CHAPTER 7

OLEFIN GROUPS

7.1
(a)

Noncyclic

Olefins

INTRODUCTION

In addition to the C = C bond, a vinyl group has three carbonhydrogen

bonds and so will have three CH stretching vibrations, three in-plane CH
bending and three out-of-plane CH bending vibrations. These vibrations each
interact to give the modes illustrated in Fig. 7.I. 1 " 3 Also illustrated are the
in-phase, out-of-plane CH wagging vibrations for trans- and c/s-disubstituted olefins, 1,1-disubstituted ethylene, and trisubstituted ethylene. The
spectral regions for the alkyl-substituted olefins are given in Table 7.I. 1 " 6
Figure 7.2 shows the general spectra expected for ethylenes with alkane
substituents.
(b)

OLEFINIC CH STRETCHING VIBRATIONS

Olefinic CH stretching frequencies occur at 3130-2980 cm"1. In trialkyl

substituted ethylenes, the lone = C H stretch band can be seen in the region
3050-2990 cm - 1 , but non-alkane substituents can raise the wavenumbers
(trichloroethylene, 3083 cm"1).6*
Both eis and trans RHC=CHR dialkyl substituted ethylenes have a = C H
stretch band about 3020-2995 cm"1. In methyl oleate, for example, the

*N. Sheppard and D. M. Simpson, Quart. Rev. Chem. Soc. 6, 1 (1952).

W. J. Potts and R. A. Nyquist, Spectrochim. Acta 15, 679 (1959.
3
J. R. Scherer and W. J. Potts, / . Chem. Phys. 30, 1527 (1959).
4
S. E. Wiberley, S. C. Bunce, and W. H. Bauer, Anal. Chem. 32, 217 (1960).
. L. McMurry and V. Thornton, Anal. Chem. 24, 318 (1952).
6
F. R. Dollish, W. G. Fateley, and F. F. Bentley, "Characteristic Raman Frequencies of
Organic Compounds," John Wiley and Sons, New York 1974.
6a
C. J. Pouchert, "The Aldrich Library of FT-IR Spectra," Aldrich Chemical Co. Milwaukee, (1975).
2

247

248

INTRODUCTION TO INFRARED AND RAMAN SPECTROSCOPY

K
?=***

OUT-OF-PHASE + \
J~ "TRANS"
CH2 STRETCH
0 = 0
CH WAG
3080 cm-'
J
>>4* " 0 cm-'
CH STRETCH
3010
IN-PHASE

CH2 STRETCH

2985
C
= C STRETCH
1640

W
J
VI4I5

"" DEFORMATION

^ooROCK
hO
A
\

CH2 ROCK
1075

P=^> ,07.
4

\f=/
7*

J*+

+ \

CH2 WAG
910

/ + 'CIS"
CH WAG
630
Q=H

r^*

+ \

TRANS
CH WAG
970

/ +
b = o CH2WAG

+ W + s

68CH

h = 0

JT\

WAG

VPQ
^ + CH WAG
,

^"^

825

FIG. 7.1. Olefinic vibrations. The left-hand column illustrates the in-plane vibrations
of the vinyl group. The right-hand column illustrates the out-of-plane vibrations ( + and )
of the vinyl group and for comparison the in-phase, out-of-plane hydrogen wagging
vibrations of trans-, eis-, and 1,1-disubstituted olefins and trisubstituted olefins. The
approximate frequencies are given for hydrocarbon-substituted olefins.

3000 cm ' = C H band is the clearest sign of unsaturation. Again, non-alkane substituents can raise the wavenumber, (eis and trans-1,2-dichloroethylene, 3079 and 3086 cm"1).6"
The out-of-phase =CH 2 stretch vibrations in vinyls (monosubstituted ethylenes) and vinylidenes (1,1-disubstituted ethylenes) give rise to a band at
3100-3070 cm -1 in hydrocarbons, and slightly higher for non alkane substituents. This band is well separated from CH3 bands below 3000 cm -1 .
The in-phase =CH 2 stretching vibration band is often obscured by alkane
substituent absorption. When the alkane substituent groups in 1,1-dialkyl
ethylenes have no CH3 group, the in-phase =CH 2 stretch band can be seen

7. OLEFIN GROUPS

W
W

3010
2985

CH 2 CH
STR

2985

r
/

CH 2 STR

2X
910

640

STR

c_c

1650

2X
890

c=c

249

V'4I5
CH 2 DEF

"V 1415
C H 2 DEF

STR

965

3010

CH STR

R'

TRANS
CH
WAG

I
V

~V^

3000

FIG. 7.2.

