 55 1095 :!:: 45 1095 :!:: 45 1110 :!:: 20
уСХ" (Х) 940 :!:: 60 900 :!:: 100 830 :!:: 90 780 :!:: 40
,сн 950 :!:: 40 950 :!:: 40 935 :!:: 35 945 :!:: 15
,сн 890 :!:: 50 880 :!:: 40 880 :!:: 40 860 :!:: 20
,сн 820 :!:: 40 810 :!:: 40 820 :!:: 40 810 :!:: 15
vPh (х) 755 :!:: 65 760 :!:: 40 720 :!:: 50 665 :!:: 25
БРh (Х) 700 :!:: 80 660 :!:: 60 630 :!:: 60 520 :!:: 70
,Ph 700 :!:: 40 700 :!:: 40 695 :!:: 35 680 :!:: 20
,РЬ (Х) 580 :!:: 50 565 :!:: 45 565 :!:: 45 530 :!:: 30
БРh (Х) 505 :!:: 85 495 :!:: 75 495 :!:: 75 430 :!:: 50
,РЬ (х) 465 :!:: 65 460 :!:: 70 450 :!:: 50 430 :!:: 30
БРh (х) 430 :!:: 70 410 :!:: 70 410 :!:: 70 350 :!:: 50
Бсх (х) 370 :!:: 80 365 :!:: 75 355 :!:: 65 280 :!:: 60
Бсх' (х) 320 :!:: 70 285 :!:: 65 285 :!:: 65 190 :!:: 30
,СХ (Х) 290 :!:: 90 290 :!:: 90 275 :!:: 75 260 :!:: 60
Бсх" (Х) 235 :!:: 65 ' 225 :!:: 55 225 :!:: 55 160 :!:: 40
,СХ' (х) 220 :!:: 70 210 :!:: 60 200 :!:: 50 165 :!:: 35
,СХ" (х) 160 :!:: 60 140 :!:: 60 140 :!:: 60 110 :!:: 30
Notes as for ТаЫе 12.10.
Compounds inc!ude:
Me Ph 2 X' 4 X" (Х', Х" = Ме, Ме [2, 172,209], Ме, NH2 [221], Ме, ОН
[173], Ме, F [2, 172], С(==О)Н, Ме [249], C=N, Ме [232], NН2, Ме [2,244],
NН2, NН2 [181], NH 2 , N02 [243], NH2, С! [236], N0 2 , NH2 [243], N0 2 , N02
12.4 Pheпy/
321
[197,205], N02, СI [214], ОН, Ме [173], F, Ме [2], F, NH 2 [220], F, F (172,216,
250], F, Сl [2, 172], cl, NH 2 [236], Cl, F [2, 172], cl, С1 [2, 172, 216], Br, Ме
[207],1, F [180], Br, Br [254]);
CICH2 Ph 2 X'A X" (Х', Х" = CI, CI [256]);
HO(0==)CCH2 Pb 2 X' 4 X" (Х', Х" = N02, N0 2 [205]);
MeO(0==)CCH2 Pb 2 X' 4 X" (Х', Х" = N0 2 , N0 2 [205]);
FзС Рh 2 Х' 4 Х" (Х', Х" = CI, СI [185]);
Н(0==)C Pb 2 X' 4 X" (Х', Х" = Ме, Ме [249], ОМе, ОМе [223], cl, С1
[219], F, F [253]);
HO(0==)C Pb 2 X' 4 X" (Х', Х" = CI, Сl [237]);
cl(0==)C Ph 2 X' 4 X" (Х', Х" = CI, СI [183, 186]);
N=C Ph 2 X' 4 X" (Х', Х" = Ме, Ме [232], F, F [202]);
H2N Ph 2 X' 4 X" (Х', Х" = Ме, Ме [198, 221], Ме, N02 [243], Ме, ОН
[193,196], Ме, Сl [236], Ме, Br [211], NH2, Ме [181], N02, Ме [2, 243], N02,
N0 2 [2], N02, СI [208,218], ОН, Ме [176], F, F [225], cl, N02 [208,218], cl,
Сl [2, 245], Br, Ме [195]);
H2NHN Ph 2 X' 4 X" (Х', х" = N02, N0 2 [2, 197]);
Me(0==)CHN Ph 2 X' 4 X" (Х', Х" = Cl, CI [241]:
02N Ph 2 X' 4 X" (Х', Х" = Ме, ОН [193, 196], НО, С(==О)Н [2], cl, Сl
[102]:
HO Ph 2 X' 4 X" (Х', Х" = Ме, Ме [173], Ме, cl [231], BrCH 2 , N0 2 [238],
С(==О)Ме, N0 2 [2], NН 2 , Ме [178], NН2, N02 [193], NH 2 , CI (178], N02,
С(==О)Ме [2], N02, N02 [2, 197, 234], ОН, С(==О)Н [2, 248], ОМе, С(==О)Н
[188], Cl, Сl [2, 215]);
MeO Pb 2 X'A X" (Х', Х" = BrcH2, N02 [238], NH2, СI [227], ОН,
С(==О)Н [188], ОМе, С(==О)Н [2, 223], ОМе, ОМе [235], CI, NH2 [227], Br,
N0 2 [224]);
F Ph 2 X' 4 X" (Х', Х" = Ме, F [2, 172,250], Ме, cl [2, 172,251], Ме, I
[180], C=N, F [202], NН 2 , Ме [220], NН2, F [2, 217], N02, N02 [2, 175,206], F,
C=N [202], F, NH2 [202], F, ОМе [202], F, С(==О)Н [253], С(==О)Н, F [253],
F, F [2, 172], F, Br [252], Cl, NH2, [ ] Cl, С1 [184], Br, F [252]);
CI Ph 2 X' 4 X" (Х', Х" = Ме, ОН [231], Ме, F [2, 172,251], Ме, С1 [2,
172], FзС, Cl, [ ] С(==О)ОН, N02 [237], NН2, Сl [177,217,245], N02, N02 [2,
106,206], N02, Сl [102,228], NHC(==O)Me, Сl [246], ОН, Ме [231], ОН, CI [2,
173], F, NH2 [222], Cl, Ме [2, 172], Сl, СFз, [] Cl, С(==О)Н [219], Cl, С(==0)С1
[183, 186], CI, NH2 [201], CI, NНC(==O)Me [246], Cl, N02 [102,213], cI, ОН
[173], Cl, F [2, 172], CI, CI [2, 172, 191], Cl, Br [203, 240], Br, С1 [203, 240]);
Br Ph 2 X' 4 X" (Х', Х" = Ме, Ме [207], Ме, NН 2 (195,211], Ме, Br [2,
212, 254], N02, Br [213], ОМе, N02 [224], F, F [252], CI, С1 [203, 240], Br, Br
[203]).
