JCK(Wiley) RIGHT Interactive

Kinetics and Mechanism of

the Oxidation of Diols by
Pyridinium Bromochromate
P. SURYA CHANDRA RAO, DEEPA SURI, SEEMA KOTHARI, KALYAN K. BANERJI
Department of Chemistry, J.N.V. University, Jodhpur 342 005, India
Received 8 January 1997; accepted 5 July 1997

ABSTRACT: The kinetics of oxidation of four vicinal diols, four nonvicinal diols, and one of
their monoethers by pyridinium bromochromate (PBC) have been studied in dimethyl sulf-
oxide. The main product of oxidation is the corresponding hydroxyaldehyde. The reaction is
first-order with respect to each the diol and PBC. The reaction is acid-catalyzed and the acid
dependence has the form: kobs ⫽ a ⫹ b[H⫹]. The oxidation of [1,1,2,2-2H4]ethanediol exhibited
a primary kinetic isotope effect (kH/kD ⫽ 6.70 at 298 K). The reaction has been studied in 19
organic solvents including dimethyl sulfoxide and the solvent effect has been analyzed using
multiparametric equations. The temperature dependence of the kinetic isotope effect indicates
the presence of a symmetrical transition state in the rate-determining step. A suitable mech-
anism has been proposed. 䉷 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 285– 290, 1998.

INTRODUCTION EXPERIMENTAL

Pyridinium bromochromate (PBC) has been used as a Material

mild and selective oxidizing reagent in synthetic or-
ganic chemistry [1]. It is structurally similar to well-
known Corey’s reagent-pyridinium chlorochromate
(PCC) and pyridinium fluorochromate (PFC). There
are only few reports on the mechanistic aspects of ox-
idation reactions of PBC [2 – 5]. There seems to be no
report on the kinetics of oxidation of diols by PBC. It
has been observed that the kinetics of oxidation of
diols by PFC [6] and PCC [7] are different. In this
article we report the kinetics of oxidation of some vic-
inal diols, nonvicinal diols, and one of their monoeth-
ers by PBC in dimethyl sulfoxide (DMSO). The mech-
anistic aspects are discussed.
Correspondence to: K. K. Banerji
Contract grant Sponsor: University Grants Commission (India)
Contract grant Sponsor: Council of Scientific and Industrial Re-
search (India)
䉷 1998 John Wiley & Sons, Inc. CCC 0538-8066/98/040285-06
The diols and the monoether (BDH or Fluka) were
distilled under reduced pressure before use. PBC was
prepared by the reported method [1]. [1,1,2,2-
2H ]ethanediol (DED) was prepared by reducing die-
4
thyl oxalate with lithium aluminium deuteride [8]. Its
isotopic purity, determined by its 1H NMR spectrum,
was 88 ⫾ 4%. Solvents were purified by the usual
methods [9]. Toluene-p-sulfonic acid (TsOH) was
used as a source of hydrogen ions.
Product Analysis
Product analysis was carried out under kinetic condi-
tions. In a typical experiment, the diol (0.1 mol) and
PBC (0.01 mol) were taken in DMSO (100 ml) and
the mixture was allowed to stand in the dark for ca.
10 h to ensure completion of the reaction. Most of the
solvent was removed under reduced pressure and res-
idue treated overnight with an excess (250 ml) of a short
saturated solution of 2,4-dinitrophenylhydrazine in standard
long
JCK(Wiley) LEFT Interactive

286 RAO ET AL.

Table I Analysis of Products in the Oxidation of Diols and 3-Methoxybutan-1-ol by PBC

m.p. of
DNP, Yielda
Diol Product ⬚C %
Ethanediol HOCH2CHO 153 89
Propane-1,2-diol MeCH(OH)CHO 94b 91
Butane-2,3-diol MeCOCH(OH)Me 114 85
Butane-1,2-diol MeCH2CH(OH)CHO 132c 92
Propane-1,3-diol HOCH2CH 2CHO 133 92
Butane-1,3-diol MeCH(OH)CH2CHO 91 90
Butane-1,4-diol HOCH2CH 2CH 2CHO 117 88
Pentane-1,5-diol HOCH2(CH 2 )3CHO 79 82
3-Methoxybutan-1-ol MeCH(OMe)CH2CHO 104 88
a
The yield is of DNP derivative after recrystallization.
b Instead of DNP, phenylhydrazone derivative was prepared.
c Instead of DNP, 4-nitrophenylhydrazone derivative was prepared.