2600cm-

2000

690

\ Ziv

CIS
CH
WAG

1675
C=C
STR

c=c
3400

50
ern

1800

1600

820
CH

WAG

1400

1200

1000

800

600

General IR spectra expected for ethylenes with alkane substituents.

about 100 cm - 1 lower than the out-of-phase = C H 2 stretch, at about 30002980 cm' 1 . Alkane CH2 groups have two stretching bands (2925, 2855 cm"1)
separated by about 70 cm"1. The CH2 angle in alkanes is about 109.5. In
= C H 2 groups, the CH2 bond angle is about 120. The increase in the CH2
angle, increases the stretch band separation (see Sec. 4.12). In 1,1 dichloroethylene, the out-of-phase and in-phase = C H 2 stretching bands are seen
at 3125 and 3030 cm" 1 . 63
In vinyl hydrocarbons (without CH3 interference) a doublet with a spacing
of about 20 cm - 1 can usually be seen at 3020-2980 cm"1 (higher in nonhydrocarbons). The bands just above and below 3000 cm"1 in hydrocarbons
are assigned most probably to = C H stretch and in-phase = C H 2 stretch
respectively.
(c)

OLEFINIC C = C

STRETCHING VIBRATIONS

The C = C stretch vibrations, illustrated in Fig. 7.1, interacts to some

extent with = C H 2 deformation vibration and to some extent with the attached single bond stretching vibration, since nonhydrogen substituent atoms
remain nearly motionless for this mode. The C = C stretching frequency will
be affected by changes in these interactions and by mesomeric and inductive
effects which alter the strength of the C = C and attached CX bonds.

250

INTRODUCTION TO INFRARED AND RAMAN SPECTROSCOPY

TABLE 7.1
SPECTRAL REGIONS FOR THE ALKYL-SUBSTITUTED OLEFINS (IN cm - 1 )

H
\
C

C=C

\
H

Vinyl

/ C = C xH
C
trans

H
\

H
/
C= C
eis

/c=cv

C
H
Vinylidine

c=c

3100-3070
3025-3012
1840-1805
1648-1638
1420-1412
995- 985
910- 905

Medium CH2 asymmetric stretch

Medium CH stretch
Medium 2 x CH2 wag
Medium C=C Stretch
Medium CH2 deformation
Strong trans CH wag
Strong CH2 wag

3020-2995
1678-1668
980- 965

Medium CH stretch
Weak or absent (strong Raman band) C=C stretch
Strong trans CH wag