322 NoтlG! Vibratio"s а1ll/ Absorptio" Regiolls о! Ri"g St/'llсtщ"еs
ТаЫе 12.12 Absorption rcgions (cт 1) of tl1C поrnзаl vibrations of 1,3,5 trisubstitutcd
bcnzcncs
Vibration tri ligllt di ligllt, Ьсауу ligl1\, di hcavy Iri llcavy
уСН 3080 :!: 30 3080 :!: 30 3075 :!: 25 3075 :!: 25
уСН 3045 :!: 45 3045 :!: 45 3045 :!: 45 3045 :!: 45
уСН 3045 :!: 45 3045 :!: 45 3045 :!: 45 3045 :!: 45
уРЬ 1610:!: 20 1600 :!: 20 1590:!: 20 1570 :!: 20
уРЬ 1610:!: 20 1580 :!: 20 1570 :!: 20 1570 :!: 20
vPh 1480:!: 40 1470:!: 30 1460 :!: 40 1430 :!: 30
уРЬ 1450:!: 40 1440 :!: 30 1410 :!: 40 1410 :!: 30
//РЬ 1300 :!: 30 1300 :!: 30 1295 :!: 25 1295 :!: 25
Бсн 1260 :!: 60 1260 :!: 40 1240 :!: 40 1230 :!: 30
уСХ (х) 1245 :!: 65 1240 :!: 50 1230 :!: 60 1130 :!: 30
БСН 1140 :!: 40 1150 :!: 30 1130 :!: 30 1090 :!: 30
БСн 1115 :!: 55 1100:!: 30 1090 :!: 30 1090 :!: 30
vPh 995 :!: 15 995 :!: 15 1000 :!: 10 990 :!: 10
уСХ' (х) 940 :!: 60 880 :!: 1 00 880 :!: 100 770 :!: 50
уСХ" (Х) 940 :!: 60 850 :!: 100 800 :!: 80 770 :!: 50
/СН 865 :!: 25 870 :!: 30 910:!: 30 865 :!: 25
/СН 865 :!: 25 860 :!: 30 860 :!: 30 865 :!: 25
/СН 835 :!: 25 835 :!: 25 835 :!: 25 835 :!: 25
,РЬ 685 :!: 25 680 :!: 20 685 :!: 25 665 :!: 15
БРh (х) 560 :!: 40 . 560 :!: 40 490:1::110 319 :!: 90
/РЬ (Х) 550 :!: 50 540 :!: 60 520 :!: 60 520 :!: 40
/РЬ (Х) 550 :!: 50 540 :!: 60 520 :!: 60 520 :!: 40
БРh (х) 480 :!: 50 470 :!: 50 450 :!: 50 390 :!: 50
БРh (Х) 480 :!: 50 470 :!: 50 450 :!: 50 390 :!: 50
БСх (х) 440 :!: 60 380 :!: 80 380 :!: 80 440 :!: 60
Бсх' (Х) 290 :!: 50 250 :!: 90 250 :!: 90 160 :!: 50
Бсх" (х) 290 :!: 50 250 :!: 90 250 :!: 90 160 :!: 50
/СХ (х) 220 :!: 40 220 :!: 40 190 :!: 40 200 :!: 30
/СХ' (х) 220 :!: 40 220 :!: 40 190 :!: 40 200 :!: 30
/СХ" (Х) 170 :!: 50 160:!: 40 140:!: 40 140 :!: 40
Notes as ТаЫе 12.10.
Compounds include: Me Ph 3 X' 5 X" (Х', Х" = Ме, Ме [2, 171,209], Ме,
NН 2 [2,171], Ме, ОН [173], ОН, ОН [2], Ме, F [2, 171, 173], Ме, СI [2, 171],
Ме, Br [2, 171], CI, CI [2]);
Et Ph 3 X' 5 X" (Х', Х" = Et, Е! [2]);
Н(0==)С Рh 3 Х' 5 Х" (Х', Х" = CI, Cl);
HO(0==)C Ph 3 X' 5 X" (Х', Х" = NO[2], N0 2 [2,237]);
Cl(0==)C Ph 3 X' 5 X" (Х', Х" = ОМе, ОМе, [ ] Cl, Сl [183]);
N=C Ph 3 X' 5 X" (Х', Х" = Cl, Cl);
H2N Ph 3 X' 5 X" (Х', Х" = Cl, Сl [177]);
J 2.4 PllellY/
323
02N Рh З Х' 5 Х" (Х', х" = cl, cl [205]);
I-Ю Рh 3 Х' 5 Х" (Х', Х" = ОМе, ОМе [194]);
MeO Ph 3 X' 5 X" (Х', Х" = ОМе, ОМе [2, 235], ОМе, cl, [] CI, CI [151]);
F Ph 3 X' 5 X" (Х', х" = F, F [2, 171, 189,204], F, Br [252]);
CI Ph 3 X' 5 X" (Х', Х" = cl, cl [2, 171, 190], cl, Br [203]);
Вr Рh 3 Х'-5 Х" (Х', Х" = Br, Br [2,171,203]).
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214. R.B. Singh, N.P. Singh and о,к Rai, /lIdiall J. P/,yS., 568, 62 (1982).
215. М.Р. Srivastava, /lIdiall J. Pllre Арр/. P/IYS., 5, 189 (1967).
216. G. Тhаkш, У.В. Singh and N.L. Singh, /lIdiaп J. Pllre Арр/. P/,yS., 7, 107 (1969).
217. S.N. Singh and N.L. Singh, /lIdiaп J. Pllre Арр/. P/,yS., 7, 250 (1969).
218. V.N. Verma and КРЯ. Nair, /lIdiaп J. Pllre Арр/. P/,yS., 8, 682 (1970).
219. H.S. Singh and N.K. Sanyal, /lIdiall J. Pllre Арр/. P/,yS., 10, 545 (1972).
220. S.N. Sharma and С.Р.О. D\vivedi, /lIdiall J. Pllre Арр/. P/IYS., 13,570 (1975).
221. М. Prasad, /lIdiall J. Pllre Арр/. P/IYS., 13, 718 (1975).
222. N.K Sanyal, S.L. Srivastava and R.K Goel, /lIdiall J. Pllre Арр/. P/,yS., 16, 719
( 1978).
223. S.J. Singh and R. Singh, /lIdiaп J. Pllre Арр/. P/,yS., 16,939 (1978).
224. м. Rangacharyulu and о. Premaswarup, /lIdiall J. Pllre Арр/. P/IYS., 19, 166 (1981).
225. R.B. Singh, N.P. Singh and О.К. Rai, /lIdiallJ. PllreApp/. P/,yS., 19, 740 (1981).
226. R.N. Singh and S.K. Singh, /lIdiall J. Pllre Арр/. P/1YS., 19,599 (1981).
227. Р. Venkatacharyulu, V.L.N. Prasad, Nаllgопdа and о. Premaswarup, /lIdiall J. Pllre
Арр/. P/,yS., 19, 1178 (1981).