2 mol dm⫺3 HCl. The precipitated 2,4-dinitropheny- ing the relation: k2 ⫽ kobs/[redutant]. All experiments,
lhydrazone(DNP) was filtered off, dried, recrystallized other than those for studying the effect of hydrogen
from ethanol, and weighed. The DNP derivatives were ions, were carried out in the absence of TsOH.
found to be homogeneous by TLC. The identity of the
products were established by comparing the m.p. of
the DNP derivatives with the literature values [10]. In RESULTS
the oxidation of ethanediol and butane-1,3-diol, the
identity of the products were confirmed by determin- The rate laws and other experimental data were ob-
ing the m.m.p. with authentic samples of DNP of hy- tained for all the diols investigated. As the results were
droxyethanal and 3-hydroxybutanal, respectively. The similar, only representative data are given here. There
melting points were obtained in open capillaries and
are uncorrected. The results are summarized in Ta-
ble I.
The oxidation state of chromium in completely re-
duced reaction mixtures, determined by an iodometric Table II Rate Constants for the Oxidation of
method, was 3.95 ⫾ 0.09. The overall reaction may, Ethanediol by PBC at 298 K in DMSO
therefore, be written as the following equation: 103 [PBC] [diol] [TsOH] 104 kobs

HOCH2 9 CH2OH ⫹ O2CrBrOpyH 哹哹

ƒ mol dm⫺3 mol dm⫺3 mol dm⫺3 s⫺1
HOCH2 9 CHO ⫹ H2O ⫹ OCrBrOpyH (1) 1.0 0.10 0.0 4.00
1.0 0.20 0.0 7.95
1.0 0.30 0.0 12.7
Kinetic Measurements 1.0 0.60 0.0 24.7
The reactions were followed under pseudo-first-order 1.0 1.00 0.0 40.4
1.0 1.50 0.0 63.1
conditions by keeping a large excess (⫻ 15 or greater)
1.0 2.00 0.0 76.9
of the diol over PBC. The temperature was kept con-
1.0 1.00 0.0 40.6a
stant to ⫻ 0.1 K by means of a refrigerated bath cir- 2.0 1.00 0.0 41.0
culator (Haake, GD-8). The solvent was DMSO, un- 4.0 1.00 0.0 40.2
less specified otherwise. The reactions were followed 8.0 1.00 0.0 40.6
by monitoring the decrease in the concentration of 10.0 1.00 0.0 41.4
PBC spectrophotometrically (Spectrochem model MK 1.0 1.00 0.1 46.7
II) at 358 nm for upto 80% of the reaction. The 1.0 1.00 0.2 53.9
pseudo-first-order rate constants, kobs, were evaluated 1.0 1.00 0.3 62.5
from the linear (r ⫽ 0.9960 – 0.9990) plots of log 1.0 1.00 0.5 71.4
[PBC] against time. Duplicate kinetic runs showed that 1.0 1.00 0.8 95.0 short
1.0 1.00 1.0 110
the rate constants were reproducible to within ⫾ 3%. standard
The second-order rate constant, k2, was determined us- a Contained 0.005 mol dm⫺3 acrylonitrile. long
JCK(Wiley) RIGHT Interactive

OXIDATION OF DIOLS 287

Table III Rate Constants and Activation Parameters of the Oxidation of Diols and 3-Methoxybutan-1-ol by PBC in
DMSO
103k2 /mol⫺1 dm3 s⫺1 ⌬ H* ⌬ S* ⌬ G*
Diol 298 K 308 K 318 K 328 K kJ mol⫺1 J mol⫺1 K⫺1 kJ mol⫺1
Ethane-1,2-diol 4.04 8.50 17.0 32.9 54.2 ⫾ 0.2 ⫺109 ⫾1 86.7 ⫾ 0.1
Propane-1,2-diol 17.0 32.8 61.5 114 49.0 ⫾ 0.3 ⫺115 ⫾1 83.1 ⫾ 0.3
Butane-2,3-diol 24.5 46.5 86.1 160 48.2 ⫾ 0.5 ⫺115 ⫾2 82.2 ⫾ 0.4
Butane-1,2-diol 71.9 127 215 404 43.8 ⫾ 1.3 ⫺121 ⫾4 79.6 ⫾ 1.0
Propane-1,3-diol 8.58 16.2 31.4 60.7 50.5 ⫾ 0.9 ⫺116 ⫾3 84.9 ⫾ 0.7
Butane-1,3-diol 10.5 22.1 43.0 83.8 53.5 ⫾ 0.3 ⫺104 ⫾1 84.3 ⫾ 0.2
Butane-1,4-diol 13.0 25.6 49.2 94.5 51.1 ⫾ 0.5 ⫺110 ⫾2 83.8 ⫾ 0.4
Pentane-1,5-diol 14.1 30.4 64.0 128 57.3 ⫾ 0.1 ⫺ 89 ⫾1 83.6 ⫾ 0.1
3-Methoxybutan-1-ol 24.0 45.6 86.6 162 49.2 ⫾ 0.6 ⫺112 ⫾2 82.3 ⫾ 0.4
DEDa 0.603 1.28 2.70 5.90 59.1 ⫾ 1.1 ⫺109 ⫾3 91.5 ⫾ 0.8
kH /kD 6.70 6.64 6.30 5.58
[diol] ⫺ 0.1– 1.0 mol dm⫺3; [PBC] ⫺ 0.001 mol dm⫺3.
a [1,1,2,2-2 H ]Ethane-1,2-diol.
4