3020-2995
1662-1631
1429-1397
730- 650

Medium CH stretch
Medium C=C stretch
Medium CH rock
Medium to strong eis CH wag

3100-3070
1792-1775
1661-1639
895- 885

Medium CH2 asymmetric stretch

Medium 2 x CH2 wag
Medium C=C stretch
Strong CH2 wag

3050-2990
1692-1667
840- 790

Weak CH stretch
Weak C=C stretch
Medium to strong CH wag

1680-1665

Weak or absent (strong Raman band) C=C stretch

Trisubstituted

c=c

Tetrasubstituted

7. OLEFIN GROUPS

251

The C = C stretching frequency near 1640 cm - 1 in vinyl hydrocarbons is

a medium intensity band which becomes inactive in the infrared region in
a symmetrical trans- or symmetrical tetrasubstituted double bond compound,
both of which have centers of symmetry. Even when the substituents are
not exactly alike in trans-ana tetrasubstituted olefins, the infrared absorption
may be quite weak.5 These double bond vibrations all appear strongly in the
Raman effect, however, where the C = C stretch vibration in all types of
ethylenes gives rise to a strong Raman band in the region 1680-1630 cm - 1 .
The trans, tri, and tetra alkyl-substituted ethylenes appear at 1680-1665 cm -1 ,
which are strong in Raman but weak or absent in the infrared. The eis, or
1,1-dialkyl, or monoalkyl ethylenes appear at 1660-1630 cm"1 with medium intensity in the infrared.5'6
Conjugation, which weakens the C = C force constant, lowers the frequency 10-50 cm""1. In 1,3-dienes the two double bonds interact to give
two stretching bands. In both eis- and irans-l,3-pentadiene, in-phase stretching bands occur at 1658 cm"1 and out-of-phase at 1605 cm"1.7 In 1,3-butadiene only the out-of-phase (asymmetric) stretch is infrared active, absorbing at 1603 cm - 1 . 7
Fluorinated olefins have an unusually high C = C frequency8 at 17551735 cm"1 for the group C=CF 2 and 1800-1780 cm"1 for the group CF=CF 2 .
Other noncyclic, nonhydrocarbon double bond bands are usually found at
1680-1570 cm"1. The C = C frequency is usually lowered if an aliphatic
group substituent is replaced by a heavy atom such as chlorine or sulfur (cis1,2-dichloroethylene 1587 cm _1 ). 6a
(d)

OLEFINIC CH AND CH2 IN-PLANE BENDING VIBRATIONS

The CH2 scissors deformation of the vinyl and vinylidine groups give rise
to a medium intensity band in the infrared and Raman spectra near 1415
cm - 1 5 In ciJ-l,2-dialkyl ethylenes, the in-plane CH rock where both CH
bonds rotate in the same direction (clockwise or counterclockwise) appears
near 1405 cm - 1 in the infrared, and the rock where the CH bonds rotate
oppositely appears near 1265 cm"1 in the Raman spectrum.1 In trans-1,2dialkyl ethylenes, the in-plane rock where both CH bonds rotate in the same
direction appears in the Raman spectrum near 1305 cm""1, and the rock where
the CH bonds rotate oppositely appears near 1295 cm""1 in the infrared spectrum.1 In monoalkyl ethylenes the CH rock shows up in the Raman spectrum
near 1295 cm"1 where all the ethylene CH bonds rotate in the same direction
to some extent.1
7
8

R. S. Rasmussen and R. R. Brattain, / . Chem. Phys. 15, 120 and 131 (1947).
L. J. Bellamy, Spectrochim. Ada 13, 60 (1958).

252

INTRODUCTION TO INFRARED AND RAMAN SPECTROSCOPY

72

Olefinic Hydrogen Wagging

(a)

THE C = C H 2 WAG VIBRATION

Vibrations

The strongest bands in olefins rise from the hydrogen wag (out-of-plane)
vibrations of the group 1 ' 2,5 ' 7,9,10 (see Fig. 7.1 and 7.2). Vinyl and vinylidene
compounds both have the = C H 2 group in common and have a = C H 2 wag
vibration where the hydrogens move out of the plane of the group, in-phase.
This essentially changes the angle between the CH2 plane and the C = C
bond, with the substituent or substituents nearly stationary. The rest of the
molecule is relatively uninvolved mechanically in this vibration (see Fig.
4.15). For alkyl substituted ethylenes the vinyl CH2 wag absorbs at 910905 cm - 1 and the vinylidene CH2 wag absorbs at 895-885 cm - 1 , as seen
in Table 7.1. Both = C H 2 wag bands have usually strong overtones, 5-15
cm"1 higher than twice the fundamental wavenumber.2
When non-hydrocarbons are considered, the CH2 wagging frequency is
not substituent mass sensitive but is quite sensitive to mesomeric effects2
(see Table 7.2). Those substituents which mesomerically withdraw electrons
from the = C H 2 carbon, increase the wag frequency and decrease its intensity, while those substituents which mesomerically donate electrons to the
= C H 2 carbon, decrease the wag frequency and increase its intensity, relative to hydrocarbon olefins. 211 These results were verified by molecular
orbital calculations.11
+

N = C - C H = C H 2 < N = C = C H C H 2
+

ROCH=CH 2 < R0=CHCH 2

960 cm"l
813 cm"1

In the vinyl ether above, the right hand resonance form has a CH2 group
with a negative charge, and the result is that this carbon has an electron pair
in a non-bonding pi orbital. If the substituent could donate a whole electron
to the CH2 carbon, this would be the structure. This is isoelectronic, with
an amine - N H 2 which has a non-planar structure. This suggests that electron
donation makes the CH2 group easier to wag and lowers the frequency. During the wag vibration, the CH2 hydrogens move from one side of the group
plane to the other. In the electron donation structure, the non-bonding pi
orbital with its electron pair, changes its shape during the wag vibration,