228. К Singh and R.N. Singh, /lIdiall J. Pllre Арр/. P/,yS., 22, 112 (1984).
229. Е.У. Huded, N.H. Ayachit, М.А Shashidhar and KS. Rao, /lIdiall J. Pllre Арр/. P/IYS.,
25, 289 (1987).
230. R.P. Singh and R.N. Singh, Pramalla, 30,217 (1988).
12.5 Pyridy/
329
231. R.B. Singh and О.К. Rai, Proc. /lIdian Acad. Sci. (Chem. Sci.), 89, 163 (1980).
232. Т.У.к. Sarma, Арр/. Spec/rosc., 40,933 (1986).
233. R.P. Singh and R.N. Singh, /ndian J. PJ,yS., 628,502 (1988).
234. R.B. Singh, М. Mukul and S.K. Sharma, /пdiaп J. PJ,yS., 628, 556 (1988).
235. л.к. Sarkar, S. Chakravorti апd S.B. Вапе*е, /пdiaп J. PJ,yS., 518, 71 (1977).
236. S.N. Sharma and с.Р.О. Dwivedi, /ndian J. PJ,yS., 50, 25 (1976).
237. U.к. Rastogi, М.Р. Rajpoot апd S.N. Sharma, /ndiaп J. Phys., 588, 311 (1984).
238. Т.У.К. Sarrna, /ш!iаll J. PJ,yS., 59В, 478 (1985).
239. R.B. Singh and О.К. Rai, /lIdian J. PJ,ys., 60В, 404 (1986).
240. S.R. Tripathi and G.N.R. Tripathi, /lIdiaп J. pиre Арр/. Phys., 18, 143 (1980).
241. Р. Venkatacharyulu, О.У. Ramanamurti and О. Premaswarup, /lIdiaп J. pиre Арр/.
PJ1YS., 20, 328 (1982).
242. S.N. Sharrna, /lIdian J. Pure Арр/. Phys., 20, 562 (1982).
243. R.B. Singh and О.к. Rai, /lIdiall J. Pure Арр/. Phys., 20, 8]2 (1982).
244. S.K. Singh and R.N. Singh, /lIdian J. Pиre Арр/. PJrys., 21,163 (1983).
245. S.к. Singh and R.N. Singh, /lIdiall J. pиre Арр/. PJ,yS., 21,744 (1983).
246. Р. Venkatacharyulu, N.V.L.N. Prasad, I.V.S.R.M. Sarma, J.V. Rao апd О. Premaswarup,
/ndiall J. Pure Арр/. PJ1YS., 23,383 (1985).
247. R. Shanker, R.A. Yadav, I.S. Singh and O.N. Singh, /пdiaп J. pиre Арр/. Phys., 23,
339 (1985).
248. Р. Venkoji, /lIdiall J. Pure Арр/. PJ,yS., 24, 166 (1986).
249. Р. Venkoji, Proc. /lIdiall Acad. Sci. (CJlel1l. Sci.), 93, 105 (1984).
250. R.P. Singh and R.N. Singh, /lIdiall J. pиre Арр/. Phys., 26, 644 (1988).
251. S. МоЬап and F. Payami, /lIdiall J. pиre Арр/. PJ,yS., 24,570 (1986).
252. М.К Aralakkanavar, R. Rao, N.R. Кatti and М.А. Shashidhar, SpectrocJrim. Асю, Par/
А, 47А, 149 (1991).
253. М.К Aralakkanavar, N.R. Katti, P.R. Jeergal, О.В. Кalkoti, R. Rao апd м-л.
Shashidhar, Spec/rociIiт. Ас/а, Par/ А, 48А, 983 (1992).
254. R.N. Singh and KN. Upadhya, /lIdiall J. PJ1YS., 51А, 88 (1977).
255. О.Р. Singh, R.P. Singh and R.N. Singh, SpeclrocJril1l. Acta, Par/ А, 49А, 517 (1993).
256. U.c. Joshi, G.G. Manchanda, N.K. Naithani and S.N. Sharma, Сап. J. Spectrosc., 32,
148 (1987).
12.5 PYRIDYL
The 27 поrrnаl vibrations of руridiпе are divided iпtо five СН strеtсhiпg vibrations
(УСН), five СН in plane deformations (Бен), five СН оut оf рlапе dеfоrrnаtiопs
(, СН), six ring strctching viЬrаtiопs (уРу), three riпg iп рlапе dеfоrrnаtiопs (оРу)
and thrce ring out of plane deformations (, Ру) [1 5, 10]. Тhe iпfrarеd spectrum of
pyridine looks like that of а monosubstituted Ьеnzепе апd the spectra of substituted
руridiпеs resemble those of substituted Ьепzепes, соuпtiпg the riпg пitrogеп as а
substituted carbon. ТаЫе 12.13 gives the аЬsоrptiоп rеgiопs of the viЬrаtiопs of
monosubstituted pyridines. In this text we ассер! that the riпg strеtсhiпg vibration
уРу 14 always has а higher wavenumber thап the СН iп рlапе deforrnation БС 3.
The ring out of plane deformation, Ру 16Ь and the C X оut оf рlапе dеfоrmаtlOП
11 are strongly coupled, so that the аssigпmепts of the two suЬstituепt sепsitivе
modes ате often interchanged.
