SPECTROSCOPIC STUDIES OF ALCOHOLS

V. INTRAMOLECULAR HYDROGEN BONDS I N 2-CYANOETHANOL AND

IN S O M E NITROALCOHOLS1

P. J. KRUEGER
AND H . D. METTEE
Department of Chemistry, University of Alberta, Calgary, Alberta
Received May 19, 1965

ABSTRACT
The enthalpy difference between the trans and the intramolecularly hydrogen bonded gauche
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conformation of 2-cyanoethanol in dilute CCI4 solution is shown to be -0.14 f 0.03 kcal/

mole from the temperature dependence of the fundamental OH stretching bands. At higher
concentrations cyclic dimers with double O H . . . O bonds form. The enthalpy change on
dimerization is -6.1 f 0.3 kcal/mole. A small percentage of dimers with acylic O H . . . O
bonds are also present, but these are thermodynan~icallyless stable than the cyclic dimers.
Intramolecular hydrogen bonds are found between OH and NO2 groups in some 2-nitro-
alcohols, leading to stabilization of the gauche form with respect to the trans form. For 2-
nitroethanol the trans conformer is in equilibrium with two intramolecularly hydrogen bonded
conformers ( A H = -0.40 f 0.10 and -0.71 f 0.09 kcal/mole respectively). 2,2-Dinitro-
propanol and 2-methyl-2-nitro-1,3-propanediol show complex VOH bands due to trans and intra-
molecularly hydrogen bonded gauche conformers. 2,2,2-Trinitroethanol has a relatively narrow
symmetrical OH peak a t teniperatures up to 55 "C which is assigned t o the exclusively popu-
lated intramolecularly hydrogen bonded conformation.

INTRODUCTION
High-resolution infrared spectra of 2-substituted ethanols in the 3 p region give valuable
information about the factors affecting intramolecular hydrogen bond strengths (particu-
larly geonletry), and about those governing frequency displacenlents of hydrogen bonded
O H groups. As a continuation of previous studies on 2-mono-, 2,2-di-, and 2,2,2-tri-
halosubstituted ethanols (3), hydrogen bonding in 2-cyanoethanol (hydracrylonitrile) and
in some nitroalcohols in dilute CCll solution has been investigated.
Cyano Groups a s Proton Acceptors
The cyano group is well known to be a moderately strong proton acceptor because
of the directed lone pair orbital on the nitrogen atom (4). The linearity of the group
prevents steric complications in inter~nolecular hydrogen bonding studies. Hydrogen
bond strengths between nitriles and phenol (AH = -4 kcal/n~ole)and methanol (AH =
-2 kcal/inole) have been measured (5)
In the formation of intramolecular hydrogen bonds to the cyano group in 2-cyano-
ethanol the geometry of the system plays a major role, prohibiting access of the proton
donating group to the nitrogen lone pair orbital. The weaker hydrogen bonds which
form involve the T-electrons of the triple bond. The O H stretching frequencies of repre-
sentative hydroxynitriles and their acetylene analogues have been studied by Allerhancl
and Schleyer (4), and intramolecular N H . . .CN interaction has been noted in o-cyano-
aniline (6). No thermodynamic investigation of the strength of intran~olecularhydrogen
bonds to nitrile groups appears to have been reported.
The gas phase electron diffraction results of Yamaha (7) on 2-cyanoethanol itself showed
' W h i l e this work was i n progress the authors were i?zfor?ned,of other studies then i n press on nitro groups as
proton acceptors i n hydrogen bonds by Schleyer et al. (1). Their work did not, however, include quantitative
thermodynamic measzlrements o n which this paper i s based. Since this work was completed, H. E. Ungnade,
E. M. Roberts, and L. TV. Kissinger have also confirmed the existence of weak hydrogen bonds between nitro
groups and alcoholic OH groups (2).
Canadian Journal of Chemistry. Volume 13 (1965)
 KRUEGER AND METTEE: SPECTROSCOPIC STUDIES. V 2889