is no noticeable oxidation of pinacol by PBC under Effect of Temperature

our reaction conditions.
The rate constants of the oxidation of diols were ob-
The reactions were found to be first-order with re-
tained at different temperatures and the activation pa-
spect to PBC. Individual kinetic runs were strictly
rameters were evaluated (Table III).
first-order in PBC. Further, the first-order rate coeffi-
cients did not vary with the initial concentrations of
PBC. The order with respect to diol was also found to Kinetic Isotope Effect
be one. The rate increased with an increase in the con-
To ascertain the importance of the cleavage of the ␣-
centration of hydrogen ions. The hydrogen-ion depen-
C 9 H bond in the rate-determining step, the oxidation
dence had the form kobs ⫽ a ⫹ b [H⫹]. The results are
of DED was studied. The results recorded in Table III
recorded in Table II.
showed that the reaction exhibited a substantial kinetic
isotope effect (kH/kD ⫽ 6.70 at 298 K).
Induced Polymerization of Acrylonitrile
Solvent Effect
The oxidation of diols by PBC, in an atmosphere of
nitrogen, failed to induce the polymerization of acry- The oxidation of ethanediol was studied in 19 different
lonitrile. Further, the addition of acrylonitrile had no solvents. The choice of solvent was limited due to the
effect on the rate (Table II). solubility of PBC and its reaction with primary and

