A STUDY OF THE ABSORPTION
CHARACTERISTICS OF THE CARBON -
CARBON DOUBLE BOND IN THE INFRARED
LEON S. PIJANOWSKI, JR.
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
The author wishes to express sincere thanks to his
research director, Dr. Armin H. Gropp, for his advice and
encouragement in this research. He is also indebted to the
other members of his committee.
The helpful suggestions of some of his colleagues
were most appreciated.
The compounds contributed by Peninsular ChemResearch,
Dr. John Savory, Dr. George Butler, Dr. Paul Tarrant and their
graduate students were invaluable.
The author also wishes to acknowledge the financial
assistance of the General Motors Corporation which contributed
significantly in making this research possible.
TABLE OF CONTENTS
ACKNOWLEDGEMENTS . . ... ... ii
LIST OF TABLES . . ... ... iv
LIST OF FIGURES . . ... ... vi
I INTRODUCTION . .. 1
II APPARATUS AND EXPERIMENTAL TECHNIQUE .... 18
Apparatus . ... 18
Techniques . ... 21
Origin and Purification of Compounds 26
III DISCUSSION OF RESULTS. . 27
IV SUMMARY . .... 74
BIBLIOGRAPHY . . ... ..... 76
BIOGRAPHICAL NOTE . .... 81
LIST OF TABLES
1. C=C Stretching Bands of Terminal Olefins of the
Type CH2=CHR . .... .30
2. C=C Stretching Bands of Terminal Olefins of the
Type CH2=C(CH3)R . .... .33
3. Influence of Increase in Symmetry Upon C=C
Stretching Bands . .... .37
4. Effect of Substitution and Chain Length on C=C
Stretching Bands . .... .39
5. Effect of Fluorine Substitution in Small Molecules
on C=C Stretching Bands .... 41
6. C=C Stretching Bands of Substituted Ethylenes 43
7. Effect of Substitution at the a Carbon Atom on
the C=C Stretching Bands of Propylenes .. 45
8. C=C Stretching Bands of Substituted Perfluoro
Ethylenes . .... 46
9. C=C Stretching Bands of Substituted Propylenes. 50
10. C=C Stretching Bands of Substituted 2-Methylpropenes 52
11. C=C Stretching Bands of Substituted Fluoropropenes 53
12. C=C Stretching Bands of Some Fluorine Unsaturated
Compounds. . . ... 56
13. C=C Stretching Bands of Some Cyclic Monoolefins 59
14. C=C Stretching Bands of Terminal Dienes .... 61
15. C=C Stretching Bands of Conjugated Olefins from
the Pure Compounds . .... 63
16. C=C Stretching Bands of Conjugated Olefins from
Carbon Tetrachloride Solutions ... 65
17. C=C Stretching Bands of Some Olefinic Silanes 69
18. C=C Stretching Bands of Some Olefinic Tin and
Phosphorus Compounds . .... .72
19. C=C Stretching Bands of Some Oxazines from the
Pure Compounds ................. 73
LIST OF FIGURES
1. Comparison of Resolving Power of Calcium Fluoride
and Sodium Chloride Prisms Using CH2=CHF 19
2. Absorption of Carbon Tetrachloride Overtone 24
3. Comparison of the Spectra of CH2=CHC1 and CF2=CFCN
with the Spectra of the Carbon Tetrachloride
Solutions . ..... .. .28 *
4. Spectra of CH2=CH(CH2)3CH3 from the Pure Compound
and the Carbon Tetrachloride Solution 34
5. Spectra of CH2=C(CH3)(CH2)2CH3 from the Pure
Compound and the Carbon Tetrachloride Solution 35
6. Effect of Substitution at the a Carbon Atom with
Substitution of Varying Electronegativities
on the C=C Stretching Frequency. ... 48
7. Effect of Substitution at the p and at the 7
Carbon Atom with Substituents of Varying
Electronegativities on the C=C Stretching
Frequency . . ... 54
8. Spectra of CH2=CHCH=CHCH3 and CF2=CFCF=CFCF3
and the Spectra of the Carbon Tetrachloride
Solutions . . ... 67
9. Spectra of CH2=CHCH=CH(CH2)2CH3,
CH2=CHCH=CH(CH2)4CH3, and CH2=CHCH=CH(CH2)7CH3
from the Pure Compounds . .... .68
Vibrational infrared spectra are related to the energy
of vibrations of the atoms relative to each other in the molecule.
Considering this fact, one would not predict on general grounds
of molecular dynamics that such things as characteristic group
frequencies should exist. However, as long ago as the 1880's
it was realized by Abney and Festing (1), that the presence in
a molecule of a certain collection of atoms, known as a functional
group, was accompanied by the presence of an absorption band at
a particular frequency in the infrared spectrum of the molecule.
In more recent years, beginning with the pioneer work of
Coblentz (2) in the infrared, and stimulated by the discovery of
the Raman effect in 1928, the concept of characteristic group
frequencies has become firmly established. Many investigators (3-7)
have centered their interests on attempts to associate absorption
bands at specific frequencies with the presence of certain
chemical groups in the molecule, one rather comprehensive treatment
being that of Bellamy (8). The concept of characteristic group
frequencies is a main reason for the present widespread use of
The present study is concerned with the influence of
intramolecular factors on the absorption characteristics of the
carbon-carbon double bond (C=C) stretching vibration. The general
range of these stretching vibrations is from 2000 to 1400 cm.-.
Before discussing the factors influencing double bond
stretching frequencies and their intensities, it is desirable
first of all to state the conditions which must be satisfied for
group frequencies to exist and appear in the infrared. The
simplest set of conditions occurs when the group consists of
a pair of atoms AB, one of which, A, is bound chemically only
to B. Under such circumstances, the molecule containing AB
will have one mode of vibration in which A will vibrate along
the AB line and B will move very little--the so-called AB--stretching
vibration. Vibrations of the neighboring atoms in the molecule
will not affect this vibration very much. This stretching
vibration resembles the oscillation of two bodies connected by
a spring and the same mathematical treatment, namely Hooke's
law, is applicable to a first approximation. For stretching of
the bond A-B, the vibrational frequency v(cm.- ) is given by
1 f 1/2
where c is the velocity of light, f the force constant of the
bond, and 4 the reduced mass of the system, as defined by
mA + mB
where mA and mB are the individual masses of A and B.
In order for the A-B stretching mode to appear in the
infrared spectrum, that is, to be "infrared active" and result
in absorption of energy from incident radiation, it is essential
that there be a change in the dipole moment of the molecule
during the vibration. A more detailed account of infrared
theory may be found in Herzberg (9).
The concept of localized group frequencies is, of
course, generally recognized as an over-simplification. The
approximate vibrational frequency of a link AB is determined
primarily by the elasticity of the bond as measured by the
force constant, and by the masses A and B. In a complex
molecule this is modified by the interplay of certain intra-
molecular factors, i.e., atomic mass, mechanical coupling,
symmetry, bond angle strain, conjugation, electronegativity,
mesomerism, and dipolar field effects. With so many potential
variables it is at first difficult to see why characteristic
group frequencies should exist at all, but it should be remembered
that many of these factors can be minimized in favorable
circumstances. The basic frequency is therefore reasonably
constant and shows only minor differences under the influence of
the above mentioned intramolecular factors. These minor
differences, however, lead to the important distinctions in
frequency which are so valuable in correlation work. In the
discussion which follows the various intramolecular factors are
considered, particularly with regard to the C=C stretching
vibration, and it will be seen that present understanding of the
factors varies greatly.
There is a good deal of evidence that the frequencies of
multiple bonds are generally not sensitive to the mass effects
of the substituent, unless these happen to be hydrogen or
deuterium atoms. Substitution of deuterium for a hydrogen atom
in the ethylene molecule has been reported (10,11) to result in a
decrease of the C=C frequency from 1623 cm.-1 to 1605 cm.-.
Halford (12) has shown that the C=0 stretching frequencies are
insensitive to mass changes of the substituents for all masses
greater than 12, and similar treatments are available for the
C-=N (13), and C=C (14) vibrations.
The effects of vibrational coupling on group frequencies
have been very ably discussed in a recent paper by Lord and
Miller (14), and are also covered by Bellamy (8). Coupling
occurs when two groups vibrating with reasonably high and
nearly equal frequencies are situated near to each other,
provided that they have the same symmetry. This explains the
relative freedom of multiple bonds from these effects, as it
is unusual for more than one double bond to be associated with
the same carbon atom. When this does happen, as in allene or
carbon dioxide, the resulting interaction is extremely strong
and the asymmetric and symmetric stretching frequencies are
very widely separated.