no evidence of an intramolecularly hydrogen bonded gauche conformation, and the

conclusion was reached that the molecule was exclusively in the trans form.
Nitro Groups as Proton Acceptors
Although chelation in o-nitrophenol is a well established fact (1, 8a) based on numerous
investigations using a wide variety of techniques, intramolecular OH. . .OzN hydrogen
bonding in systems which do not involve direct resonance interaction of the OH and
NO2 groups (which is responsible for the unusual strength of the intramolecular hydrogen
bond in o-nitrophenol and the large OH spectral shift) is subject to conflicting reports.
In connection with other studies of intrainolecular hydrogen bonds in simple systems
(3), 2-nitroethanol is of particular interest since no quantitative thermodynamic data on
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the conformational mobility of this compound appear to be available.

Flett (9) found only a broad band a t 3 588 cm-I for 2-nitroethanol in CCll solution,
significantly lower than the OH stretching frequency of 3 636 cin-I usually found for
monomeric normal primary alcohols under the same conditions. Kuhn, Luettke, and
Mecke (10) report a trans band a t 3 623 cnl-I and a gauche band a t 3 608 cin-I for 2-
nitroethanol, and conclude that the latter is inore stable because of a weak intramo-
lecular O H . . .02N hydrogen bond. For nitroalcohols with two 0-hydroxyl groups Ur-
banski and co-workers (11) have interpreted shifts in both ultraviolet and infrared peaks
associated with the NO2 group in terms of intramolecular hydrogen bonding.
Recently intran~olecularhydrogen bonding in 2-nitroalcohols, including 2-nitroethanol,
has been refuted on the basis of infrared studies in the 3 p region using a NaCl prisin
spectrophotometer of low resolution (12, 13).
Studies of intermolecular hydrogen bonding of various hydroxylic proton donors and
nitro compounds as proton acceptors show that nitro groups uniforinly form weak
hydrogen bonds as reflected in very small spectral shifts of the OH vibrational band (1).
Spectra obtained with high resolution are therefore essential for the complete inter-
pretation of the role these weak hydrogen bonds play in conformational equilibria, and
the investigation of the temperature dependence of such spectra is advisable since
frequency displacenlents do not necessarily measure the strength of weak intramolecular
hydrogen bonds.
EXPERIMENTAL
Spectroscopic measurements were made with a Beckman IR-7 infrared spectrophotometer operating a t
a calculated nominal slit width of about 1 cm-1. Matched fused quartz absorption cells of 2 and 10 cm path
length were used. Cell temperatures were controlled with a Lauda UK-70 D W Ultrakryostat. Other details
concerning technique have been described previously (3). Carbon tetrachloride (reagent grade) was dried
over P ? 0 5 and fractionally distilled through a 50 theoretical plate spinning band column. Other solvents
used were commercial products of spectroscopic quality.
Hydracrylonitrile (Eastman) was dried over anhydrous sodium sulfate and fractionally distilled through
a 23 plate spinning band column, collecting colorless material with a b.p. 82.5 "C a t 4 mm, noz3 1.4257
(lit. b.p. 82 "C a t 4 mm, noz51.4374 (14)). 2-Nitroethanol was a commercial product ( K & K Laboratories,
Inc.) which was dried over anhydrous NazSOr and distilled under reduced pressure (noz51.4497; lit. 1.438325
(15), 1.4403?O (16)). 2-Methyl-2-nitro-1,3-propanediol and 2,2-dinitropropanol were given by Dr. H. E.
Ungnade, Los Alamos Scientific Laboratory, University of California. A small sample of 2,2,2-trinitroethanol
(as a n anhydrous CC14 solution) was obtained from Dr. T. N. Hall, U.S. Naval Ordnance Laboratory,
White Oak, Silver Springs, Maryland, U.S.A. This was diluted further with d r y CCId and used directly.