J. K. Brown and N. Sheppard, Trans. Faraday Soc. 51, 1611 (1955).

H. W. Thompson and P. Torkington, Trans. Faraday Soc. 41, 246 (1945).
n
N . B. Colthup and M. K. Orloff, Spetrochim, Acta, Part A 27, 1299 (1971).
10

253

7. OLEFIN GROUPS

tending to displace the electrons in the opposite direction from the hydrogens. This suggests that electron donation increases the CH2 wag band intensity.
In vinylidenes, both groups shift the CH2 wag frequency additively. The
CH2 wag frequency has been correlated with the ortho-para directing ability
of the group,2 and with the total electron density on the = C H 2 carbon as
calculated from molecular orbital theory.11 The CH2 wag wavenumber can
be approximately by the following relationship for vinyls and vinylidenes,
for which a selection of A values are given for the X and Y substituents (R
is an alkane group).
v [(XY)C=CH2 wag] = 930 cm"1 + + 10

cm"1.

A values in cm - 1 are;
COOR +30, C==N +25, H O, CH2Cl O,
R - 2 0 , C6H5 - 2 0 , Cl - 3 0 , OCOCH3 - 5 0 ,
F-65,OR-115.
As was stated before, the CH2 wag has an unusually strong overtone,
useful as a check if there is no interference. The = C H 2 wag in olefins and
the = C H wag in acetylenes have overtones where the dipole moment changes
along the unsaturated CC bond. The greater than usual overtone intensity
suggests that there is extra anharmonicity in the fundamental. The = C H 2
or ^ C H wag vibration in these cases distorts the pi orbitals on one end of
the unsaturated bond, two times during the vibrational cycle, every time the
CHs bend in one direction or the other. This tends to displace electrons along
the unsaturated CC bond to some extent at twice the frequency of the wag
vibration. The unsaturated CH wag vibrations in aromatic rings give rise to
unusually strong CH wag combination bands, presumably from the same
type of anharmonicity (see Chapter 8).

(b)

THE TRANS HC=CH WAG VIBRATION

The in-phase, out-of-plane HC=CH wag vibration of /rans-dialkyl substituted olefins absorbs strongly at 980-965 cm"1, and is closely related to
the 995-985 cm"1 vibration in monoalkyl vinyl groups 2,3,5,9 (see Fig. 7.1).
We will call these vibrations trans-CH wag for both groups. These bands
have no prominent overtone. In addition to wagging the CH bond out of the
group plane, these vibrations also twist the C = C bond, because the two
CH bonds also rotate about the C = C axis in opposite directions. In some

254

INTRODUCTION TO INFRARED AND RAMAN SPECTROSCOPY

TABLE 7.2
CH2 WAGGING FREQUENCIES (IN cm"1)

R-0-CO-CH=CH2
NsC-CH=CH2
R-CH=CH 2
C1-CH=CH 2
R-CO-0-CH=CH2
RCONCH=CH2
R-0-CH=CH2

961
960
910
894
870
840
813

na C ^> - C H 2

985

Nl= C ^

R
>-CH
R- -OCO
Ns

Cl

/C-CHi

939

916

R
/C-CH2
R

890

Cl
/C-CH2
Cl

867

R
/C-CH2
R- - O

795

RR-

>-CH2

711

studies these vibrations are called C = C twist. In both irans-disubstituted

ethylenes and vinyls, the substituents are nearly stationary and are mechanically uninvolved in these vibrations.