The effect of symmetry on group frequency may sometimes
become quite complex, for if the effective symmetry of a
functional group changes, the change in the group is sometimes
so drastic that it may even be regarded as a new group, with
new characteristic frequencies. Therefore, only two effects of
symmetry are considered, that on the coupling of vibrations and
that on intensities.
There are four requirements for strong coupling of group
vibrations: close proximity of the vibrating atoms, strong
forces between the vibrating groups, approximate equality of
the group frequencies, and identical symmetry of the group
vibrations. Two group vibrations must have the same symmetry
in order for them to interact or couple. This is an important
restriction for vibrations of highly symmetrical molecules like
acetylene, benzene, carbon tetrachloride, etc. For molecules
with very low symmetry the requirement is easily satisfied,
and interactions are more generally permitted.
The effect of symmetry on the intensity of a group
frequency in infrared absorption is quite pronounced. The
absence of a group frequency from a spectrum is often taken to
mean the absence of the group from a molecule. It is well
known that a vibration which is symmetric with respect to a
molecular center is forbidden to appear in infrared absorption
as, for example, the C=C stretching frequency in ethylene. When
the symmetry center is removed, as in propylene, the vibration
Formally speaking, assymetrical substitution of
acetylene should always make the C=C vibration active. If
the two substituent groups have equal electrical and mass
effects on the two carbon atoms of the triple bond, however,
the symmetry of the group is not changed and the group vibration
is extremely weak or unobservable in the spectrum. Thus
n-propyl n-butyl acetylene (nona-4-yne) shows no triple-bond
frequency in the infrared spectrum (15).
A closely related situation exists when symmetry results
in drastically reduced intensity because of the nature of the
group vibration. It is well known that the C=C frequency in
cyclic monoolefins is often very weak or missing from the
infrared spectrum. The simplest example is cyclobutene. In
this molecule there is a plane of symmetry perpendicular to
the C=C bond axis. This plane prevents the development of a
dipole moment parallel to the bond line during the double-bond
vibration, despite the fact that the motion of the carbon
atoms is along this line. Therefore, any dipole-moment change
produced by the vibration must take place in other bonds and
is expected to be very small.
The angles formed when a carbon atom bonds to other
atoms are quite definite. These angles are, approximately,
tetrahedral for four-coordinated carbon, trigonal planar for
three-coordinated carbon and linear for two-coordinated carbon.
Molecules whose over all structure causes a departure from these
angles for one reason or another are said to be strained. Strain
has a definite effect on bond strength, and consequently
frequencies are altered by strain.
When the C=C is present in a ring, the bond angles may
be distorted considerably from the trigonal. If the interior
angles are decreased below 1200 because the ring is small, the
double-bond frequency drops. Cyclopropenes are the exception to
this rule. Closs and Closs (16), Breslow and Peterson (17), and
others (18,19) have reported the C=C stretching frequency of some
cyclopropenes in the range from 1865 to 1755 cm.- In cyclo-
butene, where the interior angles are presumably 950 or less, the
frequency is 1566 cm.-1 (14,20), in cyclopentene the value is
1612 cm.-1 (14,21,22), in cyclohexene, 1646 cm.-1 (14,21,22),
and in cycloheptene, 1650 cm.-1 (14). Cycloolefin rings with six
or more carbon atoms are non-planar and can adjust the C=C angles
to approximately 1200. As a result, the ring strain is not noticeable
and no evidence is provided by the spectra for the effect on the
double-bond frequency of an increase in the interior angle beyond
1200. It is of interest to note that the C-H stretching frequencies
associated with a strained C=C also vary regularly with the amount
of strain, though in the opposite direction. Since an atom such
as an olefinic carbon has only one s orbital and two p orbitals
available for hybridization, an increase in the s character of one
bond must be counterbalanced by an increase in the p character of
another. The above results imply an increase in the directional
component of the C-C bonds, so that the C-H bonds take on more s
character, become shorter and their frequencies rise.
Jones et al. (23), have made a comparative study of
steroids containing ethylenic linkages at different positions
and have shown that the frequency of the maximum in the region
of the C=C stretching vibration (1580-1680 cm.- ) is specific
for a given location of the bond in the steroid molecule.
Henbest et al. (22), made a spectroscopic examination of steroids
containing disubstituted cis-double bonds in the various positions
in the rings. In the simplest steroid cis-olefins the frequency
order reported was A2> A3 1 >A6 > A11 ranging from 1653 cm.-1
to 1620 cm.-. Henbest et al. (21), recorded the spectra of
groups of compounds containing cis-double bonds in different
environments and reported that cyclohexenes substituted in the
three position still had a C=C absorption at 1651 cm.-l, however,
the C=C of cyclohexenes substituted in the four position absorbed
over a range from 1649 to 1662 cm.-1. Jones and Herling (24)
have reviewed past work and reported that steroids have a
characteristic C=C absorption between 1672 to 1619 cm.-.
This paper included 53 references with specific references for
C=C stretching bands.
The effect of conjugation has been recognized for a
good many years (25-28). When the double bonds are conjugated,
the C=C stretching frequency drops by 20 to 40 cm.-, and a
similar decrease is observed for C=0 stretching frequencies.
The electrons in a double bond are known to be relatively
polarizable, i.e., mobile under external influences, and when
two double bonds are conjugated, the electrons of the double
bonds are presumed to move to some extent into the single bond
located between the double bonds. This charge migration
strengthens the single bond and weakens the double bonds, and
therefore the C=C or C=0 force constant decreases with the
consequent decrease in the group frequency.
Despite the multiple bond's usual freedom from mass and
mechanical coupling effects, the frequencies of multiple bonds
vary widely. These shifts have been reported as due to inductive
and mesomeric effects of the substituents (28). This is borne
out by the results of more recent investigations (14,29,30),
and by the many quantitative relationships which have been found
between group frequency shifts and other physical properties
which depend upon the same factors (29,31). In special cases,
field effects can also give rise to frequency shifts but these
are relatively small and will not be further considered.
Inductive effects can lead to either a rise or a fall
in the frequency of a multiple bond depending upon its original
polarity. In a non-polar compound such as butene-2, the charge
cloud of the double bond is initially central. Replacement of
a methyl group by chlorine displaces the cloud away from the
bond center leading to a more polar bond of lower frequency.
When mesomerism is absent, the frequency shifts arising from
induction will be a direct function of the electronegativities
of the substituents. Contributions from ionic forms are usually
too small to have any significant effect upon the frequencies
of multiple bonds.
Mesomeric effects arise only in unsaturated molecules
and are subject to the steric restriction that the groups
producing the effect must lie in the plane of the double bond.
It is known that in the substituted ethylenes CH2=CHC1 and
CH2=CFCl the mesomeric effects give rise to only about 4-5 per cent
double bond character (32) so that in vinyl and vinylidene halides
this frequency should be a direct function of the sum of the
electronegativities of the RIR2 substituents. That this is
realized in practice is shown by the linear relationship found
by plotting the electronegativities of the RlR2 groups against
the observed CH deformation frequencies (29). In an unsaturated
compound in which the substituents at the double bond lie in
the same plane, it is to be expected that any mass insensitive
vibrations involving the double bond will be subject to the
resultant of both inductive and mesomeric effects, and the
frequency shifts following changes in the substituents should
be a quantitative measure of the resultant effect.
Mesomerism of the group of R-C=0 to the polar structure
+ I -
R=C-0 occurs through the donation of an electron pair from R.
It will always increase the polarity of the multiple bond and
lower its frequency. In the case of a C=C link it follows that
both induction and mesomerism will lead to lower frequencies,
and this is supported by the fact that, in general, no C=C
frequencies are found at significantly higher values than that
of the purely covalent butene-2. The only exception to this
are fluorinated olefins which form a special group which is
discussed below. The direct connection between the frequency
changes of normal olefins and the polarity of the double bond
is well shown by the smooth relationship which connects the
frequency shifts with the enthalpies of hydrogenation (33).
Conjugation and mesomerism both involve some degree
of delocalization of the electrons over the atoms of the
resonating group, and are therefore very sensitive to the
planarity of the bonds concerned. Steric factors which decrease
or increase the coplanarity of the systems will, therefore,
lead to frequency shifts by alterations in the contributions
of resonance forms.