RESULTS A N D DISCUSSION
2- Cyanoethanol
Concentrations of the order of M in CC14 were necessary to eliminate a broad
concentration and temperature dependent absorption band centered a t 3 500 cin-l. A t
these low concentrations a concentration independent but temperature dependent doublet
 2890 C A N A D I A S JOURNAL OF CHEMISTRY. VOL. 43, lDii5

remained in the 3 p region. The more intense high frequency component (3 633.9 cm-I)
must be due to the trans conformation, \\it11 the low frequency coinpoilent (3 619.0 cm-1)
due to the intramolecularlj~hjrdrogen bonded gnz~checonformation.' Figure l ( a ) s h o ~ ~ - s
some tj.pica1 spectra.
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3700 3600 3500 3400 3300

FREQUENCY (crn-'1

FIG.1. F~lndalmentalOH stretching bands of 2-c~~anoethanol in dilute CCll solution: (1) concentration
4 X 10-1 A/, path length 10.0 cm, te~mperature20 "C; (2) concentration 2.5 X 10FJ 116, path length 2.00 cm,
telnperat~lre20 "C; (3) sarne as (2) but a t (! OC; (4) concentration 2.5 X 10F3 111, and 0.65 M with respect
t o acetonitrile in both s a n ~ p l eand reference cell; (5) concentration 2.5 X 10-: Ad, and 0.5 111 with respect
to diethyl ether in both sample and reference cell; (6) capillary film of pure 2-cyanoethanol.

The relative intensity of the t~an,s/gauchedoublet is increased slightly by intermo-

lecular association which sets in a t the higher concentrations (-lO-\If). The first
associated species to appear \vith increasing concentration ~vouldbe expected t o be the
dimer (vide supra) which could conceivably have one of the follo~vingstructures.

In I and 111 the proton acceptor molecule could also be in the intran~olecularlyhydrogen
bonded gauche form.
Figure l(b) sho~vscomparative spectra of the 2-cyanoethanol-acetonitrile and the
2-cyanoethanol - diethy1 ether complexes respectively in dilute CC14 solution, as ~vell
a s a spectrun~of a thin film of pure 2-cyanoethanol. I t is lcno~vnt h a t the frequencies of
bonded 01-1 groups can s h o ~ va 111arlted dependence on the proton acceptor concentratioil
(17) so that these band positions do not represent values extrapolated to infinite dilution,
but they are useful in identifying the nature of the 2-cyanoethanol dimer. Since the G
value (17) of diethyl ether (G = 64) is very close to that of CCld (G = 69) little change
2TIzese bands have bee12 repol led at 3 626 and 3 610 cnz-I ( 9 ) and at 3 639 and 3 617 cm-I (4) i n very dilute
CCI I solzrtion.
 KRCEGER AND METTEE: SPECTROSCOPIC STUDIES. V "8'31

in the 2-cyanoethanol-EtnO complex band is expected as the Et?O concentration is

altered, but the 2-cyanoethanol-acetonitrile complex band is expected to shift to some-
what higher frequency on extrapolation to infinite dilution (G for CI-ISCN is 93). The
basicity of the N at0111 in 2-cyanoethanol is expected to be less than that of the I i atom
in a ~ e t o n i t r i l eso
, ~ that the frequency shift on inter~nolecularhydrogen bond formiation
a s in I11 should be less than that in N=CCH2CH?OI-I. .N=CCI-Ia hydrogen bond for-
mation. This is not the case. On the other hand the electron-m-ithdrawing nature of the
C=N group 11-ould increase the acidity3 of the OH but decrease the basicity of the
hydroxyl oxygen atom in 2-cyanoethanol,~maltingit a poorer proton acceptor than the
oxygen atom in diethyl ether. Therefore the frequency shift on intermolecular hydrogen
bond formation a s in I is expected to be less than that on N=CCI-I,CH201-I.. .OEt,
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hydrogen bond formation, and this is observed experimentally. A dimer like I1 is expected
to have a bonded OH frequency like that of I , or perhaps a little higher.
The hydrogen bond strength of 6.1 Itcal/mole in the 2-cyanoethanol dimer a s
deterinined in this work rules out 111 and favors I1 over I. Strengths of O H . . . N C
hydrogen bonds involving phenol and methanol have been found to be only 4 and 2
Itcal/mole respectively (5) whereas the AH values for dimerization of simple alcohols are
6-7 kcal/mole (20), in line with the 2-cyanoethanol value. There is considerable evidence
favouring cyclic di~nerswith tu7o non-linear OI-I. . .O hydrogen bonds for simple alcohols
(Sb), and this may also apply to the 2-cyanoethanol dimers. The capillary film shows
extrenlely broad OH absorption, presumably due to a variety of molecular aggregates.
Figure 2(b) s11011,s the temperature dependence of the trans/gaziche absorbance ratio