255

7. OLEFIN GROUPS

The trans-CH wagging vibration of the vinyl- and /AYws-disubstituted

olefins is relatively insensitive to mass or mesomeric effects but shows some
sensitivity to the inductive power of the group. Electronegative groups tend
to lower this frequency relative to hydrocarbons. 2 In /ra/w-disubstitution,
both groups shift the frequency. See Table 7.3. 2
TABLE 7.3
Trans-CH WAGGING FREQUENCIES (IN cm"1)

(CH 3 ) 3 Si-CH=CH 2
R-CH=CH2
R-0-CO-CH=CH2
R-CO-N-CH=CH2
R-0-CH=CH2
R-CO-0-CH=CH2
C1-CH=CH 2
R - 0 - C O - C H = = C H - C O - 0 - R trans
C H 3 - C H = C H - C O - 0 - R trans
R - C H = C H - R trans
CH 3 CH=CH-C=N trans
CH 3 -CH=CH-C1 trans
C 1 - C H = C H - C = N trans
C1-CH=CH-C1 trans

1009
990
982
972
960
950
938
976
968
964
953
926
920
892

The intensity for the XHC=CHX trans-CH wag band is two or three
times greater on the average than the intensity for the XHC=CH 2 trans-CH
wag band, as was predicted from molecular orbital calculations.11 As seen
in Fig. 7.1, in both the irans-disubstituted ethylenes and the vinyl groups,
the trans-CH wag vibration moves the two trans hydrogens in the same
direction, but in the vinyl group, the third hydrogen moves in the opposite
direction, tending to reduce the dipole moment change here.
(c)

OTHER = C H

WAG VIBRATIONS

The in-phase, out-of-plane CH wag of the ds-disubstituted hydrocarbon

olefins gives rise to a more variable, less reliable, weaker band near 730640 cm - 1 in hydrocarbons. Unlike the trans in-phase CH wag, the eis inphase wag does not twist the C = C bond. The two CH bonds rotate about
the C = C axis in the same direction, which accounts for why the eis wag
wavenumber is much lower than the trans (see Fig. 4.16). The in-phase eis
wag vibration is related to the lowest frequency vinyl CH wag vibration,

256

INTRODUCTION TO INFRARED AND RAMAN SPECTROSCOPY

which gives rise to a weak variable band near 630 cm"1 (See Fig. 7.1). In
the Raman spectra this band appears weakly at 634-621 cm - 1 in hydrocarbons. We shall call this vinyl vibration eis-CU wag also, since it moves the
two eis hydrogens in the same direction.
In both the hydrogen wag vibrations discussed previously, the motions of
the hydrogens are partially balanced by countermotions of the substituents
(See Fig. 4.15). This makes the substituents more mechanically involved in
the vibrations which makes these vibrations more variable in frequency than
those discussed. When rotational isomers are possible in the c/s-olefins, the
wag band can be broadened. Cyclohexenes absorb at the low frequency end
of the eis region.
The lone = C H of a trisubstituted ethylene has the out-of-plane wag frequency near 840-790 cm"1 in hydrocarbons. Like the vibrations discussed
above the substituents are mechanically involved to some extent, making
the frequency somewhat variable. This medium intensity band is not always
easy to pick out among other bands.
The out-of-phase, out-of-plane = C H vibrations in the eis, trans, or vinylidene hydrocarbon olefins do not usually result in useful infrared bands.
In the Raman spectra, c/s-dialkyl ethylenes have a medium intensity band
at 970-952 cm"1 and the irans-dialkyl ethylenes have a very weak band at
776-745 cm -1 , assigned to the out-of-phase, out-of-plane CH wag vibrations6
(see Fig. 4.16). The vinylidene CH2 twist has a weak Raman band at 7 1 1 684 cm"1 in hydrocarbons.6
(d)

CIS-TRANS CONJUGATED POLYENES

In conjugated polyenes containing conjugated trans- and cw-substituted

double bonds, mechanical interaction can affect the 965 cm"1 region.12 The
in-phase trans-CH wag vibration and the infrared inactive out-of-phase eis
CH wag vibration have about the same frequency, 965 cm"1.9 This means
that both kinds of groups will be excited at the same time, but with various
phase relationships. The expected frequencies and relative intensities of a
few examples are listed in Table 7.4 where, for example, the last entry
indicates that a cis-trans-cis conjugated triene has bands within 10 cm"1 of
994 and 936 cm"1, each about one-third as intense as an isolated trans group
band at 965 cm" 1 . 12
If a vinyl group is conjugated to a trans CH=CH group, the CH wag
vibrations of the two groups can interact also. The compound trans-1,3pentadiene,2 for example, has wag bands at 1001, 948 and 895 cm"1.