Bellamy (34) states that ionic forms such as F-[FC=CH2]+
will not be favored if alternative mesomeric structures as
Cl =CH-CH2- of lower potential energy are available. The ionic
forms are therefore most likely to arise in compounds with
fluorine substitution as this element alone combines a very high
inductive power with a very limited capacity for mesomerism
due to its high ionization potential. Contributions from the
form F-(FC-O)+ may, therefore, play some part in the very
high carbonyl frequency (35) of COF2 (1928 cm.-1), and it is
suggested by Bellamy (34) that similar effects are responsible
for the abnormal C=C frequencies of fluorinated olefins.
The behavior of olefinic bonds with multiple fluorine
substitution has long presented a major group anomaly. Vinylidene
fluoride (36) absorbs at 1728 cm.-1, and the frequency rises
steadily with further substitution to 1872 cm.-1 (as shown by
Raman spectra (37)) in perfluorethylene. Torkington and
Thompson (38) measured the infrared absorption of a number of
partially and fully fluorinated ethylenes and related compounds,
and correlated the band contours with the molecule structure and
attempted to assign the normal vibration frequencies. Many
other fluoroethylenes and related compounds have been studied
extensively and all of the fundamental vibrating frequencies of the
investigated samples have been assigned (39-49). Morino et al. (50),
using a normal coordinate treatment calculated the mean amplitudes
of the thermal vibrations in CF2=CF2 and CH2=CF2. Mann et al. (51),
performed the normal coordinate analysis of the fundamental
vibrations of 27 perhalogenated ethylenes which contained F, Cl,
or Br, and comparison with experimental results have been made
where possible and indicate good agreement.
In the fluoroethylenes, the C=C frequency rises
significantly above the value of 1675 cm.-l of the covalent
bond of butene-2, suggesting that some unique property of
fluorine is involved. Bellamy (34) suggests that ionic forms
such as -F[FC=CH2]+ might then make some larger contribution
than normal to the final structure of fluoroethylenes. It has
already been noted that the C=C frequencies of normal olefins
are directly related to the enthalpies of hydrogenation and the
frequencies fall as the reactivity rises (33). This situation
has been shown to reverse for fluorinated olefins and for
frequencies above 1675 cm.-1, the reactivity rises steadily
with the frequency (33). This is consistent with the idea of
ionic contributions which would lead to more reactive double
bonds. Bellamy (34) also states that it is not necessary to
postulate the existence of triple bonded structures to account
for the high C=C frequencies, as the orbital of the fluorinated
carbon atom which forms the C-C a bond in -F[FC=CH2]+ must have
a bigger proportion of s character than in the normal trigonal
state, and this will result in a shorter C-C distance and a
higher frequency. The F-C-F angle of CF2=CH2 closes down (52),
by as much as 100 to 1100; this would be expected if the carbon
orbital directed towards the CH2 carbon atom were taking on an
increased s character.
Edgell (53) recorded the Raman and infrared spectra of
C3F6 and assigned the fundamental vibration frequencies thereby
proving that C3F6 was hexafluoropropene and not a cyclic compound
as first was suspected. Brice et al. (54), have reported the C=C
stretching frequencies for a short perfluorobutene series. Some
cyclic perfluoroolefins have been investigated by Burdon and
Whiffen (55) and the C=C stretching frequencies reported for the
perfluorobutene, perfluoropentene, and perfluorohexene series
are 1799, 1754, and 1746 cm.-1, respectively. This is exactly
the inverse of the same cyclic hydrocarbon series and no
explanation was presented.
Haszeldine (56) has reported the C=C frequencies of a
series of partially and fully fluorinated olefins. The range
of frequencies for these series extend from 1613 to 1795 cm.-.
Haszeldine (57) in a later paper states that terminal
fluorinated olefins absorb at 1799 cm.-1 and that internal
fluorinated olefins have an absorption band at 1733 cm.-.
Simons (58) gives a brief review of fluorine containing olefins
and lists their C=C stretching frequency together with references
to the original articles.
Infrared absorption bands associated with the various types
of double bond found in hydrocarbons have been extensively studied,
so that recognition of the presence and type of unsaturation in
an unknown compound is usually possible with reasonable certainty.
Bellamy (8) gives the range of 1680-1620 cm.-l for non-conjugated
C=C stretching vibrations. Gullikson and Nielsen (59) recorded
the infrared spectra for gaseous samples of the vinyl halides and
assigned the fundamental frequencies. These values agreed quite
well with the earlier reported work of Thompson and Torkington (60).
Sheppard (27) and others (61,62) have studied some propene and
butene series and have assigned all the normal modes of vibration.
The infrared spectra of the vinyl compounds of mercury, cadmium,
zinc, tin and phosphorus have been investigated by Kaesz and
Stone (63), who report values for the C=C stretching frequency
from 1595 to 1565 cm.- with an accuracy of -5 cm. -
Sheppard (64), McMurry and Thornton (65), and Sheppard
and Simpson (66), presented three independent reviews which
have definitely narrowed the range of frequencies in which
different types of olefins absorb.
Sheppard (64) lists the following frequencies for the
olefin types: CH2=CHR, 1645 cm.-1; CH2=CRlR2, 1650 cm. -
RICH=CHR2(trans), 1675 cm.-1; RICH=CHR2(cis), 1660 cm.-1;
RICH=CR2R3, 1675 cm.-l. Sheppard also used line figures to
give approximate measures of absorption intensity.
McMurry and Thornton (65) in most cases give a narrow
range of frequencies for the olefin types: CH2=CHR, 1645-
1639 cm.-1; CH2=CRIR2; 1661-1639 cm.-l; R1CH=CHR2(trans),
1667 cm.-1; R1CH=CHR2(cis), 1661-1631 cm.-1; RICH-CR2R3
1692-1667 cm.-l. These coworkers also reported the lowest and
the highest absorptivity coefficient recorded for each type of
Sheppard and Simpson (66) report an average value of
the C=C frequencies of the olefin types: CH2=CHRI, 1643 cm.-1.
CH2=CR1R2, 1653 cm.- ; RICH=CHR2(trans), 1673 cm.-l; RCH=CHR2(cis),
1657 cm.-l; R1CH=CR2R3, 1670 cm.-1. No intensity data are given
in this review. The values given in the three works have also
been reported independently by other investigators (67-69).
Rasmussen et al. (70), Theus et al. (71), and several
other researchers (72-75) working with cis-trans isomers of
compounds have confirmed the general rule that the trans
isomers have a stretching frequency that is 10 to 20 cm.-1
higher than the cis isomers.
The characteristic olefinic absorptions of a number of
polar allyl, vinyl, and isopropenyl compounds have been measured
in solution by Davison and Bates (76). New correlations were
established for the esters, ketones, and ethers. The correlations
for acrylates and methacrylates include absorptions associated
with the ester group. Conjugation explained some of the shifts
of the C=C stretching frequency and an additivity rule was
suggested and tested but the results were inconclusive.
Rasmussen et al. (77) reported that experimental data
indicated that at room temperature the trans form of 1,3-butadiene
predominates. Cis-butadiene is the lower energy form. The cis
form predominates at the temperature of a dry ice bath, while
at room temperature the trans form predominates. Rasmussen
and Brattain (78) recorded the spectra of 1,3-butadiene,
1,2-butadiene, isoprene, and cis and trans 1,3-pentadiene
vapor. They report absorption bands at 1605 and 1594 cm.-1
for 1,3-butadiene, isoprene has two bands at 1612 and 1603 cm.-,
and cis pentadiene showed two bands at 1656 and 1608 cm.-, and
finally trans pentadiene absorbed at 1661 and 1610 cm.-.
From the infrared spectra of various types of conjugated
ethylenic and acetylenic compounds, Allan, Meakins, and Whiting (79)
established correlations facilitating the recognition of these
systems. In many of the compounds investigated geometrical
isomerism was possible. Examination of both cis and trans
isomers led to useful spectral distinctions between them.
Blout et al. (80) determined the infrared spectra
of 26 compounds containing two or more conjugated double bonds
in the region of double bond vibrational absorption. Polyene
aldehydes and polyene azines show at least one strong absorption
maximum which shifts toward lower frequencies as the length of
the conjugated system is increased.
In infrared measurements of some of the compounds in
which isopropylidene-isopropenyl isomerism was possible, there
appeared to be an inverse relation between the C=C stretching
frequency of the isopropylidene groups (range 1656-1680 cm.-1)
and the corresponding out-of-plane hydrogen bending frequency
(range 812-858 cm.-l). Werner and Lark (81) collected data to
investigate this point and a statistical analysis was carried
out on values from 31 compounds having the group R1R2C=CR3H.