1
-0.5-
W
0
Z - (cl
I a
m
-
(Z
0
-
cn
m -
-a -1.0 -
w -
0
J -
-
-
-1.5 - , I

3.0 3.5 4.0

I/T x lo3
FIG. 2. ( a ) Temperature dependence of trans/gazrche absorbance ratio of monomeric 2-c) anoethanol a t
concentrations where some dimerization occurs. ( b ) Temperature dependence of trans/gazrche absorbance
ratio in monomeric 2-cyanoethanol in very dilute CCI I solution ( < 4 X lo-' 111). ( c ) Temperature depend-
ence of dimerization constant for 2-cyanoethanol a t higher concentrations in CC14 ( 4 X lo-' < concen-
tration ,< 2.5 X ill). Apparent equilibrium constants ICI and K ~ calculated
I on the basis of open and
I cyclic di~nersrespectively. For convenience the factor 2 in the K I I expression is omitted.

I 3T1~eTuft u* values ( 1 8 ) for HOCH2CH2- aud N=CCH2CH?- groups are esti717ated to be $0.20 and
I $0.46 respectzvely relative to a valz~eof zero for tlte CH3- grozrp. Electron-withdrawing groups O,L a nztrile
decrease tlte frequency shift observed on inter~~zoleczrlarhydrogen bond for??zatz07~with a gioelt proton doltor (4).
Y t has been demonstrated that this zs the case i n 2,2,2-trifEuoroetlzano1 (19).
 2892 CANADIAN JOURNAL O F CHEMISTRY. VOL. 43. 1965

a t concentrations in CC14 where intermolecular association is absent. Evaluation of the

slope of the log,, (D,/D,) vs. l / T plot by the least squares method gives A H = -0.14 f
0.03 kcal/mole for the process in which the hydrogen bond forms. Considering the
interactions between non-bonded atoms on the adjacent carbon atoms in the trans and
gauche forms (21), it follows that the trans --,gauche process is accompanied by the gain
of one weak repulsive interaction (H-H) and the loss of two stronger repulsive inter-
actions (H-CN and H-OH) as well as the gain of the attractive OH-CN interaction.
The observed - A H is therefore probably greater than would be expected on the basis
of the intramolecular hydrogen bond alone because of the lost repulsive interactions, i.e.
the hydrogen bond strength itself is less than 0.14 kcal/rnole. The very weak nature of
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this interaction accounts for the fact that no bonded OF1 peak is observed for compounds
of the type HO-(CH2),-CN when n = 3 or 4 (4).
From measurements a t higher concentrations the enthalpy change on intermolecular
association can be determined. Using absorbances a t the maxima of the intermolecularly
bonded peak (D,), the trans peak (D,) and the gauche peak (Do) as estimates of the
respective relative concentrations, the following approximate equilibrium expressions
apply for the formation of I and I1 respectively.