330 Norllla/ Vib/.atiolls alld AIJsorptioll Regio1/s о! Rillg St1'llctllres
ТаЫе 12.1З Absorption regions (cт 1) of tllC normal vibrations of MonostlL1stitutcd pyridincs
ViЬrзtiоп \V,lson 2 X-substitutcd 3-X-substitutcd 4 X substitutcd
pyridincs pyridincs pyridincs
Х = С, N, О, F x=s, CI, Br, 1 Х = С. F Х =CI. Br, 1 Х = С, N Х = CI, Br
vCH 20з 3085 :1: 15 3080:1: 1 О 3085 :1: 15 3075 :1: 1 О 3075 :1: 15 3075 :1: 10
vCH 20Ь 3075 :1: 15 3070:1: 15 3070 :1: 15 3070 :1: 10 3055 :1: 15 3070:1: 10
vCH 2 3055 :1: '5 3055 :1: 15 3045 :1: 15 3045 :1: 10 3040 :1: 15 3040:1: 10
//СН 7Ь 3020 :1: 20 3035 :1: 15 3020 :1: 20 3035 :1: 10 3025 :1: 15 3035 :1: 15
//Ру 8з 1595 :1: 15 1575:1: 10 1590:1: 10 '570 :1: 10 '600 :1: 10 1570 :1: 05
vPy 8Ь 1570:1: 10 1560:1: 10 1570:1: 10 1560 :1: 10 1565 :1: 20 1565 :1: 02
vPy 19з 1480 :1: 20 1455 :1: 10 1480 :1: 20 1462 :1: 02 1490 :1: 20 1483 :1: 02
vPy 19Ь 1435 :1: 15 1425 :1: 10 1420:1: 10 1415 :1: 05 '410:l: 10 '405 :1: 05
//Ру 14 \305 :1: 40 1325 :1: 40 1305 :1: 35 1320 :1: 02 13 20 :1: 40 1350:1: 10
бсн 3 1270 :1: 30 1260 :1: 30 1260:1: 40 1215 :1: 15 1265 :1: 30 1316 :1: 02
vCx 13 (Х) 1215:1: 35 1110:1:25 1215 :1: 35 1090 :1: 15 1225 :1: 25 1095 :1: 10
бсн 9з 1155 :1: 10 1150:1: 05 1180:1: 15 1190:1: 02 1210:1: 20 1218:1: 02
бсн 15 1085 :1: 15 1080:1: 10 1110 :1: 15 1095 :1: 15 t 095 :1: 20 1077 :1: 03
бсн 18з 1040:1: 15 1040:1: 10 1040:1: 10 1030 :1: 10 1060 :1: 20 1063 :1: 02
vPy 1 995:1: 10 990 :1: 10 1025 :1: 05 1010 :1: 05 1000 :1: 10 994 :1: 02
,сн 17з 980 :1: 15 965 :1: 15 970 :1: 20 975 :1: 05 965 :1: 25 960 :1: 05
,сн 5 930 :1: 35 925 :1: 25 935 :1: 10 945 :1: 05 905 :1: 35 914:1: 02
,сн 10з 855 :1: 50 865 :1: 15 905 :1: 20 915 :1: 02 850 :1: 30 848 :1: 12
J CH 10Ь 770 :1: 25 760 :1: 10 795 :1: 15 790 :1: 05 805 :1: 25 808 :1: 04
Ру 12 (х) 740 :1: 85 735 :1: 55 785 :1: 45 705 :1: 25 785 :1: 50 700 :1: 20
JPY 4 725 :1: 20 730 :1: 10 710:1: 10 700 :1: 10 730 :1: 20 722 :1: 02
Ру 6Ь 620:1: 10 620 :1: 10 620 :1: 10 613 :1: 02 660 :1: 10 662 :1: 02
БРу 6з (х) 460 :1: 100 390 :1: 130 495 :1: 50 345 :1: 85 520 :1: 60 365 :1: 55
,Ру 16Ь (х) 470 :1: 50 470 :1: 20 450 :1: 20 445 :1: 15 490 :1: 60 485 :1: 10
Jc 16а 410:1: 10 400 :1: 10 400 :1: 10 400 :1: 10 395 :1: 20 390 :1: 02
18Ь (х) 320 :1: 70 270 :1: 40 300 :1: 65 260 :1: 40 290 :1: 70 280 :1: 25
,СХ 11 (х) 175:1: 65 185 :1: 25 205 :1: 45 190:1: 10 180 :1: 40 180 :1: 05
(Х) = substituenHensitive viЬrзtiоп.
Wilson: Not3tion зссоrdiпg 10 Wilsпп (see Sесtiоп 12.4 for equiv31enl пumЬеrs).
Х Ру compounds
Х = 2 Me [g.....10], 3 Me [6----10], 4 Me [9 IЗ], 4 Et [11], 2 and 4
H[2C==CH [15], 2 , з and 4 N=C [16], 2 (2IPy) [17, 18J, 2 ,
3 and 4 Н(0==)C [16], 2 , 3 and 4 Me(0==)C [14], 2 , з and 4
HO(O==)C [19], 2 H(S==)CNH and 2 Me(S==)CNH [21], 2 and
4 Mc2N [22], 2 MeO [23], 2 PhS , 2 PyS , 2 PhS(==0)2 and 2
PyS(==0)2 [24], 2 and 3 F [9, 16, 20], 2 , 3 апd 4 CI [9, 20J, 2 ,
з and 4 Br [9, 20], 2 and 4 I [20].
References
1. L. Corrsin, B.J. Fax апd R.C. Lord, J. C/lem. P/,YS., 21, 1170 (1953).
2. L. Harsanyi and F. Kilar, J. Mol. S/rllct., 65,141 (1980).
J 2.6 Pyriтidi"y/
331
3. A.J. Ashe, G.L. Jones and ЕА. Miller, J. Mol. Struct., 78, 169 (1982).
4. I-I.K.J. Koser, SpectrocIliт. Acta, Part А, 40А, 125 (1984).
5. G. Pongor, Р. Pulay, G. Fogarasi and J.E. Boggs, J. Ат. Cllem. Soc., 106, 2765
(1984).
6. О. Gandolfo and J. Zarembowitch, Spectrocllim. Acta, Part А, 33А, 615 (1977).
7. D.W. SCOtl, W.D. Good, G.B. Guthrie, S.S. Todd, I.A. Ноssепlорр, A.G. Osbom апd
J.P. McCullough, J. P//ys. CI/em., 67, 685 (1963).
8. D.W. SCOtl, W.N. I-Iubbard, J.F. Messerly, S.S. Todd, I.A. Hossenlopp, W.D. Good,
D.R.Douslin and J.P. McCullough, J. P//ys. Chem., 67, 680 (1963).
9. J.I-I.S. Green, W. Kynaston and Н.М. Paisly, Spectrochim. Acta, 19,549 (1963).
10. J.A. Draeger, Spectroc//im. Acta, Part А, 39А, 809 (1983).
11. D.L. Cummings and J.L. Wood, J. Mol. Struct., 20, I (1974).
12. Е. Allenstein, W. Podszun, Р. Kiemle, H.J. Mauk, Е. Schlipf апd J. Wеidlеiп,
SpectrocIlim. Acta, Part А, 32А, 777 (1976).
13. D.A.Thomton, Р.ЕМ. Verhoeven, G.M. Watkins, н.о. Desseyn and BJ. Уа" der Vеkеп,
В//II. Soc. СЫт. Belg., 100,211 (1991).
14. к.с. Medhi, l"dia/l J. P//ys., 51А, 399 (1977).
15. J.H.S. Green and D.J. Harrison, Spectrocllim. Acta, Part А, 33А, 249 (1977).
16. J.H.S. Green and D.J. Harrison, Spectrocllim. Acta, Рап А, 33А, 75 (1977).
17. О.А. Thomton and G.M. Watkins, В//II. Soc. СЫт. Belg., 100,221 (1991).
18. М. Muniz Miranda, Е. Castelluci, N. Neto and G. Sbrana, Spectrochim. Acta, РаП А,
39А, 107 (1983).
19. S. Chatlopadhyay and S.к. Brahma, Spectrocllim. Acta, Part А, 49А, 589 (1993).
20. Н. Abdel Shafy, Н. Perlmutter and Н. Кimmel, J. Mol. Strl/ct., 42. 37 (1977).