This has been extended to include a skeletal vibration frequency
(range 789-810 cm.-l) which appeared when the group in question
formed part of a cyclohexenyl ring.
This analysis revealed highly significant correlations
between the bands and yielded two sets of regression equations
of possible value in structural investigations.
In order to calculate the higher variation of the higher
normal frequencies in the chain of conjugated polyenic aldehydes,
Scrocco and Salvetti (82) introduced an interatomic potential
and used it to derive the corresponding secular equation. The
calculations showed that the highest frequency is basically due
to the valency oscillations of the C=0 group; the next highest
frequency is mainly determined by the oscillation of the C=C
group with highest binding energy, and so on. Agreement with
experimental results is satisfactory for the first two terms
of the series. The experimental data available at present are
not sufficient to draw definite conclusions concerning the other
Many other informative studies on the 2000 to 1400 cm.-1
region have been conducted. The above discussion was limited
to those works which were of interest in the present study.
For a more extensive bibliography on infrared studies a text
on that subject should be consulted. Bellamy (8) lists many
references at the end of each chapter in his text. Most of
the articles consulted in this study gave further references.
Although a great deal of work has been done on the
C=C stretching region of the infrared spectrum, it still holds
many unanswered questions. This present study was carried out
with the hope of elucidating some of these problems by illustrating
that C=C are not sensitive to mass effects above a mass of 12
and also to illustrate the relationship between the C=C stretching
frequency and the inductive effect of various substituents.
APPARATUS AND EXPERIMENTAL TECHNIQUE
A Perkin-Elmer Model 21 double-beam infrared recording
spectrophotometer was used in this research. This spectrophotometer
is normally equipped with a sodium chloride (NaCl) prism, but is
designed in such a way that the prism can' be changed. It was
decided to use the calcium fluoride (CaF2) prism, which has
better resolution than the NaCl prism in the range of this
investigation. Figure 1 illustrates the difference in the
resolving power of the NaCl and CaF2 prisms.
The range of the spectrophotometer with the CaF2 prism
is from 5000 cm.-I to 1050 cm.-1. This study, however, was
concerned only with the C=C stretching region which lies between
2000 and 1400 cm.-.
For a more detailed description of the spectrophotometer
and the ranges and resolving power of the various prisms, the
manuals prepared by the Perkin-Elmer Corporation should be
Whenever the prism of the spectrophotometer is changed
several calibrations must be made. These are also described in
the manuals which are supplied with the prism and its interchange
Frequency in cm.-I
Figure l.--Comparison of Resolving Power of Calcium Fluoride and
Sodium Chloride Prisms Using CH2=CHF.
Because the research was concerned only with the range
of 2000 cm.-I to 1400 cm.-1 and to increase the accuracy of the
recorded frequencies, changes were made in the procedure given
in the manual for calibration of the frequency. The bands
usually used for calibrating the CaF2 prism are the 1340 cm.-1
atmospheric H20 band at low frequencies, and the 3335 cm.1
NH3 band or the 3741 cm.-1 atmospheric H20 band at high frequencies.
Instead of employing the recommended frequencies, the atmospheric
H20 bands at 1870, 1773, and 1637 cm.-l were used for calibration
and resulted in a frequency accuracy of -1 cm.-1 over the range
of frequencies utilized in the research.
A frequent check was made of the frequency using the
1870, 1773, and 1637 cm.-1 atmospheric H20 bands. Since
frequency remained constant, no adjustment was needed until
the prism was changed.
The procedure followed for the zero setting of the
spectrophotometer was that prescribed in the manuals prepared
by the Perkin-Elmer Corporation. Before each spectrum was
determined, the zero setting was checked and was adjusted
The spectrophotometer instruction manual recommended a
slit program dial reading of 987 which resulted in a slit width
of 91 microns at 2000 cm.-, and a slit width of 147 microns
at 1400 cm.-. In order to obtain maximum resolution of the
instrument, the slit program dial reading was decreased to
give narrower slit openings. A slit program dial reading of
950 was used, which gave a slit width of 50 microns at 2000 cm.-1
and a slit width of 84 microns at 1400 cm.- The narrower slit
widths employed resulted in a resolution of 3 cm.-1 over the
previously stated range of frequencies.
All spectra were determined with the gain set as
illustrated in the instruction manuals. The scanning time was
generally about 10 minutes per micron. When a major band
appeared, the speed was further reduced and the instrument
stopped at the peak of the band, and the frequency was then
recorded from the counter on the prism drive. A minimum of
three spectra of each compound was recorded to determine the
amount of absorption of each major band, and the reproducibility
of peak absorption was within the .5 per cent tolerance quoted
in the instruction manuals. The concentrations of the compounds
investigated were prepared to give an absorption between 50 per
cent and 80 per cent for the major bands. For some of the liquid
samples, as for some solutions, the available cell size prevented
such as absorption.
Since the compounds under investigation were in the
gaseous, liquid, and solid states, a variety of techniques was
needed. The gaseous samples were run in a gas cell of 5 cm.
path length. The cell was first evacuated, the gaseous sample
was then allowed to fill the cell to the desired pressure, and
the pressure was measured with a manometer attached to the gas
cell filling apparatus. The pressure at which the samples were
run depended on that required to give the major bands an absorption
between 50 per cent and 80 per cent. The pressure varied among the
samples depending on the infrared activity of the compound being
studied. The extremes were 2 mm. Hg pressure for some unsaturated
fluorine compounds and 300 mm. Hg pressure for some unsaturated
Carbon tetrachloride solutions of known concentration of
the compounds that are gases at room temperature were prepared.
The gaseous samples were condensed in a "Dry Ice" and acetone
bath and then quickly transferred, as liquids, by a length of
cooled small bore tubing to volumetric flasks containing carbon
tetrachloride. The volumetric flasks were weighed before and
after addition of the sample, and the difference equaled the
weight of sample put into solution. The volumetric flasks
were filled to their calibrated capacity after sufficient
time was allowed for the solution to come to room temperature,
since the condensed gases produced a cooling effect upon
addition to the carbon tetrachloride.
The prepared solutions were run in fixed cells of
various thickness to give the major band an absorption between
50 per cent to 80 per cent. The sizes of the fixed cells
utilized in the solution study were 0.048 mm., 0.099 mm.,
0.214 mm., 0.49 mm., and 0.93 mm. The thickness of all cells
used was accurately determined by the interference fringe
method of Smith and Miller (83).
Generally when compounds are run in solution, two cells
of approximately the same size are used. One contains the
solution and is placed in the sample beam while the other
contains only the solvent and is placed in the reference beam.
This allows the instrument to compensate for any band due to
the solvent. Carbon tetrachloride has an overtone absorption
band at approximately 1550 cm.-l, which becomes quite appreciable
when using cells of 0.1 mm. or greater thickness. Figure 2
shows the overtone absorption band produced in a 0.214 mm. cell,
and also illustrates effective compensation.
The spectra of most of the solutions were recorded
without any interference from the overtone absorption band of
the solvent. However, difficulty was experienced in determining
the amount of band absorption for a few solutions which required
the largest size cell, and where the sample absorbed at approx-
imately the same wavelength as the carbon tetrachloride overtone.
The problem encountered was due to partial compensation of the
sample peak by the carbon tetrachloride in the reference beam,
and prevented the determination of the amount of sample absorption
in this solvent.
A large number of the compounds investigated were liquid.
This included compounds with varying degrees of absorption, and
therefore various sample sizes were needed. The compounds with
high absorption such as the unsaturated fluorine samples, were
run in demountable cells. Since the absorption of the unsaturated
hydrocarbons was weaker than the fluorine compounds, fixed cells
were used. The cell size was determined by obtaining the desired
amount of absorption. Three different cell sizes were used to
Frequency in cm.
Figure 2.--Absorption of Carbon Tetrachloride Overtone Band in
0.214 mm. Cell.
Curve A: Compensated
Curve B: Uncompensated
run the pure liquids. These were the 0.019 mm., 0.0246 mm.,
0.048 mm., and 0.214 mm. fixed cells.
The liquid samples were run in carbon tetrachloride
solutions. These solutions were treated in the same manner
as the solutions of the gaseous samples. However, due to the
weak absorption characteristics of some of the liquid samples,
the 3.0 mm. fixed cell, which is the largest cell available at
this laboratory, had to be used.