In the first expression the total monomer absorbance (D, + Do) is corrected for the
absorbance of "tern~inal" OH groups of open dirners, which probably contribute to the
trans band (8c). Extinction coefficient differences for the bands are ignored since the
behavior of K vs. l / T will be affected little if E l = E,, which is reasonable for such a
weak intramolecular hydrogen bond. Furthermore, the diiner concentration was always
relatively small. Figure 2(c) shows the temperature dependence of K 1 and K,,. The
linearity of K I Ivs. l / T implies that cyclic diinerization is the dominant type of association
in this concentration range, with A H = -6.1 f 0.3 kcal/mole (least squares method,
90% confidence limits), which reflects the intermolecular hydrogen bond strength of the
two angular OH. -0bonds in the cyclic dimer. The plot of K 1 vs. l / T is linear a t high
temperatures where the dimer concentration is small, but curves upward a t lo\irer tein-
peratures where d i n e r concentration is larger.
Figure 2(a) also shows the increase in D,/Do in solutions where dirnerization occurs.
This increase indicates the contribution of some 'terminal" OH absorption from a small
amount of the acyclic dimer I to the trans band. At these low concentrations the mono-
meric confornlational equilibrium should not be affected by the presence of a minute
amount of dimer. Because the measurements were made a t several concentrations these
points are spread over a narrow belt, the edges of which can be extrapolated to meet line
(b) in Fig. 2 a t -35 "C, where all I would have reverted to the more stable 11.
Acetone Cyanohydrin
Weak intrainolecular OH interaction with a nitrile group leading to a formal four-
lnembered ring also seems possible. Thus, for acetaldehyde cyanohydrin, only one OH
band has been reported a t 3 607 cin-I (ref. 4, interpreted as "bonded" vOH)and 3 604 cm-I
(ref. 9, interpreted as "free" voH). For acetone cyanohydrin we have found a single sharp
symmetrical band a t 3 600.4 cm-I, AvllzU = 16.6cm-I a t 28 "C, shifting to 3 602.6 cm-I
with Avllza = 17.3 cm-I a t 55 "C, and becoming slightly asymmetric on the high frequency
side. The low value of this OH frequency indicates that it belongs to a hydrogen bonded
 KRUEGER AND METTEE: SPECTROSCOPIC STUDIES. V 2893

group. Rotation about the C-0 bond to move the hydroxyl proton from the gauche to the
trans position with respect to the CN group would bring repulsive forces between the
oxygen lone pair orbitals and the CN T-electrons into play, and this may help to stabilize
-
the gauche form. Intramolecular hydrogen bonding involving O H . .O=C interaction in
four-membered rings is well known in carboxylic acids (22), and similar N H . . .O=C
interaction in partially deuterated primary acid amides leads to cis-trans isomerism of
the -NHD groups (23).
Nitroalcohols
Figure 3(a) shows the fundamental OH stretching bands of 2-nitroethanol (0.0038 M
in CC14) obtained a t room temperature. The maximum a t 3 630 cm-I is assigned to the
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trans conforiner, and maxima a t 3 620 and 3 612 cm-I are assigned to two intramolecularly
hydrogen bonded gauche conformers. These measurements agree well with those of
Schleyer et al. (1).

0.8
2-nitroethanol 0.0038 M

slit
a
m
~r0.4
-
0
V)
m
a 0.2-

3600
FREQUENCY (cm-'1
P
L

FIG.3. ( a ) Fundamental OH stretching bands o f 2-nitroethanol, 0.0038 M in CCII,path length 2.00 c m ,

temperature 28 "C. ( b ) Temperature dependence o f OH absorbance ratios for 2-nitroethanol.