Table IV Rate Constants for the Oxidation of Ethanediol by PBC in Different Solvents at 298 K
103 k2 103 k2
Solvent mol⫺1 dm3 s⫺1 Solvent mol⫺1 dm3 s⫺1
Chloroform 1.06 Cyclohexane 0.054
Carbon disulfide 0.205 Toluene 0.395
1,2-dichloromethane 1.35 Acetophenone 1.72
Dichloromethane 1.32 Tetrahydrofuran 0.691
DMSO 4.04 t-Butylalcohol 0.424
Acetone 1.26 1,4-Dioxane 0.686
N,N-Dimethylformamide 2.25 1,2-Dimethoxyethane 0.354
Butanone 0.972 Acetic acid 0.130
Nitrobenzene 1.61 Ethyl acetate 0.514 short
Benzene 0.498
standard
[Diol] ⫺ 1.0 mol dm⫺3; [PBC] ⫺ 0.001 mol dm⫺3. long
JCK(Wiley)
288 RAO ET AL.
Table V Reaction Constants of the Oxidation of
Vicinal Diols by PBC in DMSO
T/K ⌹* r2 sd ⌿ Swain’s equation [14] of cation- and anion-solvating
298 ⫺1.28 ⫾ 0.03 0.9991 0.02 0.02
308 ⫺1.20 ⫾ 0.03 0.9989 0.02 0.03
318 ⫺1.13 ⫾ 0.03 0.9982 0.03 0.03
328 ⫺1.12 ⫾ 0.03 0.9987 0.02 0.03
secondary alcohols. There was no reaction with the
solvents chosen. The kinetics were similar in all the
solvents. The values of k2 are recorded in Table IV.
DISCUSSION
The values of log k2 at 298 K for the nine compounds
are linearly related (r ⫽ 0.9911) to the corresponding
values at 328 K (Table III). The isokinetic temperature
evaluated from this plot is 788 ⫾ 45 K [11]. The lin-
ear isokinetic correlation implies that all the com-
pounds are oxidized by the same mechanism and the
changes in the rate are governed by the changes in both
the enthalpy and entropy of the activation [11]. The
linear correlation here involves a typical monohydric
alcohol, 3-methoxybutan-1-ol. Thus, it seems likely
that the diols also behave like monohydric alcohols
towards PBC. This is further supported by the isolation
of the hydroxyaldehydes as the products (Table I) and
the resistance of pinacol towards oxidation by PBC.
In correlation analyses, we have used coefficient of
determination (R2 or r2), standard deviation (sd), and
Exner’s parameter [12]. ␺, as the measures of good-
ness of fit.
The rate constants of oxidation of ethanediol, k2
(Table IV), in eighteen solvents (CS2 was not consid-
ered as the complete range of solvent parameters was
not available) were correlated in terms of linear sol-
vation energy relationship of Kamlet et al. [13].
log k2 ⫽ A0 ⫹ p␲ * ⫹ b␤ ⫹ a␣ (2)
In this equation, ␲ * represents the solvent polarity, ␤
the hydrogen bond acceptor basicities, and ␣ is the
hydrogen bond donor acidity. A0 is the intercept term.
The results of correlation analyses in terms of eq. (2),
a biparametric equation involving ␲ * and ␤, and sep-
arately with ␲ * and ␤ showed that Kamlet’s tripara-
metric equation explain ca. 85% of the effect of sol-
vents on the oxidation. However, by Exner’s criterion
the correlation is not satisfactory [12]. The major con-
tribution is of solvent polarity. It alone accounted for
ca. 80% of the data. Both ␤ and ␣ play relatively minor
role.
LEFT Interactive
The rate constant of the oxidation of ethanediol, k2,
in the nineteen solvents were analyzed in terms of
concept of the solvents also.
log k2 ⫽ aA ⫹ bB ⫹ C (3)
A represents the anion-solvating power of the solvent
and B the cation-solvating power. C is the intercept
term. (A ⫹ B) is postulated to represent the solvent
polarity. The rates in different solvents were analyzed
in terms of eq. (3), separately with A and B and with
(A ⫹ B).
log k2 ⫽ 0.29(⫾ 0.01)A
⫹ 1.75(⫾ 0.01)B ⫺ 4.38 (4)
R2 ⫽ 0.9996; sd ⫽ 0.01; n ⫽ 19; ␺ ⫽ 0.01
log k2 ⫽ 0.05(⫾ 0.58)A ⫺ 4.82 (5)
r2 ⫽ 0.0004; sd ⫽ 0.47; n ⫽ 19; ␺ ⫽ 1.02
log k2 ⫽ 1.73(⫾ 0.05)B ⫺ 4.29 (6)
r2 ⫽ 0.9844; sd ⫽ 0.06; n ⫽ 19; ␺ ⫽ 0.09
log k2 ⫽ 1.27 ⫾ 0.19(A ⫹ B) ⫺ 4.34 (7)
r2 ⫽ 0.7318; sd ⫽ 0.24; n ⫽ 19; ␺ ⫽ 0.39
Here n is the number of data points, i.e., the number
of solvents studied.
The rate constants of oxidation of ethanediol in dif-
ferent solvents show an excellent correlation in
Swain’s equation with the cation-solvating power
playing the major role. In fact, the cation-solvation
alone accounts for ca. 98% of the data. The solvent
polarity, represented by (A ⫹ B), accounted for ca.
73% of the data. In view of the fact that solvent po-
larity is able to account for ca. 73% of the data, an
attempt was made to correlate the rate with the relative
permittivity of the solvent. It was observed that a plot
of log (rate) against the inverse of the relative permit-
tivity is not linear (r2 ⫽ 0.4560; sd ⫽ 0.34; ␺ ⫽
0.59). In earlier studies with PBC also [2 – 5], it was
observed that the effect of the 19 solvents on the re-
action rate did not exhibited a significant correlation
in terms of Kamlet’s equation whereas the correlations
with Swain’s equation were excellent.
Correlation Analysis of Reactivity
short
The rate constants of oxidation, k2, of the four vicinal standard
diols in DMSO (from Table III) showed an excellent long
JCK(Wiley) RIGHT Interactive

OXIDATION OF DIOLS 289

correlation with Taft’s 兺␴ * values [15] with negative

reaction constants, ␳ * (Table V). Here 兺␴ * represents
the sum of the substituent constant for the substituents
present on the two alcoholic carbons of the vicinal
diols.