The solid compounds required more time for investigation
than either the liquids or gases. There are several methods for
obtaining the spectra of solids. A list of most of these methods
in given by Silas (84), and the technique manuals prepared by
the Perkin-Elmer Corporation. In this investigation only three
methods were used. The solids were run as mulls, potassium
bromide disks, and in solution. The mull method suspends a
finely ground sample in some mulling oil or grease. The
mulling oil used in this work was a mineral oil, generally
Potassium bromide disks are prepared by mixing a
finely ground sample with some finely ground potassium bromide,
and the mixture placed in a special die where it is subjected
to high pressure under a vacuum. The product of this treatment
is a clear disk of potassium bromide with the sample imbedded
Carbon tetrachloride solutions of the solids were run
as described above. Two substituted ureas and two allyl ammonium
bromide salts were insoluble in carbon tetrachloride, and no
appropriate solvent could be found.
Origin and Purification of Compounds
All of the compounds used in this investigation were
obtained either from the laboratories of this University or
Dr. John Savory and Dr. Paul Tarrant, and his group
of the Chemistry Department supplied most of the unsaturated
fluorine compounds. Dr. George Butler, and his group, of the
Chemistry Department furnished many of the unsaturated hydro-
carbons. Peninsular ChemResearch contributed the majority of
the samples which were not available from University laboratories.
Those compounds used in this study which were not obtained from
the above sources were purchased from commercial companies.
A few of the compounds had to be repurified. Distillation
at atmospheric pressure was used to purify the liquids.
A gas chromotograph, equipped with a column packed with
diamylphthalate on chromosorb,was used to remove impurities from
the gaseous samples.
DISCUSSION OF RESULTS
The spectra of all samples studied were obtained from
the pure compound and whenever possible from carbon tetrachloride
solutions. The compounds were recorded from the carbon tetrachloride
solutions to eliminate the rotational contours which appear in most
of the gaseous samples, and because spectra recorded from solutions
generally produce sharper peaks which facilitate accurate
determination of band position. A comparison of the difference in
spectra recorded from the pure gaseous sample and from the carbon
tetrachloride solutions, is illustrated in Figure 3.
The values of the.various frequencies for the pure
compounds and the carbon tetrachloride solutions are listed in
the tables in this chapter. The values in parenthesis indicate
peaks which appeared on the sides of the major band. The
following notations are used to indicate the relative band
intensities of the pure compounds: vs = very strong, s = strong,
m = medium, w = weak, and vw = very weak. Notations are not
used with the solution frequency values since the molar
absorptivities, calculated mainly from the carbon tetrachloride
solutions, are listed to the right.
The molar absorptivities were calculated from peak
heights through the use of the "Beer-Lambert Law" which was
Frequency in cm.-I
1710 1525 1870 1650 1905 1680
I I I I I I
Figure 3.--Comparison of the Spectra of CH =CHC1 and CF2=CFCN
with the Spectra of the Carbon Tetrachloride Solutions.
assumed to hold true for the concentration of solutions used.
The values obtained were used as an aid in the qualitative
interpretation of the spectra.
The molar absorptivity (85), E, is defined as the
product of the absorptivity, a, and the molecular weight of the
E = a(M.W.)
where the absorptivity, a, is equal to the absorbance, A, divided
by the product of the concentration of the substance (in g./l.) and
the sampel path length (in cm.),
Molar absorptivity, E, will be listed in the tables in units
The C=C stretching frequencies of the CH2=CHR type
olefins listed in Table 1 agree very well with values given
by Davison and Bates (76), and McMurray and Thornton (65), and
the average value of the solution frequencies omitting ethylene,
is 1643 -2 cm. The molar absorptivity values listed in the
table also fall within the range of values reported by the
above mentioned workers (65,76). The consistency of the C=C
vibrational frequency confirms what was predicted in Chapter I
and proved by this study that an increase of mass above 12 has
little effect on the C=C vibration.
- 4J \
CN N- 00 00 CM
S Co CO) It r
C4 CO cM Co C
\'0 \0 \0 \0 %O
H H H H H
O CM 0C
Hl rH rH
S 02 0
.v t 0
CO CO CO CO CO 0 0
m 0 0 a 0 0 a
SC- 0 0 0 0 Z 0
CO O C Co V O CO O
0 N C 4 Cl N c CN
Co C 4 a
C4 cq C14 CM C14 Cl Cl Cl C14 CM4
C4 CO lO
CO CO CO
in H C
\o0 0 \O
H H H
cz E 65 E w
Co 0 r-H 0 I
CM 10 \0 10 I 110
\0 '0 \'0 0 '.0 '0
H H H H H H
E F E V u)
r- D %0
H H H
^ > C
0 *Q 4
H H H
O U 11
U u L-
Table 2 lists the C=C stretching frequencies of the
CH2=C(CH3)R type olefins. The average value of the C=C solution
bands is 1651 1 cm.-l excluding CH2=C(CH3)H. The molar
absorptivity values and the average frequency value agree well
with the values listed by the aforementioned workers (65,76).
As in the previous series, the consistency of C=C frequency proves
the absence of any mass effect except for that in the first
The increase in frequency of the C=C absorption band
of the compounds listed in Table 2 is about 8 cm.-1 over those
compounds listed in Table 1. Since the electronegativity of a
CH3 group is a little less than that of the H atom, the increase
is not due to an electrical effect. A mass effect would lower
the C=C stretching frequency of CH2=C(CH3)R type olefins as
compared to CH2=CHR type olefins. The increase in frequency
is explained as a result of a loose type of coupling in which,
as the C=C vibrates the C-R bond has to bend a little in order
for the molecule, as a whole, to maintain its center of mass.
Since the CH3 group is heavier than the H atom, it is entirely
plausible that as the C=C stretches it will require more energy
to bend a C-CH3 bond than a C-H bond, thereby increasing the
frequency of vibration bf the C=C.
In almost all compounds listed in Table 2 as well as
some compounds in Table 1, a small side peak appears at the
consistent frequency of 1657 1 cm.-1. Figures 4 and 5 illustrate
the 1657 cm.-1 peak as it appears in the CH2=CHR and CH2=C(CH3)R
c '0 CI) 110 o rH) )
o -i r-l r- O o l r O
L O L L) LO ) LV tn LO
0 \00 0 '0 '0 %0 '.0 \0
H H H H H H H -
: N r- \0 %0 '\0
s0 '0 'o \0 '0 \0 \0
P LO O
0 0 H H H H H H H
LI) V) V) LI) LI) LI LI)
E -1 E M L M M M M L )
0 /3n m i i i S io
0 N 3 "> \0 \0 \0 '0 \0 \0 \0
O O N o
o N 04 BY 6 ) io ira
CV0 CI4 04 0 C C4 0
nC -) C I V O i)
0-) CO CI O CV) CO CIO CV) CO CV
0 0' 0 0 0 0 0 0 0
Frequency in cm.-l
Figure 4.-Spectra of CH2=CH(CH2)3CH3 from the Pure Compound and
the Carbon Tetrachloride Solution.
Frequency in cm.
Figure 5.--Spectra of CH2=C(CH3)(CH2)2CH3 from the Pure Compound
and the Carbon Tetrachloride Solution.
.... 00 I-';
type olefins, respectively. There is no explanation, at present,
as to the origin or meaning of this peak.