The tenzperature dependence of the spectra, shown in Fig. 3(b), indicates that bands
B and C arise from conformers which are thermodynamically more stable than the
trans conforiner (band A) by -0.40 f 0.10 and -0.71 f 0.09 kcal/mole respectively
(least squares method, 90% confidence limits). Since the barrier to rotation about a
C-NO2 bond is known to be insignificantly small (6 cal/mole, ref. 24), hydrogen bonded
conformations involving one or both oxygen atoms of the nitro group have been suggested
(I). In the conformer where the OH group bonds to one of the nitro group oxygen atoms,
I
the proton may be imbedded in an oxygen p-orbital, forming a six-membered ring. I t is
I doubtful whether more specific assignments of bands B and C can be made a t the present
1 time. The -AH values observed are probably larger than the hydrogen bond strengths
I
I themselves because of the loss of repulsive non-bonded interactions on going from the
trans to the gauche form.
 2894 CANADIAN JOURNAL O F CHEMISTRY. VOL. 43, 19(i5

The present measureil~ents on 2-meth~~l-2-nitro-1,3-propanediol(Fig. 4(a)) are in

agreement with those of Schleyer et al. ( I ) . The main maximum a t 3 608.1 cin-I and
the shoulder a t -3 591 cm-I are attributed to OH intramolecularly bonded to NO? in
t ~ v odifferent ways, the pronounced high frequency shoulder a t 3 633 cm-I is due to
"free" OH groups, whereas the very weak l o ~ vfrequency shoulder a t -3 553 ~ 1 1 1 - I must
be due to intramolecular O H . . . O bonding in a seven-membered ring. Although O H . . .OzN
interaction is weaker than O H . . . O interaction the former is favored because of the
proxiinity of the two groups in the molecule.
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0.4

0.2

0
3700 3600 3500
FREQUENCY (cm-I)

FIG.4. Fundamental OH stretching bands of several nitroalcohols in dilute CCll solution, path length
2.00 cm, temperature ambient unless indicated: ( a ) 2-1neth~l-2-nitro-l,3-propanediol (1.8 X 10-"il/l);
( 0 ) 2,2-dinitropropanol (J.1 X 1 0 - W ) ; (c) 2,2,2-trinitroethanol (-6 X 1 0 - q f ) .

In 2,2-dinitropropanol (Fig. 4(8)) the relative intensity of the "free" 01-1 shoulder
(3 628 cm-') has diminished with respect to the intrainolecularly hydrogen bonded band
(3 602.7 cm-') because of the enhanced acidity of the OH group due to the electron-
withdrawing effect of two NO2 groups, and the possibility of hydrogen bonding to tu7o
NOz groups. In the extreme case of 2,2,2-trinitroethanol a narrow (Avl,?' = 20 cm-')
synlinetrical 011 band is observed a t 3 593.? cm-I a t room temperature (Fig. 4(c)). At
55 'C the peak has moved to 3 596.6cnl-l, but it is still symmetrical. T h e low frequency
and narrow syininetrical nature of this band iinply a single intran~olecularlyhydrogen
bonded conformation. T h e acidity of the OH group would be enhanced by the electron-
withdra~vingeffect of three NOz groups. Further, "free" OH groups can only arise by
rotation about the C-0 bond, bringing strong repulsive forces between the lone pair
orbitals on the hydroxyl oxygen atom and the nitro groups into play. Thus even a weak
O H . . .O?N bond would be sufficient to lieep all the OH groups hydrogen bonded.
Nitro groups are therefore capable of acting a s proton acceptors in intrainolecular
hydrogen bond forination in aliphatic systems.
 KRUEGER AND MIZTTEB: SPISCTROSCOPIC STUDIES. V 2895

ACKNO\VLEDGR/IENTS
T h e a u t h o r s are g r e a t l y i n d e b t e d to Drs. T. N. I-Iall a n d I-I. E. U i l g n a d e for g i f t s of
c h e m i c a l s , a n d to Drs. P. v o n R. S c h l e y e r a n d I-I. E. U n g n a d e for p r e p r i n t s of their
n l a n u s c r i p t s . This w o r k \\;as s u p p o r t e d f i n a n c i a l l y by the N a t i o n a l Research C o u n c i l
of C a n a d a .