Mechanism
The absence of any effect of a radical scavenger, ac-
rylonitrile (Table II), indicated that a hydrogen ab-
straction mechanism, giving rise to free radicals, is
unlikely. The presence of a substantial kinetic isotope
effect (Table III) confirms the cleavage of an
␣-C 9 H bond in the rate-determining step. The neg-
ative value of the polar reaction constant (Table V)
indicated that the transition state approaches a carbo-
cation in character. Therefore, transfer of a hydride-
ion from the diol to the oxidant is suggested. The hy-
dride-ion transfer mechanism is also supported by the
greater role of cation-solvating power of the solvents
in the reactions.
The hydride-ion transfer may take place either by
a cyclic process via an ester intermediate or by an acy-
clic one-step bimolecular process. Kwart and Nickle
[16] have shown that a dependence of kH/kD on tem-
perature can be successfully employed to determine
whether the loss of hydrogen proceeds through a con-
certed cyclic process or by an acyclic one. The data Scheme I
for protio and deuterioethanediols (Table III),
fitted to the familiar expression kH/kD ⫽ AH/AD posed to involve the formation of a chromate ester in
exp(⫺ ⌬Ea/RT) show a direct correspondence with the a fast preequilibrium and then a decomposition of the
properties of a symmetrical transition state in which ester in a subsequent slow step via a cyclic concerted
the activation energy difference (⌬Ea) for kH/kD is symmetrical transition state leading to the product.
equal to the zero-point energy difference for the re- The observed hydrogen-ion dependence (Table II)
spective C 9 H and C 9 D bonds (⬇ 4.5 kJ/mol) and suggests that the reaction follows two mechanistic
the frequency factors and entropies of activation of the pathways, one acid-independent and another acid-de-
respective reactions are nearly equal [17,18]. Similar pendent. The acid-catalysis may well be attributed to
phenomena were observed earlier in the oxidation of a protonation of either PBC to yield a protonated
benzhydrol by PBC [1] and that of diols by PFC [6]. Cr(VI) species which is a stronger oxidant and elec-
Bordwell [19] has given very cogent evidence trophile or the chromate ester, with both the protonated
against the occurrence of concerted one-step bimolec- and unprotonated forms being reactive. Similar obser-
ular processes by hydrogen transfer and it is evident vations were recorded earlier in the reactions of struc-
that in the present reaction also the hydrogen transfer turally similar PFC [6].
does not occur by an acyclic bimolecular process. It is
well established that intrinsically concerted sigma- +