The data in Table 3 illustrate that an increase in
symmetry has a more pronounced effect on the molar absorptivity
than on the C=C stretching vibration. The values for the
C=C stretching vibrations are in accord with literature average
values (66) of 1657 cm.-1 for cis compounds and 1672 cm.-1
for the trans compounds. The absorption band listed for trans
CH3CH=CHCH3 is probably due to an overtone. The absorption
band listed for trans CH2C1CH=CHCH2C1 probably is due to an
impurity because selection rules prohibit the appearance of
this band in this compound, although forbidden absorption
bands occasionally do appear as weak bands. The trans-4-
methyl-2-pentene configuration must be quite symmetrical since
the hydrocarbon shows only a very weak band and the perfluoro-
compound does not have any C=C absorption band visible even
when the sample is run in a 0.0246 mm. fixed cell as the pure
compound. The octene series C=C absorption bands appear as
expected, except for the trans-4-octene isomer which had a
very weak absorption though none are allowed according to
infrared selection rules, although as stated above, forbidden
absorption bands occasionally do appear as weak bands. Therefore,
the absorption probably is due either to some overtone or slight
Substitution, one or more carbon atoms away from a C=C,
has little or no effect upon the C=C stretching frequency as
is verified by the values listed in Table 4. An interesting
H 0 00co o 00
S\o o\ 0 -
\0 \o \0 0 '10
H H H .-
co z4 r
I-- \o \o
H co 4
11 % e N
/^C CO C
co .- 0 ( c C C
co co | co -
m ) C) C c m) C
C CO 0 o 0 0 Iu O C
c0 c0 c0 0 c0 C0 c0 c0
cu cd w0
a% C4 CO
0 SO i-l
Ct o O ra C oo -- ~
\a 0 \0 \' 0 \0 '% '0
SH- H H H H H
m co aC
Cl l (| *I ', c) C
tl ,. 0,1 U: v v
C [ O CO Cl C
'- C) U Cl C4
C) C) Cl II II '
m c m c o
S I) C C M :2 C) C
0 M CM II II C Cl
Sm U U Cm Co
a 0 0 a 0 0 a
S0 CJ O 0 C? 0
"H H1 H m~ 1 co c1 co C
U) 1 o
E-4 CO co o o CO )
IZV Ir I 1 4,
z0 \0 \0 %0'0 0
0 o N CO --
O_ 0 /-s c-s ->r
1 00 I co -
S% 0 \ 0 \ \0
0 % 0
0 N 3 C 0 0
C* H 4 C 1 aN a
0- csi c CM O O CN CN
0" 0 0 0 0 0 0
trend is found in the values of the molar absorptivities, for
here substitution two carbon atoms away decreases the C=C
absorption intensity. As the substituted atom is removed from
the C=C the intensity rises until there is a separation of
four carbon atoms. At this point the intensity of the C=C
absorption attains the value of the unsubstituted analog.
No explanation has been offered for this behavior.
Fluorine has a very pronounced effect on the C=C
stretching frequency when it is substituted at the C=C bond.
Additional fluorine substitution on the same carbon atom
further increases the C=C stretching vibration. This trend
is indicated in the vibrational frequency values listed in
Table 5. The molar absorptivity also increases greatly when
one or two fluorine atoms;are substituted on the same carbon.
When a third fluorine atom is added the molar absorptivity
decreases greatly and is found to be about one-third the value
of the singly substituted compound.
The increase in molar absorptivity is due to an increase
in the C=C dipole moment when one or two fluorine atoms are
added to the same carbon atom. Addition of fluorine to the second
carbon atom has a tendency to neutralize part of the electrical
effect present across the C=C from the fluorine on the first
carbon atom. This neutralization results in a decrease in the
dipole moment of the C=C with a subsequent decrease in molar
The C=C stretching frequencies for the substituted
compounds in Tables 6, 7, and 8 have been arranged according
r-H H H
00 0 0\ \0 CO
0o C I0 %
H H- r-H H H
> CI ,1 .0 CU)
0 C0 c H H r-
r- N- o o LO Ln -0
r-H H H H H H H
i- II 4 0 4 r
C CM C14 CM3 0 0 0 lw
r P-i0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 g 0
H- H Cf)
LO C') 00
%0 r- N
H- H H
\o co to
^f 10 m f o
,. r-- I
'0 10 '0
o C II
4.) C ..)
C4 CM1 CM4 C CM CM
C.) C.) 0i C.
(*n a a K a
S c >
Cr-N CMH o c
C4 LO COH H HI
\0 '0 '0 \0 '0 \0
r r-l r l l H H
C4 N- LO LI ) C4
%0 0 ) m L) u) L) w)
H HH H H-I H
CM C4 C) cO)
- A) CI) r4- CJ CM 0%
H co H %0
C C rr- I
0 .\ r 0 '0 N- r f
LI) Co H 0 0 0% 0% 0'
\0 %0 %0 %0 '0 i) L) LI)
rHl r- H r -I H Hl Hl
C4 cr) CO M
CM CM CM
CM CM CO C
-. .-., CJ-
NC CO CO q'..I ,I e
w w C 0 C14
C4) C-) Cq 04 04 C1 C4 C04 C4 '-
g u g
co > > >
c00 cc C4 4
U) U) \0 \0 \0
H H H r-H
CO (1 CO
:> > >
Uf) cc co
Cf) I4 r
CH ) L
0 0 0
C4 C c- C4
u Q u u
UO H U)
H H H
cl *H co
co 0 l S
Co Co CO LO
co co co
u u > r: Mq M
a p 0 00 '0o
V V F V V V v
0 U CJ 0 0 C0 4 0
C t0 0o o0 H
CO 00 10 U)
O) Co co co \o
SI co r- v4 c
\0 \0 \o \o \0
Hr r r-H r
H co H
c co co
0o '0 'o
H H H
H '.4 Z '.0 *- -'
C4 0 m C i-i) L
p4 0 4 P 4 0. r. ..4 0
C C04 C C44 C0 C14 C4 C4 4
P4 A4 p4 0 4 | 0 4 W4
u- ) C)i C) Q 0 0 u
ao U) mc
> c > >
LO 00 C 0 C) 0
\0 00 \0 C4 CM4
H H H H H
O 0 o N H
co o \0 r- c
Co 00 0 to 0l
rH H -l H H
to decreasing solution frequency values. A study of the compounds
listed reveals a general decrease in the electronegativity as
the vibrational frequencies decrease. Figure 6 is a plot of the
C=C stretching frequency versus the Pauling electronegativity
value of the substituted atom. As is shown in the figure there
is a linear relationship between the electronegativity, according
to the Pauling scale, of the substituted halogen and the C=C
stretching frequency. Except for the tin, mercury, and silicon
substituted ethylenes none of the compounds have substituted
species which have been assigned as electronegativity value.
An attempt was made to plot the frequency values along the lines
of the corresponding series and assign electronegativity values.
However, there was no correlation between the compounds of the
individual series which had identical substituents and their
position with respect to the abscissa representing the Pauling
scale of electronegativities. Therefore, these compounds are
not shown in the figure.
It was noted in Chapter I that in vinyl compounds the
mesomeric effects give rise to only about 4-5 per cent double
bond character (32). According to Halford (12) the vinyl
halides should be mass insensitive. Assuming the remainder of
the intramolecular factors, except for electronegativity, are
minimized or absent, the C=C frequency of vibration should vary
according to the electronegativity of the substituent. That
this is true is shown by' Figure 6. Mass effect is probably the
factor responsible for the high value of the hydrogen substituted
compounds and their failure to lie along the corresponding
1600. .4 CF
I I I
1.9 2.1 2.5 2.8 3.0 3.5 4.0
Figure 6.--Effect of Substitution at the a Carbon Atom with
Substituents of Varying Electronegativities on the
C=C Stretching Frequency.
lines. The difference, between the experimental value and the
value the compound would have if it fell on the appropriate
line, is approximately 50 cm.-1 for each of the three hydrogen
substituted compounds. This indicates a common cause, which as
stated above, is probably due to mass. The slopes of the lines
of the CH2=CHX and CH2=CXCH2 compounds are approximately the same.
The slope of the CF2=CFX compounds is steeper. This may be due
to the presence of the ionic forms, discussed in Chapter I,
which are believed present in fluoroethylenes and not present in
the other two series of compounds.
The vinyl ethers listed in Table 6 have two C=C absorption
bands. These are due to conjugation with the oxygen atom and
the formation of rotational isomers which are known to be
temperature dependent (76).
Tables 9, 10, and 11 are also arranged so that the
compounds are listed according to decreasing solution C=C
vibrational frequency. The same trends are revealed in these
tables that were found in the previous three tables, i.e.,
as the frequency decreases the electronegativity of the
substituent decreases. Figure 7 shows the linear relationship
obtained when the C=C stretching frequency is plotted against
the Pauling electronegativity. The nitroso compounds were
placed on the line at the positions of their respective C=C
stretching frequencies and indicate an electronegativity value
of approximately 3.17. Since the substituted atom is one
carbon removed from the C=C, the only reasonable explanation
of the substituent's effect upon the C=C would be an inductive
C44 \0 t 10 0 0
c H H- H c4 C' v '0
E E m ( m m e E
0 0 r- 0 0 O \0 \0 \0 In C
Uf) UO It *7:4 .1 wv
HH r-l r- H H H -i
-' r t r_
%0 0 oO 0 o \o .