21. D.N. Sathyanarayana and S.V.к. Raja, J. Mol. Strиct., 157,399 (1987).
22. S.P. Gupta, S. Ahmad and R.K. Goel, l"dia/l J. PJ,yS., 61В, 427 (1987).
23. к.С. Medhi, В//II. С//ет. Soc. JP/l., 57, 261 (1984).
24. А. Bigotto, У. Galasso, G.C. Pappalardo and G. Scarlata, SресtюсJ/im. Acta, Part А,
34А, 435 (1978).
12.6 PYRlMIDINYL
Pyrimidine (1,3 diazine) has 24 поrmal viЬrаtiопs: four СН strеtсhiпg modes
(vСН), four СН in p]ane dсfоrmаtiопs (бен), fош СН оut оf рlапе dеfоrmаtiопs
(,. СН), six ring stretching viЬrаtiопs (vPym), three riпg iп рlапе dеfоrmаtiопs
(БРуm) and three ring оut оf рlапе dеfоrmаtiопs (1' Рут) [1 5]. Kartha iпtеrprеtеd
the spectra of 4 methyl and 5 methy] pyrimidine [12] and the 2 X pyrimidines
Ьауе Ьееп studied Ьу several authors [6----11]. Table 12.14 sho\ys the absorption
rеgiопs of 2 Х руrimidiпеs, based оп а few interpretations in the Iiterature. Just as
for substitиlcd benzenes (5ection 12.4), the HW side of IЬе ехtепsivе regi ns of
thc substituent sensilive modes (Х) is occupies Ьу руrimidiпеs substituted wlth ап
electron donating alom (N, О) and the LW side Ьу руrimidiпes substituted with
а Ьеауу atom (5, CI, Br, 1). The normal viЬrаtiопs зrе also dеfiпеd Ьу а Wilson
number. ТаЫе 12.4 gives the possibIe equivalent пumЬеrs.
332 Nor1llal Vibra/io"s alld Absorp/io" Regio"s о[ Ri"g S/rис/ш'еs
ТаЫе 12.14 AIJsorption regions (сш l) of the normal vibrations of 2
substituted pyrirnidincs
Vibration Wilson Region Vibration Wilson Region
vCH 20а 3100::!: 20 vPym 1 985 ::!: 1 О
vCH 2 3070 ::!: 15 /,СН 5 920 ::!: 70
vCH 7Ь 3040 ::!: 20 /,СI-I 10а 820 ::!: 20
vРуш 8а 1570::!: 20 БРуш 12 (Х) 795 ::!: 75
vPym 8Ь 1555 ::!: 15 /,СН 17Ь 780 ::!: 20
vPym 19а 1415 ::!: 40 /,Рут 4 770 ::!: 20
vPym 19Ь 1400 ::!: 30 БРуm 6Ь 630 ::!: 10
vPym 14 1300 ::!: 50 БРуm 6а (х) 380::!: 110
vCX 13 (Х) 1180::!: 120 /' Руш 16Ь (Х) 485 ::!: 40
Бсн 3 1185 ::!: 35 /' Руш 16а 400 ::!: 15
БСн 15 1165::!: 30 БСХ 18Ь (Х) 350 ::!: 120
Бсн 9а 1080 ::!: 20 /,СХ 11 (Х) 195 ::!: 40
2 X Pym compounds
Х = Me [7], H2N [8, 11], D2N [11], MeO [11], 2 RS (R = Ме, Et,
iPr, nBu, СН2==СНСН2, PhCH2, PhCH2CH2, РhО(СН 2 )з) [9], F , Br and
I [6], Cl [5,6, 10, 11].
References
1. G. Sbrana, G. АdешЬri and S. Califano, Spectrocl,illl. Acta, 22, 1839 (1966).
2. L. Bokobza Sebach and J. Zarembowitch, Spectroc/,illl. Acta, Part А, 32А, 797 (1976).
3. S.G. Stepanian, G.G. Sheina, Е.О. Radchenko and Уи.Р.. Blagoi, J. Mol. Strllct., 131,
333 (1985).
4. У.А Sarma, Spectrocl,illl. Acta, Part А, 34А, 825 (1978).
5. У.А Sarma, Spectrocl,illl. Acta, Part А, 30А, 1801 (1974).
6. Е. A1lenstein, Р. Kiemle, J. Weidlein and W. Podszun, Spectroclliт. Асщ Part А, 33А,
189 (1977).
7. Е. A1lenstein, W. Podszun, Р. Кiemle, H. J. Mauk, Е. Schlipf and J. Weidlein,
Spectroc/,illl. Acta, part А, 32А, 777 (1976).
8. М. Maehara, S. Nakama, У. Nibu, н. Shimada and R. Shiшаdа, BIIII. CI,elll. Soc. Jp""
60, 2769 (1987)
9. G. Мillе, М. Guiliano, J. Кister, J. Chouteau and J. Metzger, Spect/"Ocllilll. Acta, Part
А, 36А, 713 (1980).
10. н. Gauthier and J.M. Lebas, Spectroclliт. Acta, Part А, 35А, 787 (1979).
11. AJ. Lafaix and J.M. Lebas, Spectroclliт. Acta, Part А, 26А, 1243 (1970).
12. S.B. Kartha, Spectrocllilll. Acta, Part А, 38А, 859 (1982).
12.7 TНIENYL
The 21 normal vibrations of thiophcne are divided into four ring stretching
vibrations (vTh), thrce ring in plane dcformations (15Th), two ring оut оf рlапе
12.7 Thieпy/
333
dcformations (,Th), fош СН strctching viЬrаtiопs (vСН), four СН iп рlапе
deformations (ЬСН) and four СН out of plane dсfоrmаtiопs (,СН) [1----6]. ТаЫе
12.15 shows the 21 normal viЬrаtiопs of 2 monosubstituted thiорhепes. ТЪе
absorption rcgions оС thc ring stretching viЬrаtiопs are iп good аgrееmепt with
thosc found Ьу Angclclli et 0/. [12] fют the spectra of twепtу fоur 2 substituted
thiophencs. Thc high valuc (1554 cm l) for the ring stretch of 2 tluоrothiорhепе
howcver, falls outsidc thc rcgion. Just like iп Ьепzепеs, 'Ье suЬstituепt sепsitivе
modc vC Х (1110 ::J: 170 cm l) is partly а riпg vibration. ТЪе spectral роsitiоп
of this vibration dcpcnds uроп the rеsопапсе, inductive апd mass effects of the
substitucnt (see Scction 12.4). The compound 2-МеТЪ absorbs а! 1236 cm l,
2 02NTh аl 1126, 2 HSTh аl 1022, 2 CIТh а! 1000 апd 2 ITh а! 945 cm l.
ТЬе absorption regions оС З Х thiорhепеs resembIe those of the 2 Х-thiорhепеs.
Scott interpreted thc spcctrum оС 3 теthуlthiорhепе [10], Раliапi апd CataJiotti
the spectra of З hаlоgепоthiорhепеs [13] and АJЬеrghiпа et 0/. those of 3
thiophenecarboxamides [11].