12

N. B. Colthup, Appl Spectrosc. 25, 368 (1971).

257

7. OLEFIN GROUPS

TABLE 7.4
APPROXIMATE CH WAG FREQUENCIES AND RELATIVE INTENSITIES FOR eis (C), trans (T)
CONJUGATED POLYENES

Diene

986 cm- 1

944 cm- 1

Triene

994 cm" 1

965 cm" 1

TT
CT

2
*
0

0
*
0

TTT
CTT
CTC

cc

7.3

4
3

1
3

936 cm" 1
0
1
3

Cyclic C=C

An external C = C H 2 on an otherwise saturated six-membered ring is not

noticeable different from its noncyclic vinylidine counterparts. As the ring
gets smaller, the double bond-single bond angle increases due to strain.
There is a steady increase in the C = C stretching frequency13 due predominantly to an increasing interaction with the CC bonds directly attached 14
(see Fig. 4.7). As the double bond stretches, the attached single bonds must
be contracted, the amount of this interaction varying with the double bondsingle bond angle. 14 See Table 7.5.
TABLE 7.5
H 2 C = C EXTERNAL CYCLIC DOUBLE BOND STRETCHING FREQUENCIES (IN cm" 1 )

6-Membered
5-Membered
4-Membered
3-Membered
(2-Membered

ring
ring
ring
ring
ring)

Mthylne
Mthylne
Mthylne
Mthylne
(Aline)

cyclohexane
cyclopentane
cyclobutane
cyclopropane

1651
1657
1678
1781
1980

Substitution of the hydrogens of the C = C H 2 group with methyl groups

increases the frequency,17 due in part to out of phase interaction with the
attached CC bonds.
CH2

H3C^

^CH3

^C^

CH 2

3C^C/CH3

1657 cm" 1
13

1687 cm-'

1651cm -1

1668 cm"

R. C. Lord and F. A. Miller, Appl. Spectrosc. 10, 115 (1956).

N. B. Colthup, / . Chem. Educ. 38, 394 (1961).
15
E. J. Blau, Diss. Abstr. 18, 1628 (1958).
16
G. Herzberg, " Infrared and Raman Spectra of Polyatomic Molecules," Van NostrandReinhold, Princeton, New Jersey, 1945.
17
G. Chiurdoglu, J. Laune, and M. Poelmans, Bull. Soc. Chim. Belg. 65, 257 (1956).
14

258

INTRODUCTION TO INFRARED AND RAMAN SPECTROSCOPY

An unsubstituted C = C H 2 group on a bridged five-membered ring is

under more strain than mthylne cyclopentane and resembles mthylne
cyclobutane.17
CH

CH 2

1672 cm*1

1678 cm" 1

An internal CH=CH in an otherwise saturated six-membered ring

is not noticeable different from its noncyclic eis counterpart. As the ring
gets smaller, the C = C stretching frequency decreases from the six- to the
four-membered ring case as the double bond-single bond angle decreases to
90. 13,18 This is due predominantly to changes in the interaction with the
CC bonds directly attached, which are altered in length as the double
bond vibrates (see Fig. 5.12). This interaction is at a minimum at 90 and
increases as the angle gets larger or smaller than 90. 14 The = C H stretching
frequency is also sensitive to ring size.14 See Table 7.6.
TABLE 7.6

CH=CH INTERNAL CYCLIC DOUBLE BOND AND CH BOND STRETCHING FREQUENCIES (IN cm-1)
3017 13
3045' 3
3060 13
3124, 3158
3374 16

1646
1611
1566
1656*
1974

Cyclohexene
Cyclopentene
Cyclobutene
Cyclopropene
(Acetylene)

6-Membered ring
5-Membered ring
4-Membered ring
3-Membered ring
(2-Membered ring)

Raman, 1647 cm '

Substitution of the remaining hydrogens with carbons will change the

interaction.
CH3

1566 cm- 1

18

13

1641cm"1

20

H3C

1675 cm-'