N 0l 0 '0 0 0r- l
'0 0 0 0 0 v v
If) U O a\co 0
\10 C14 cy 0o CO
u 0 0 z e -' C) 0 H
o 0 0 0 0 z C N U U
m C4 C4 C C4 C4 C 4 Cl
9? w w w w 9 ? '14 ? w?
cN C4 N C14 C4 04 Cl cd C4 Cl
^ r 3= r u u 0 0 3
0 0 0 0 0 0 0 0 0
U) o0 C C\h 00 \ 0 \0 \0
v4 U) l 14 *: 4 v' v v
\0 \q q \0 '0 \0 \o0 '0 \0
H HH H H H rH -
O \0 O \ \o
H C + r4
co co r
) Hr- 0 0
\o \o \0 'o
0 0 o H 0LO
c 'o o r, oo t,:
Co co? cJ 4t o 0 4
o o \o U) U) H- U)
0o o to Co )o %o to
1, c' CO CO mO CO C14
rl -H H H H H r
00 H LO U) U to C14 '0
H H r-H H HrH
Sm s m c
+ U U o 3
C1 4 K3 (M
C M )S I
ci C4 M Co M
Zc cli Z mc uC CM X C EC CM 14
C5 C9 C1 -4 v.
C'/ C"J CNI-' '-' CO C14 C4 C4 C Cl C
9? 9? 9? ~d X 9? U 9?U 9
V V C'I C U C'4 C' v C4
C H 4-)
\0 \0 \0
5H H HH
C14 C4 Ci 0
%0 0 \0 \0
U) V) to \0
\0 \0 \0 H
H r-H H -
Z \ H 0 o -4 i1n
u 0 u 0 z cq~ in C
Ue) cq C\ C C4
U" -d UC U
U) Uo Um U) U) U Y) Uco
C14 C4~ C14 C4 Clj Cl 4
0 0 C U u u
0 vv v 0 0 0 I H
H- U 00 00 m 4 I U) Q\ U)
H U; O\ co U) Q\ U)
co N H H H H '4 H r
Hl U) 0' N~ N~ Nz N v
to \0 If) to to to to to '
Ho oo o o 00 %0 o H 0o
0) At O 0c) CO CO co cV) LI)
.r c C. O 0) N4) 0 V %
4J \0 LO 0 00 o 0 Go rN cO
o oo co C1o oo 0 a N oo o Ci Hi 0'
C) Vo U) ) If) in 0 0' Co 0' Co Co S
0 P rH 4w 0 r
u u u uuu u 0 G
1775 Cl- NO-
,x I -- I- Br
4U 1650C--12:iH' ,, C :+- X
B r- C1 CH2= CCH
-_- Br CI CH2=CHCH2CH2X
2.1 2.5 2.8 3.0 3.5 4.0
Figure 7.--Effect of Substitution at the p and at the y Carbon
Atom with Substituents of Varying Electronegativities
on the C--C Stretching Frequency.
one. The slopes of all four of the propene series have the same
value and are not as steep as those of the previous series. Once
again the hydrogen substituted compounds are found above the line
and the cause is again believed to be mass effect. The position
of the hydrogen substituted compound for the CH2=CHCH2X series
is 12 cm.-I high. The hydrogen substituted compound for the
CH2=C(CH3)CH2X series is 6 cm.-1 high. The hydrogen in the
CH2=CHCH2X series is one unit of a total of 16 mass units
attached to the C=C as compared to the CH2=C(CH3)CH2X series
where the hydrogen is one unit of a total of 30 mass units.
It is reasonable that the mass effect results in a larger
deviation for the CH2=CHCH2X series than in the CH2-C(CH3)CH2X.
The plot of some substituted 1-butenes is also shown in Figure 7.
In this case the substitutent is too far removed from the C=C
to cause any effect at all and the plot is a horizontal straight
line indicating constant C=C stretching frequency.
Table 12 lists the C=C stretching frequencies of some
fluorine unsaturated compounds. The first five compounds in
this table contain the CF2=CFCH- group and have a strong band
between 1803 to 1797 cm.-1. These values agree with Haszeldine's
statement (57) that terminal fluoronated olefins absorb at
The sixth to tenth compounds listed in Table 12 contain
the CF2=CFCR2- group in which at least one R represents some
atom or group more electronegative than hydrogen. This set of
compounds has a C=C absorption between 1793 to 1785 cm.-1. The
first compound on the second sheet of Table 12 has two C=C
0r 4 +J O OC% m
C' I N a CI)
0.0 0 00
P 0 H-
C) Z oo0 c H
0 C) C O m) Co
C4 C) C4 C) 0 C) 0
W O 4 C W 0 0
r N S
4P o0\ N
a o o 00
C) H H
mIm >m a,
Q 0 CO0 'C
I-I C l)
6 00 00 0 0
i-o \ o \ o \ o to o
HH H H H H H-
0O 0 ul
C1 C O O
0 0 O Q 0 0
'-S CO C 0 0 P ( 0
<'' 0 0 0
0 II II CC C 0 0
0 0 0 co 0 0 0
O CO CO co CO co
0 0 0 U-' 0 0 0
absorption peaks. Since this compound may have geometric cis-trans
isomers, the peak at 1791 cm.-l is ascribed to the trans form
and the peak at 1776 cm.- to the cis form. The rest of the
compounds did not fit any specific group and are listed in no
The cyclic compounds listed in Table 13 fall into three
categories: hydrogen containing cyclics, chlorine and fluorine
containing cyclics, and fluorine cyclics. The C=C stretching
frequency for the cyclopropenes agree with the values put forth
by Breslow and Peterson (17), Doering and Mole (18), and
Closs and Closs (16). The hydrocarbon cyclic monoolefins C=C
stretching frequencies agree quite well with the values mentioned
in Chapter I. Attention is also called to the trend of increasing
frequency with increased ring size for the hydrocarbon cyclics.
The chlorine and fluorine containing cyclics have approximately
the same C=C frequency of vibration for the C4 and C5 cyclics,
with the C6 cyclic frequency occurring at a slightly lower value.
The increase in the C=C stretching vibration of the perfluoro-
cyclobutene over the perfluorocyclopentene is believed to be
due to some interaction of the C=C stretching frequency with the
C-F bending frequency.
Table 14 list the C=C stretching frequencies of terminal
dienes. It is assumed that coupling is the reason for the high
CH2=C=CH2 vibrational frequency. Conjugation explains the single
peak at lower energies in butadiene. The table reveals that
if two CH2 groups separate two C=C groups then each C=C behaves
like a terminal monoolefin with the result that the C=C absorption
band is approximately doubled compared to the monoolefins.
io *i -H
4 co H H 00 H
H 0 \0 %0 0 coN 0
H H H H H r-
H i 0 11 Co H0 Co -I H 0 H
C '.o r-o LO LI) miO o o Co
O i) \0 \0 \0 \0 \0 \C \0
H H H H H H H H H
S0- u UI-
\.0 0' Co4
C14 C" C4
LO LO C [j
C0 0 C )
0 0 H3-4
C) CI) C)
LI LI n ) Z V O
0o If t
r-q Cr4 ('
cq CO c0
C0 0N N0
i o LO l
4 C) N C) H4 C0 00
0 4 H C14
c'H C H CO Co C CO
4-' U' ) CO v 4 ^f
;j % i \o \o
S rH H H H H H
S O cw
al q71 00 w v
C) '.0 U') \0 \0 '0 '. '0
HI i H H H H
C I I I
0 LO 0 In C
'H '.0 N '0 .0
oo 0 U) LV) LO L LO
S> U) 0 \0 \0 \0
LOO 1I C00
o 11 0
S C V S
a' .0 E
SH H 4
M II II I IM
C4 C M C M C C' C') 0
M 0 CM 0 0 SC,0
ffi S s a a
II1 -' C. C) _5 C- 0 <_ (
The stretching frequencies of some conjugated C=C
compounds are tabulated in Table 15 for the pure compounds
and in Table 16 for the carbon tetrachloride solutions. The
C=C stretching absorption for 1,3-butadiene and 1,3-hexachloro-
butadiene agree very well with the values given by Haszeldine (57).