ТаЫе 12.15 Absorption rеgiопs (cm l) of [Ье normal viЬrаtiопs of 2 substituted thiорhепеs
Vibration
2 X substituted thiорhепеs
ViЬratiоп
2 X substituted thiорhепеs
х = С, N, О, F Х = S, CI, Br, 1 Х = С, N, О, F Х = S, CI, Br, 1
vCH 3120::J: 10 3115 ::J: 05 vTh 855:!: 15 850 :i: 10
vCH 3095 ::J: 15 3095 ::J: 10 ,СИ 825 :i: 30 830:!: 15
vCH 3080 ::J: 10 3080 ::J: 10 15ть 755:!: 15 745:!: 10
vTh 1520 ::J: 20 1510 ::J: 10 ,сн 700 :i: 25 695 :i: 25
vTh 1425 ::J: 25 1405 ::J: 10 15ть 665 :i: 25 645 :i: 20
vTh 1355 ::J: 10 1342 ::J: 07 ,ТЬ 560:!: 15 560:!: 10
Бсн 1230::J: 10 1222 ::J: 07 , Th (Х) 495 :i: 55 460 :i: 20
Бен 1080::J: 05 1077 ::J: 07 15ть (Х) 395 :i: 80 305 :!: 25
Бсн 1040 ::J: 15 1047 ::J: 07 БСХ (х) 295 :i: 45 220 :i: 40
vCX (Х) 1200 ::J: 80 985 :i: 45 ,СХ (Х) 220 :i: 30 200 :i: 30
,сн 910 ::J: 20 900 ::J: 10
2 X Th compounds
Х = Me [7, 10], Et , N=CCH2 , HON==HC , HO(O==)CC=C ,
N=C , Н(O==)C , Me(O==)C , Et(O==)C , CICH2(O==)C ,
Cl(O==)C , HO(O==)C , ЕtO(о==)с , 02N , MeO , HS and
Cl(O==)2S [7], Сl and Br [7 9], I [7,8].
References
1. J.M. Orza, М. Rico and J.F. Biarge, J. Мо/. Spectrosc., 19, 188 (1966).
2. J. Loisel and У. Lorenzelli, Spectroc/riт. Acta, Part А, 23А, 2903 (1967).
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4. О. Paliani, R. Cataliotti and А. Poletti, Spectroe/riт. Лещ Part А, 32А, 1089 (1976).
334 Norтa/ Vib,'atiolls ат/ Absorpti01l Regi01ls о/ Rillg Structl1res
5. G. Paliani, А. Poletti .1I1d R. Cataliotti, CI/c11l. PI/ys. LC/l., 18, 525 (1973).
6. М. Kofranek, Т. Kovar, Н. Lischka and А. Karpfen, J. Mol. S/тc/., 259, 181 (1992).
7. J.1. Peron, Р. SаUП1аgпе and J.M. Lebas, Spec/rocl/i11l. Ас/а, par/ А, 26А, 1651 (1970).
8. М. Horak, 1.1. НуаП1S and E.R. Lippincott, Spec/rocl/i11l. Ас/а, 22, 1355 (1966).
9. G. Paliani and R. Cataliotti, Spec/rocJ/i11l. Ас/а, Par/ А, 37А, 707 (1981).
10. D.W. Scott, J. Mol. Spec/rosc.. 31, 451 (1969).
11. G. AlberghiI1a, S. FisiclleIla and S. Occhipinti, Spec/rocJ/i11l. Ас/а, Par/ А, 36А, 349
( 1980).
12. J.M. Angclelli, A.R. Katritzky, R.F. Pinzclli and R.D. Topsom, Te/raJ/edro/1, 28, 2037
(1972).
13. G. Paliani and R. Cataliotti, Spec/rocIJi11l. Ас/а, Par/ А, 38А, 751 (1982).
12.8 FURYL
The 21 normal vibrations оС furan сап Ье dividcd into four ring stretching modes
(vFu), three ring in plane dcformations (БFu), two ring out of plane dcformations
(, Fu), four сн stretching vibrations (vCH), four сн in plane deformations (Бен)
and four сн out of plane deformations [,сн) [1 ]. ТЬе 21 normal vibrations
of 2 monosubstituted furans are listed in ТаЫе 12.16. ТЬе absorption regions of
the three ring stretching vibrations with the highest wavcnumbcrs agree well with
those found Ьу Angelclli et а/. [18] in the spectra of sixteen 2 substitutcd furans.
Thc extreme values assigned in the spectra of 21 Fu 2 Fu (1645R and 1542),
2 MeOFu (1520) and 2 IFu (1457 cm 1) are outside thcse regions. The fourth
ring stretch is tlle brcathing and occurs а! 1015 :f: 15 cm 1. ТЬс extensive regions
1200:!: 105 and 485 :f: 180 cm 1 for the substituent sensitive modcs: respectively
vC X, partly а ring vibration (see Section 12.4) and БFu, narrow to 1215 :f: 90
and 550 :f: 1 15 cm 1 for C substitutcd furans. Furans substituted with Cl, Br or 1
absorb а! lo\ver wavenumbers, 11 10 :f: 15 and 400 :f: 95 cm 1 respectively. The
spectra of 3 substituted furans Ьауе Ьееп studied Ьу Alberghina et а/. [16] and Ьу
Volka et а/. [17] and those of 2,5 disubstituted furans Ьу Grcen et а/. [8].
ТаЫе 12.16 АЬsоrptiоп regions (СП1 I) of the поmзаl vibrations of 2
substitutcd furans
ViЬratiоп C s Region Vibration C s Region
vCH а' 3155 :f: 15 БFu (Х) а' 920 :f: 35
vCH а' 3135 :f: 15 БFu а' 875 :f: 15
vCH а' 3115 :f: 15 ,сн а" 865 :f: 20
vFu а' 1575 :f: 30 ,СН а" 790 :f: 40
vFu а' 1485 :f: 25 ,СН а" 740 :f: 30
vFu а' 1380 :f: 20 ,Fu а" 625 :f: 30
Бсн а' 1235 :f: 20 БFu (Х) а' 485 :f: 180
vCX (Х) а' 1200 :f: 105 ,Fu а" 590:!: 10
Бсн а' 1170 :f: 25 Бсх (Х) а' 280 :f: 65
Бен а' 1075 :f: 20 ,СХ (Х) а" 200 :f: 55
vFu а' 1010:!: 15
12.8 Fиry/
335
х Fu compounds
Х = Mc [5 8], B , H2NCH2 [7], HOCH2 [7, 9], HSCH2 [7],
21 Fu , N=C [7, 17J, Н(O==)C [7, 8, 1 13], Мс(О==)С [7J,
CI(O==)C [7, 14], HO(O==)C [7,8], С02' [8, 15], McO(O==)C and
ЕtO(о==)с [7], N=C(O==)C , H2N(0==)C , McHN(O==)C and
MC2N(O==)C [16], R РЫ-IN(О==)С (R = Н, 3 and 4 Me, 3 апd 4
МеО, з and 4 N02, 3 and 4 Cl), McO [7J, CI [8], Br [5, 7, 8J,
I [8].