CH3

21

R. C. Lord and R. W. Walker, /. Amer. Chem. Soc. 76, 2518 (1954).

R. W. Mitchell, E. A. Dorko, and J. A. Merritt, J. Mol. Spectrosc. 26, 197 (1968).
20
F. F. Cleveland, M. J. Murray, and W. S. Gallaway, /. Chem. Phys. 15, 742 (1947).
21
R. Srinivasan, /. Amer. Chem. Soc. 84, 4141 (1962).
19

259

7. OLEFIN GROUPS

All the above cyclobutene double bonds are equally strained, but the added
out-of-phase interaction with the noncyclic CC bonds increases the
frequency.14
If the carbons in the ring which are not part of the C = C group are substituted, there is little mechanical effect and frequency shifts are small.
A band at 1684 cm" 1 is reported for 1,2-dimethylcyclobutenes where the
3 and 4 positions are substituted.22 The same thing occurs in alkyl-substituted
cyclopentenes23 and cyclohexenes.24

a"

1617-1614 c m - 1

1657-1650 c m - 1

p.

1686-1671 c m - 1

"

1655-1645 cm" 1

1682-1668 cm" 1

1685-1677 cm" 1
(Raman)

As seen above the frequencies for the 1,2-dialkyl cyclo-enes are nearly the
same from the six- to the four-membered ring (1690-1670 cm" 1 ). This is
markedly different from the unsubstituted case (1646-* 1611-+1566 cm" 1 ).
The decrease in the cyclic single bond-double bond angle as the ring gets
smaller which reduces interaction and frequency is compensated for by an
increase in the noncyclic single bond-double bond angle which increases
interaction and frequency. The effect of interaction is to leave the frequencies
nearly unchanged even though the strain is altered. 14 The 1,2-dialkylcyclopropenes have a ring angle much less than 90 where interaction again increases the frequency, and this combined with an increased noncyclic single
bond-double bond angle 25 of about 150 markedly increases the frequency

22

R. Criegee and G. Louis, Chem. Ber. 90, 417 (1957).

L. M. Sverdlov and E. P. Krainov, Opt. Spectrosc. (USSR) 6, 214 (1959).
24
"Landolt-Brnstein Tables," 6th ed., Vol. 1, Part 2, pp. 480-510. Springer-Verlag,
Berlin and New York, 1951.
25
P. H. Kasai, R. J. Myers, D. F. Eggers, Jr., and K. B. Wiberg, / . Chem. Phys. 30, 512
(1959).
23

260

INTRODUCTION TO INFRARED AND RAMAN SPECTROSCOPY

TABLE 7.7
INTERNAL CYCLIC DOUBLE BOND, 1,2-DISUBSTITUTED (IN crrr X)

6-Membered
5-Membered
4-Membered
3-Membered
(2-Membered

ring
ring
ring
ring
ring)

Cyclohexenes, 1,2-dialkyl
Cyclopentenes, 1,2-dialkyl
Cyclobutenes, 1,2-dimethyl
Cyclopropenes, 1,2-dialkyl
(Acetylene, 1,2-dimethyl)

1685-167724
1686-167123
1685-16752122
1900-186526-28
231316

which occurs at 1900-1865 cm" 1 . 26 ^ 28 The compound 1-methylcyclopropene absorbs at 1788 cm""1 29 somewhat lower than the 1,2-disubstituted
case as expected.
Table 7.7 lists double bond stretching frequencies (some from Raman
data) of the 1,2-disubstituted cyclo-enes. Other positions as well as 1 and 2
may be substituted.
Bridged rings with unsubstituted internal double bonds such as in dicyclopentadiene have extra strain resulting in smaller bond angles than in unbridged rings of the same size, resulting in absorption at lower frequencies
for these double bonds (ca. 1570 cm" 1 for a bridgedfive-memberedring and
ca. 1615 cm" 1 for a bridged six-membered ring13,18).

1568 cm"

26

1566 cm"

1614 cm - 1

1611cm"1

W. E. Doering and T. Mole, Tetrahedron 10, 65 (1960).

R. Breslow and H. Hover, /. Amer. Chem. Soc. 82, 2644 (1960).
28
K. Faure and J. C. Smith, /. Chem. Soc, London p. 1818 (1956).
29
R. W. Mitchell and J. A. Merritt, Spectrochim. Ada, Part A 25, 1881 (1969).
27