Isoprene and compounds containing an isoprene type structure
have strong C=C absorption band at 1597 cm.-1 and a weak band
at 1640 cm.-l which appear consistently. Even though the
compound contains a conjugated system there is only a single
absorption band which appears for (CH3)2C=CHCH=C(CH3)2 at a
frequency of 1622 cm.-l. A series of 1,3-hydrocarbondienes
consisting of the C5, C7, C9, and C12 members gave very consistent
C=C stretching frequencies. The samples were mixtures of the
cis-trans forms of these dienes and their absorption spectra are
illustrated in Figures 8 and 9. Attention is called to the fact
that the perfluoronated 1,3-pentadiene shows only one band at a
Using the values recorded by Rasmussen and Brattain (78)
and using the frequency values from solutions the absorption
bands for the 1,3-hydrocarbondienes at 1657 cm.-1 and 1603 cm.-1
can be assigned to the trans form and the bands at 1651 cm.-l and
1593 cm.-1 to the cis form. No attempt will be made to assign
the band occurring at 1645 cm.-.
Nasich and Post (86) give the C=C stretching vibration
of allyl silane as 1639 cm.-. Table 17 list the C=C vibrational
frequencies observed for various olefinic silanes. The vinyl
group has an absorption band at 1595 t2 cm.-1, the allyl C=C
Cl U) 0' Co H H 'o U)
H 0 0' C0 H 0 Co Co
\0 0o U) r- 0 0o \0o \o
H r- H H- l H H H
Co H Co 0' H H lv
r-I H H H- H H
(0 0 0*iC.
C CM CM C I
) C 0 O 0 D
I II II Co
C c Cl Cq r-4 C C
0 0 0 U 0 0 u
Jia m n 1 1 o c
SC00 0 K L -
S o c
.1 0 I
CI (_) 0-C
CO II II
Sco o a0 11
0 0 Co 0 0
'.0 '0 \.0 \0 \0
H r-H Hr- H Hi
> Uw E E E
L) CM1 %0 C0 0 V) \0
00 CM l41 :v
rN \o0 \o0 \o0 o
H r-H H H r- H H
'0 N- 0
If) if) LO
'10 \0 \0
H H H
rl Hl C4
H H H
cl Co I I Co) Co
1-1 z C114
Co' Q 0 Z 0 0
cl C-4 0 j
0 C Cl q Z
V Cq C,4 C-4N
II 01 0 v0
H -r' 0 '-'
0 U 0- 0 O
E H CO r- N r- C4 r-l U O
U C' cli LO \0 0 CO 0 0 0
U \o0 o ID U) 1O r- U) \o
H H H
0 C 00 C
0U 0' H m CO CO
N N 'r- \0 \0 N N \0
SC ral' H H H Hl Hr l rH
SU' 0 01
0 g X C M
C4 C-4 CO c- O K ; 4
0 0P II II 0 II
S ( C' II C Q QV u Z
S pJ-J 0u
0 0 0 0 0 0 0 0 0 0 0
o0 o o0 Co 0 U V
r- C4 1:. -
N '\0 \% 0 0 \0 '0
r- H H-l- r l H Hl
CM CO II Co
C) N CM ,S
P4 II O -
CO CC ) i M
C() ) S C) C Z4 C)
II II C ) 11I II ) I1
0 0 u u u j u
11 II C0 ll 11 C II
C) C) a- C) C) II CM
U 0 O 0 (-V (_
-- 0 co
Lf 0 ) rl
Hr y y
Nq O CN14
C40 cq- m 0
U)~ U) 0)
co Cc4 NO C-
o 0 O Go N-- s: N-
' U 0 014 ) ) )
C O CO N' C Cl C
04 0 ) Cl c Cl C
U) U) 0) 0n cu N c
C4 C4 C+ C4
i 0 0 0 0
0~ 0, 0 0 -: '- N-- N
CO \ CO C\ C ON m m Ho c NO
C' ^ Ca r GO LO \O O\ O\
H -- Hl H
LO oU rrl rOi N C4 l
O( \ o O\ O\ co co c co co co
O U) UO U) U) \O NO \O NO \O \0
SH Hr H Hr-I r r-H H H H
03> 0 0 00 0 \Q z
ns *H 0 0o LO CO \O \0
rP J H H H o
*H H- 00 00 00 00
4- co CO Co Co co
S\ \0 \0 \0 0\0
H H H H H r-H H
U)C CU) ) M S U)
S C 0 0 CD co
O co co q44 I 4 4
r f o )H c
-r-4 -, ~
0 C4 C4 Vc) C\4
Z^ 00 0 '0 0 C
0 U 0 -
3 C Cl Cl) *H C) Z
o Z CM CM MJ CM C _)
S H~ Cl cMi CM CM *j
o cl) c n Cl
00 00 0 C
C co co co co 0
c1 C4 c- C1 C4 1 1
absorbs at 1632 cm. and the methallyl C=C absorbs at 1640 cm.-
One.butenyl group was run and the C=C absorption appeared at
Some unsaturated compounds of tin and phosphorus are
listed in Table 18. The tin compounds indicate the same
consistency of C=C vibrational frequencies as with the silanes
of the previous table, but at a lower frequency. Vinyl diphenyl
phosphine shows no absorption band.
Table 19 list the C=C stretching vibrations of some
oxazines. The C=C vibrational frequencies of the following
cyclic configurations may now be assigned with certainty;
CH2CH=CHCH20N- absorbs at 1663 cm.-, CF2CF=CHCH20N- absorbs
at 1719 cm.-1, and CF2CH=CFCH2ON- absorbs at 1722 cm.-1.
C \ .0 \0
I m a I
I It ,
\0 \.0 \0
r-H H H
~N e- 1) 1-1
\.Dc q 1.
.0 C .0
1-11 I-N I-
c ) C) cq ) '4
cu U )1 U ) rN '. C
Cl l ~ U) )N C14
C1 CC) CC4 Cq C1
C4 C) C4 C) 14
III II C) C) C) C)
Cl Cl Cl Cl i II II
Z 5: cu Cl Cl Cl
C) C) ) C)
'C- %V' V C C C C
H N \O U)
00 clq l Cl
UO \.O \0 \.D
H- H H- H-
00 C C
C=C STRETCHING BANDS OF SOME OXAZINES
FROM THE PURE COMPOUNDS
Compound Frequency in cm.-
In this study, the infrared spectra of various C=C
stretching bands were investigated with regard to position and
intensity. The region of interest was limited to the 2000 to
1400 cm.-l range which includes the C=C stretching vibrations of
fluorinated unsaturated compounds as well as of the unsaturated
The spectra of all compounds were determined from the
pure compounds, and whenever possible, from their carbon
Two types of olefins were examined in this study.
The data which were obtained demonstrated the insensitivity of
the C=C stretching frequency to the mass effect of increased
alkyl chains whenever the mass was greater than 12. The
frequencies for the carbon tetrachloride solution of the
compounds were 1643 2 cm.-1 for the CH2=CHR series and 1651 1 cm.-l
for the CH2=C(CH3)R series.
A study of a few series of substituted ethylenes and
propylenes showed that the C=C stretching frequency increased or
decreased according to an increase or decrease in electronegativity
of the substituent. A plot of C=C stretching frequencies versus
halogen electronegativities, according to Pauling's scale,
for the halogen substituted compounds resulted in a linear
The absorption characteristics of some fluorine
unsaturated compounds, cyclic monoolefins, conjugated dienes,
silanes, and oxazines were also examined. Some trends in the
frequency shift as well as changes in the molar absorptivity
were noted. Some frequencies were definitely assigned.
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Leon S. Pijanowski, Jr. was born April 29, 1931, at
Philadelphia, Pennsylvania, and received his early education
in the parochial schools of that city. He graduated from
La Salle High School, Philadelphia, Pennsylvania, in June, 1949.
He studied at Villanova University from September,
1949, until he entered the United States Navy in March, 1951.
He was honorably discharged from the United States Navy in
February, 1955, and returned to Villanova University to complete
studies for the Bachelor of Science degree. He graduated in
Graduate studies were undertaken at the University
of Florida in September, 1958. While a graduate student, he
was employed as Graduate Assistant in the Department of Chemistry.
In September, 1960, he was awarded a General Motors Fellowship.
He is a member of Alpha Chi Sigma Chemical Fraternity and
of the American Chemical Society.
This dissertation was prepared under the direction of
the chairman of the candidate's supervisory committee and has
been approved by all members of that committee. It was submitted
to the Dean of the College of Arts and Sciences and to the Graduate
Council, and was approved as partial fulfillment of the requirements
for the degree of Doctor of Philosophy.
April 20, 1963
Dean, College of Arts and Sciences
Dean, Graduate School
UNIVERSITY OF FLORIDA
3 1262 08553 5218