References
1. М. Rico, М. Barrachina and 1.М. Orza, J. Мо/. Spec/rosc., 24,133 (1967).
2. 1. Loisel and У. Lorenzelli, SpectrocIiim. Ас/а, Par/ А, 23А, 2903 (1967).
3.1. Loisel, 1.Р. Pinan Lucarre and У. Lorenzelli,J. Мо/. Strllct., 17,341 (1973).
4. G. Paliani, R. Cataliotti and А. Poletti, SpectrocIiim. Acta, Part А, 32А, 1089 (1976).
5. С. РоисЬап, 1. Raymond, Н. Sauvaitre and М. Chaillet, J. Мо/. Strllct., 21, 253 (1974).
6. D.W. Scott, J. Мо/. Spectrosc., 37, 77 (1971).
7. М. Senechal and Р. Saumagne, J. СЫт. P/IYS., 69, 1246 (1972).
8. 1.I-I.S. Green and D.J. Наrrisоп, SpectrocIiiт. Ас/а, Part А, 33А, 843 (1977).
9. L. Strandman Long and 1. Murto, SpectrocIiiт. Acta, Part А, 37А, 643 (1981).
10. 1. Banki, F. Billes, М. Gal, А. Grofcsik, G. 1alsovszky and L. Sztraka, Acta Chiт.
HI/l/g., 123, 115 (1986).
11. 1. Banki, F. Billes, М. Gal, А. Grofcsik, G. 1alsovszky and L. Sztraka, J. Мо/. Strиc/.,
142, 351 (1986).
12. G. Allen and H.J. Bemstein, Сап. J. C/leт., 33, 1055 (1955).
13. Р. Adamek, К. Volka, Z. Ksandr and 1. Stibor, J. Мо/. Spectrosc., 47, 252 (1973).
14. G. Cassanas Fabre and L. Bardet, J. Мо/. Strllct., 25, 281 (1975).
15. L. Bardet, 1. Maillols and G. Fabre, J. C/l;т. P/IYS., 68, 984 (1971).
16. G. Alberghina, S. Fisichella and S. Оссhiрiпti, Spec/roc!liт. Acta, Part А, 36А, 349
( 1980).
17. К. Volka, Р. Adamek, 1. Stibor and Z. Кsadr, Spectroc/l;т. Ас/а, Par/ А, 32А, 397
(1976).
18. 1.М. Angelelli, A.R. Katritzky, R.F. Pinzelli and R.D. Topsom, Tetralledroп, 28, 2037
(1972).
Acetates, OC(==O)Me, 22, 157, 274
Acetamides, NHC(==O)Me, 22, 157,
242
Acetanilides, PhNHC(==O)Me, 245
Acetoxy, OC(==O)Me, 22, 157, 274
Acetyl, C(==O)Me, 20, 155
Acetylamino, NHC(==O)Me, 242
Acetyloxy, OC(==O)Me, 22, 157, 274
Acids, C(==O)OH, 163, 261
Acid bromides, C(==O)Br, 152
Acid chlorides, C(==O)CI, 148
Acid fluorides, C(==O)F, 145
AJcohols
primary, CH20H, 64, 98, 261
secondary, CН(OН) , 128,261
tertiary, >C(OН) , 261
AJdehydes, C(==O)H, 137
AJkane fragments, 13, 89, 100
AIkenes, 15, 204
A1kynes, 15, 104,225
halogen substituted, C=CX, 227
Amides
primary, C(==O)NН2, 179, 236
secoI1dary, C(==O)NНMe, 17,190,
241
tertiary, C(==O)NMe2, 246
Amines
primary, NН 2 , 80, 233
secondary, NНMe, 17, 239
tertiary, NMe2, 246
Amine salts, CH2NНj, 83
Amino acids, +НзN R СО , 83, 198
Aminocarbonyl, C(==O)NH2, 179
Index
Aminomethyl, CH2NH2, 80
AmiI1osulfoI1yl, S02NН2, 294
AmiпоthiосаrЬопуl, C(==S)NH20 184
Ammопiоmеthуl, CH2NН;, 83
Aromatic hуdrосаrbопs, 306, 329
Aromatic suЬstitutiоп, 310
Aziridiпуl, cNCzH4, 303
Вепzепе derivatives, 306
mопоsuЬstitutеd, 313
disubstituted, 314
trisubstituted,318
ВепzуlЬromidеs, PhCН2Br, 59
Benzylchlorides, PhCH2CI, 53
ВrоmосаrЬопуl, C(==O)Br, 152
Bromoethynyl, C=CBr, 228
Bromoformyl, C(==O)Br, 152
Bromomethyl, CH2Br, 57
Bromomethylene, CHBr , 126
ButyI, tertiary, С(Ме)з, 40
Carbamoyl, C(==O)NН2' 179
Carbamoylchlorides, >NC(==O)Cl, 150
Carbonyl соmроuпds, 137
Carboxyl, C(==O)OH, 163, 261
Carboxylates, C02' 198
Carboxylic acids, C(==O)OH, 163,
261
CarboxyIic acids salts, C02' 198
Chlorocarbonyl, C(==O)CI, 148
Chlorocarbonyloxy, OC(==O)Cl, 150,
273
Chloroethyl, CH2CH2Cl, 95
338
Chlorocthynyl, C=CCI, 227
Сhlоrofоmшtеs, OC(==O)CI. 150,273
Cllloroformyl, C(==O)CI, 148
Chloroformyloxy, OC(==O)CI, 150,
273
Chloromethyl, CH2CI, 51
Chloromcthylene, CHCI , 126
Chlorosulfonyl, S02CI, 291
Cyanomcthyl, CH2C=N, 108
Cyanomethylene, СН(С=N) , 127
Cyclopropyl, сСзНs, 301
Dibromomethyl, CHBr2, 117
Dibromomethylene, CBr2 , 134
Dichloromethyl, CHCI2, 115
Dichloromethylene, CCI2 , 133
Difluoromethyl, CHF2 , 114
Difluoromethylene, CF2 , 132
Dihalogenomethyl, CHX2 113
Dihalogenomethylene, CX2 132
Dimethylamino, NMe2, 246
Dipolar ions, +НзN R СО , 83,
198
Dissimilar, СХ з bonds, 11, 28
Disulfides, SSMe, 19,279
Dithioesters, C(==S)SMe, 279
Esters
ethyl, C(==O)OEt, 174,271
methyl, C(==O)OMe, 23, 169
of sulfonic acids, S020R', 292
Ethenyl, CH==CH2, 204
Ethenylene, CH==CH , 218
Ethenylidene, >С==СН 2 , 212
Ethers