REFERENCES
I . 117. F. BAITINGER, P. \TON R. SCIILEYEII,T. S. S. R. ~ ~ c I I T Yand
, I>. RORIXSOX.Tetrahedron, 20,
1635 (1964).
2. H. E . UNGNADE, E. M. ROBERTS, and L. \\I. I~ISSINGER. Unpublished results.
3. P. J. I ~ R U E G EandR H. D. METTEE. Can. j. Chem. 42, 326 (1964) and other papers in this series.
4. A. ALLEKHAND and P. VON R. SCHLEYER.J. Am. Chem. Soc. 85, 866 (1963).
Can. J. Chem. Downloaded from cdnsciencepub.com by 117.235.167.50 on 01/26/24

5. S. S. MITKA. J. Chen~.Phys. 36, 3286 (1962).

6. P. J . I ~ R C E G E KCan.
. J. Chem. 40, 2300 (1962); 42, 201 (1964).
7. M. YAMAHA.Bull. Chem. Soc. Japan, 29, 876 (1956).
8. G. C. PIMENTEL and A. L. MCCLELLAN.The hydrogen bond. \\'. H. Freeman and Co., San Fran-
cisco. 1960. ( a ) Chap. 5 (b) p. 99 (c) pp. 96-97.
9. M. ST. C. FLETT. Spectrochim. Acta, 10, 21 (1957).
10. M. I ~ U A N W., LUETTKE, and R. MECICE. Z. Anal. Chetn. 170, 106 (1959).
11. T. URBANSKI.I f t Hydrogen bonding. Ediled by D. Hadzi. Pergamon Press, N.Y. 1959. p. 143.
12. H. E . UNGNADE and L. \V. I~ISSINGEII. Tetrahedron, 19, Suppl. 1, 121 (1963).
13. H. E. UNGNADE, E. D. LOUGHIIAN, and L. W. I<ISSINGB~I.J. Phys. Chem. 66, 2643 (1962).
14. E. F. D U P I ~ E Anal.
. Chern. 27, 1878 (1955).
15. I.\ E. NO~ILAND and P. J. HARTMAN.J . Am. Chem. Soc. 76, 3227 (1954).
16. Z. ECKSTEIN, P. GLUZINSKI, W. SOROTKA, and T . UI~BANSKI. J. Chem. Soc. 1370 (1961).
17. A. ALLEKHAND and P. VON R. SCHLEYER.J. Am. Chem. Soc. 85, 371 (1963).
18. R. W. TAFT,JR. I n Steric effects in organic chemistry. Ediled by M. S. Newman. J . \b'iley and Sons,
Inc., New York. 1956. Chap. 13.
19. B. D. NAGESWAIIA RAO, PUTCHA VENKATESWAI~LU, A. S. N. MUTHY,and C. N. R. RAO. Can. J .
Chem. 40, 387 (1962). C. N. R. RAO, R. VENICATARAGHAVAN, I<. R. BHASKAII,and A. BALA-
SUBIIAIIANIAN.I n Proceedings of the Xth Colloquium Spectroscopicurn Internationale. Ediled by
E. R. Lippincott and M. Margoshes. Spartan Books, Washington, D.C. 1963. p. 505.
20. U. LIDDEL and E. D. BECICEII. Spectrochim. Acta, 10, 70 (1957).
21. L. P. I<UHNand R. A. WII~ES.J . Am. Chem. Soc. 86, 2161 (1964).
22. M. 01cr and M. HIROTA. Bull. Chem. Soc. Japan, 34, 374 (1961).
23. A. G. MORITZ. Nature; 195, 800 (1962).
24. E. ' ~ A N N E N B A U R.I ~D.
, JOHNSON, R. J . MYERS,and \V. D. GWIXN. J. Chern. Phys. 22, 949 (1954).
E. TANNENBAUM, R. J . MYERS,and W. D. GWIXN. J. Chem. Phys. 25, 42 (1956).