tropic reactions, characterized by transfer of a hydro- O2CrBrOPyH ⫹ H⫹ 哹哹

gen in a cyclic transition state, are the only truly sym-
metrical processes involving linear transfer of
hydrogen [20]. Littler [21] has also shown that a cyclic
hydride-ion transfer, in the oxidation of alcohols by
Cr(VI), involves six electrons and, being a Huckel-
type system, is an allowed process. Thus, a transition
state having a planar, cyclic, and symmetrical structure
can be envisaged for the decomposition of the ester
intermediate. Hence, the overall mechanism is pro-
´ƒ OBrCr(OH)OPyH
哹哹 (12)
The observed negative values of entropy of activation
(Table III) also supports a polar transition state. As the
charge separation takes place in the transition state,
the charges become highly solvated. This results in an
immobilization of a large number of solvent mole-
cules, reflected in the loss of entropy. The mechanism short
depicted in Scheme I accounts for all the observed standard
data. long
JCK(Wiley)
290 RAO ET AL.
It is of interest to compare the mode of oxidation
of diols by PFC [6], PCC [7], and PBC. The oxidation
of diols by all the three oxidants led to the formation
of corresponding hydroxyaldehydes. The oxidation by
PFC exhibited a Michaelis – Menten type kinetics
while the oxidations by PCC and PBC exhibited first-
order kinetics with respect to diols. This may be due
to the higher electronegativity of fluorine atom than
bromine and chlorine atoms which causes the central
metal atom to be more electron-deficient. This, in ad-
dition with the smaller size of fluorine atom, might
explain the formation of a kinetically detectable com-
plex in the oxidation by PFC. The observed kinetic
isotope effect is similar in all the three cases. Both the
PFC and PBC are reported to involve two mechanistic
paths, one acid-dependent and another acid-indepen-
dent. In the case of PCC the effect of acidity was not
studied. In the oxidation of diols by PFC and PBC,
excellent correlations were obtained in term’s of
Swain’s equation with the cation-solvating power of
the solvents playing the major role. Solvent effect was
not studied in the oxidation by PCC. The oxidations
by all the three oxidants showed an excellent corre-
lation by Taft’s ⌺␴ * values with negative polar re-
action constant. The correlation analysis, in the case
of PCC, was performed by us for this study (r2 0.9996;
␳ * ⫺ 1.18 ⫾ 0.02). Though the data are not conclu-
sive, the difference in the observed kinetics suggest
that the mode of oxidation depends on the nature of
the halogen atom present in the Cr(VI) species.
It may be mentioned here that pinacol is oxidized
by chromic acid but not by PBC. Chatterjee and Mu-
kherji [22] reported an abrupt change from butane-2,3-
diol to pinacol, the latter reacting very fast. As pointed
out by Littler [21] a cyclic ester mechanism is forbid-
den in the diol-Cr(VI) reaction. Chromic acid oxida-
tion of pinacol may therefore involve two one-electron
steps. Chromic acid oxidations are known to induce
polymerization of acrylamide under certain conditions
[23]. No such observation has yet been recorded with
PBC. Thus, the capability of chromic acid and the in-
ability of PBC to act as a one-electron oxidant may
explain the different behavior of pinacol towards these
two oxidants.
Thanks are due to the University Grants Commission (India)
and the Council of Scientific and Industrial Research (India)
for financial support.
LEFT Interactive
BIBLIOGRAPHY
1. N. Narayanan and T. R. Balasubramanian, Ind. J.
Chem., 25B, 228 (1986).
2. A. Pareek, S. Kothari and K. K. Banerji, Ind. J. Chem.,
34B, 968 (1995).
3. P. Aparna, S. Kothari and K. K. Banerji, J. Chem. Res.,
(S), 367 (1994); (M) 2123; Proc. Indian Acad. Sci.,
(Chem. Sci.), 107, 213 (1995).
4. A. Grover, S. Varshney and K. K. Banerji, Indian J.
Chem., 33A, 622 (1994).
5. S. Rathore, P. K. Sharma and K. K. Banerji, J. Chem.
Res. (S), 504 (1994).
6. R. Khanchandani, P. K. Sharma and K. K. Banerji, J.
Chem. Res. (S), 432 (1995); (M) 2622.
7. K. K. Banerji, Ind. J. Chem., 22B, 650 (1983).
8. T. J. Kemp and W. A. Waters, Proc. Roy. Soc. Ser. A,
274, 480 (1963).
9. D. D. Perrin, W. L. Armarego, and D. R. Perrin, Puri-
fication of Organic Compounds, Pergamon Press, Ox-
ford, 1966.
10. S. Coffey (ed.), Rodd’s Chemistry of Carbon Com-
pounds, Elsevier, Amsterdam, 2nd Ed., 1965, Vol. I D;
E. H. Rodd (ed.), Chemistry of Carbon Compounds, El-
sevier, Amsterdam, 1951, Vol. I A; J. Buckingham et
al (ed.), Dictionary of Organic Compounds, Chapman
and Hall, New York, V Ed., 1982, Vol., 3; R. C. West,
CRC Handbook of Chemistry and Physics, CRC Press,
Ohio, 58th Ed., 1977–78, Vol. 3.
11. O. Exner. Collect. Chem. Czech. Commun., 29, 1094
(1964).
12. O. Exner. Collect. Chem. Czech. Commun., 31, 3222
(1966).
13. M. J. Kamlet, J. L. M. Abboud, M. H. Abraham, and R.
W. Taft, J. Org. Chem., 48, 2877 (1983).
14. C. G. Swain, M. S. Swain, A. L. Powell, and S. Alumni.
J. Am. Chem. Soc., 105, 502 (1983).
15. K. B. Wiberg, Physical Organic Chemistry, Wiley, New
York, 1963, p. 416.
16. H. Kwart and J. H. Nickel, J. Am. Chem. Soc., 95, 3394
(1973).
17. H. Kwart and M. C. Latimer, J. Am. Chem. Soc., 93,
1971 (3770).
18. H. Kwart and J. Slutsky, J. Chem. Commun., 1182
(1972).
19. F. G. Bordwell, Acc. Chem. Res., 5, 374 (1974).
20. R. W. Woodward and R. Hoffmann, Angew. Chem. Int.
Ed. Eng., 8, 781 (1969).
21. J. S. Littler, Tetrahedron, 27, 81 (1971).
22. A. C. Chatterjee and S. K. Mukherjee, Z. Phys. Chem.,
207, 372 (1957); 208, 281 (1958); 209, 166 (1959).
23. M. Rahman and J. Rocek, J. Am. Chem. Soc., 93, 5462
(1971); F. Hasan and J. Rocek, J. Am. Chem. Soc., 94,
3181 (1972).
short
standard
long