ethyl, OEt, 91, 269
methyl, OMe, 24, 68, 263
Ethoxy, OEt, 91, 269
Ethoxycarbonyl, C(==O)OEt, 174,
271
Ethyl, СН2СНЗ, 13, 89
Ethyl esters, C(==O)OEt, 174,271
Ethyl ethers, OEt, 269
Ethylthio, SEt, 91, 281
Ethynyl, C=CH, 225
Fluorocarbonyl, C(==O)F, 145
Fluoroformates, OC(==O)F, 146
Fluoroformyl, C(==O)F, 145
Fluoromethyl, CH2F, 48
Fluoromethylene, CHF , 125
/lIdex
FluorosulfoI1yl, S02F, 289
Formamides, 140
Fоmшtеs, OC(==O)H, 140, 272
Fomlyl, C(==O)H, 137
Fomlyloxy, OC(==O)H, 140, 272
Fundamental vibrations
of а molecular fragment, 1
of а molccule, 2
Furan derivatives, 334
Furyl, Fu, 334
Halogen compounds, 28, 48, 94, 113,
125, 132, 148, 152, 227, 273, 291
Halogenomethyl, CH2X, 48
Halogenomethylene, CHX , 125
Hydroxy compounds, OH, 64, 98, 128,
258
Hydroxyethyl, CH2CH20H, 98
Hydroxylamines, >N OH, 261
Hydroxymethyl. CH20H, 64
Hydroxymethylene, CH(OH) , 128
II1terpretation of spectra, 3
Iodoethynyl, C=CI, 229
Iodometllyl, CH2I, 62
Isocyanates, CH2N==C==O, 87
Isocyanalomethyl, CH2N==C==O, 87
Isopropyl, CН(Me)2, 119
Isothiocyanates, CH2N==C==S, 88
Isothiocyanalomethyl, CH2N==C==S,
88
Ketones
methyl, C(==O)Me, 20, 155
ethyl, C(==O)Et, 91, 160
Mercaptomethyl, CH2SH, 72
Methanesulfonamides, > NS0 2 Me,
289
N phenyl PhHNS02Me, 289
Methanesulfonates, OS02Me, 289
Mcthanesulfonylhalides, XS0 2 Me, 289
Methoxy, OMe, 24, 68, 263
Methoxycarbonyl, C(==O)OMe, 23,
169
Methoxymethyl, CH20Me, 68
Methoxythiocarbonyl, 24
Methyl, СНз, 10
Methylamino, NHMe, 17,239
Methylaminocarbonyl, C(==O)NНMe,
17,190,241
Mclhylaminosulfonyl, S02NHMc, 17,
24], 296
MClhylaminoth iocarbony 1,
C(==S)NHMc, ]7, ]95,241
MClhylcarbamoyl, C(==O)NHMc, 17,
190,241
Mcthyl cstcrs, C(==O)OMc, 23, 169
Mcthyl clhcrs, OMc, 24, 68, 263
Mcthylphosphinatcs, >Р(==О)ОМс, 24,
266
Mcthylphosphonatcs, P(==O)(OMC)2'
266
Mcthylsilancs, >Si(Mc) , 20
Mcthylsulfinyl, S(==O)Mc, 20,
284
MClhylsulfonyl, S02Mc, 20, 286
Mcthylsulfoxidc, S(==O)Mc, 20, 284
Mcthylthio, SMc, 17,75, 277
Mcthy Ithiocarbamoy 1, С( == S )NH Мс,
17,195,241
Mcthyllhiomcthyl, CH2SMc, 75
Mcthyllhiophosphinatcs, >P(==S)OMc,
24, 266
Mcthy Ithiophosphonatcs,
P(==S)(OMe)2' 266
Nitratcs, ON02, 254
Nitrilcs
cyanomcthyl, CH2C=N, 108
branchcd, СН(С=N) , 127
Nitro, N02' 250
Nilroamincs, >N N02, 254
Normal vibrations
of а mo]ccular fragmcnt, 1
of а molcculc, 2
Oximcs, >N OH, 261
Oxirany], СС2НЗО, 303
Оху compounds, 258
Oxymcthyl compounds, 64
Oxysulfonyl, S020R', 292
Phcnols, PhOH, 259
Phcnyl, Ph, 306
mcthyl substituted, 13
monosubstitutcd, 313
disubstitutcd,314
trisubstitutcd, 318
Phosphinatcs, >Р(==О)ОМс, 24, 266
Phosphonatcs, Р(==О)(ОМС)2, 266
Propanoy], C(==O)Et, 91, 160
/lIdex
339
Propionyl, C(==O)Et, 91, 160
n Propyl, СН2СН2СНJ, 13, 100
Propynyl, CH2C=CH, 104
Pyridinc dcrivativcs, 329
Pyridyl, Ру, 329
Pyrimidinc dcrivalives, 331
Pyrimidinyl, Pym, 331
Silanols, >Si(OH) , 26]
Substituent scnsitive modc, 307
Sulfides, 17, 75, 277
Sulfinates, 24, 266
Sulfonamides
primary, S02NH2' 236, 294
N mcthyl, S02NHMe, 17,241,
296
N phenyl MeS02NHPh , 289
sccondary, S02NH , 295
Sulf(on)atcs S020 , 292
Sulfoncs
S02 , 296
S02Mc, 286
Sulfonyl, S02 , 296
Sulfonylchlorides, S02CI, 291
Sulfonylfluorides, S02F, 289
Sulfoxides, S(==O)Me, 20, 284
Sulfur compounds, 277
Tcrtiary butyl, С(Ме)з, 40
Thicnyl, Tb, 332
Thioacctates, SC(==O)Me, 22, 157
Thioamidcs
prirnary, C(==S)NН2' 184, 236
sccondary, N mcthyl, C(==S)NHMe,
17, 195,241
Thiocarbamoyl, C(==S)NH2, 184
Тhiocyanates, CH2SCN, 78
Thiocyanatomethyl, CH2SCN, 78
Тhioestcrs, C(==O)SMc, 279
Thioethcrs, SMe, 17,75,277
Thioethyl compounds, SEt, 91, 281
Thioformatcs, SC(==O)H, 140
Thiols, CH2SH, 72
Thiomcthyl соmроuпds, SMe, 17,75,
277
Thiophcnc dcrivatives, 332
TribromomcthyI, СВrз, 36
TrichlorocthyI, СН2ССlз, 94
Trichloromethyl, ССlз, 34
Trifluoroacetyl, С(==О)СFз, 3О
Trifluoromethyl, СFз, 29
340
Trifluoromethylbenzencs,
Рh
СFз,
33
Trihalogenomethyl,
СХЗ, 28
Ureas, >N
C(==O)NH2, 182
J т/ех
Vinyl,
CH==CI.12' 204
Vinylcne,
CH==CH
, 218
Vinylidene, >С==СН 2 , 212
Zwilter
ions, +НзN
R
СО
, 83,198