The kinetics and mechanism of the reaction between l-chloro-2,3-epoxypropane and p-cresol in the presence of basic catalysts

Article abstract of DOI:10.1002/(SICI)1097-4601(1997)29:1<73::AID-KIN9>3.0.CO;2-I

Rate constants for the reaction of 1-chloro-2,3-epoxypropane with p-cresol in the presence of basic catalysts were studied at the temperature range of 71 - 100°C. It was found that in the presence of sodium p-cresolate, three consecutive reactions pro-ceeded giving the following products: l-chloro-3-(tolyloxy)-2-propanol (CTP), l-(p-tolyloxy)-2,3-epoxypropane (TEP) as a main product, and l, 3-di(p-tolyloxy)-2-propanol (DTP). Their rate constants at 71°C were: k₁ = 0.030 ± 0.009, k₂ = 1.58 ± 0.02, and k₃ = 0.033 ± 0.005 dm³/mol -min, respectively. In the presence of quaternary ammonium salts, this process consisted of 5 reactions which led to CTP as a main product as well as TEP and l, 3-dichloro-2-propanol (DCP). The rate constant of CTP formation at 71°C was established, k₁ = 0.130 ± 0.030 dm³/mol·min, as were the ratios of the other rate constants k₂/k_-4 = 1-5 ± 0.2. k₅/k₄ = 20.0 ± 5.0, and k₄/k₁, = 0.6 ± 0.7. Based on the changes in Cl^- ion concentration during the reaction, the cata-lystic activity of quaternary ammonium salts was explained. The kinetic model of these reactions in the presence of basic catalysts has been proposed and appropriate kinetic equations have been presented.

Full text of DOI:10.1002/(SICI)1097-4601(1997)29:1<73::AID-KIN9>3.0.CO;2-I

The Kinetics and
Mechanism of the Reaction
between 1-Chloro-2,3-
Epoxypropane and p-Cresol
in the Presence of Basic
Catalysts
JAN CHLEBICKI,1 LARISA YU. SHIMAN,2 ANDREY K. GUSKOV,2 MIKHAIL G. MAKAROV,2
VALERIJ F. SHVETS2
1 Institute of Organic and Polymer Technology, Technical University of Wroclaw, 50-370 Wroclaw, Poland
2 Mendeleev Institute of Chemical Technology, 125190 Moscow A-190, Russia
Received 5 January 1996; accepted 22 May 1996
ABSTRACT: Rate constants for the reaction of 1-chloro-2,3-epoxypropane with p-cresol in the
presence of basic catalysts were studied at the temperature range of 71–100°C.
It was found that in the presence of sodium p-cresolate, three consecutive reactions pro-
ceeded giving the following products: 1-chloro-3-(tolyloxy)-2-propanol (CTP), 1-( p-tolyloxy)-
2,3-epoxypropane (TEP) as a main product, and 1,3-di(p-tolyloxy)-2-propanol (DTP). Their
rate constants at 71°C were: k1 ϭ 0.030 Ϯ 0.009, k2 ϭ 1.58 Ϯ 0.02, and k3 ϭ 0.033 Ϯ 0.005
dm3/molиmin, respectively.
In the presence of quaternary ammonium salts, this process consisted of 5 reactions
which led to CTP as a main product as well as TEP and 1,3-dichloro-2-propanol (DCP). The
rate constant of CTP formation at 71°C was established, k1 ϭ 0.130 Ϯ 0.030 dm3/molиmin, as
were the ratios of the other rate constants k2 /kϪ4 ϭ 1.5 Ϯ 0.2, k5 /k4 ϭ 20.0 Ϯ 5.0, and k4 /k1
ϭ 0.6 Ϯ 0.7. Based on the changes in ClϪ ion concentration during the reaction, the cata-
lystic activity of quaternary ammonium salts was explained.
The kinetic model of these reactions in the presence of basic catalysts has been proposed
and appropriate kinetic equations have been presented. © 1997 John Wiley & Sons, Inc. Int J Chem
Kinet 29: 73–79, 1997.
INTRODUCTION
cidyl ethers which are important intermediate prod-
ucts in manufacturing antielectrostatic agents, emulsi-
fiers, solubilizators, and detergents.
A great deal of articles being published are de-
voted to the reaction of epichlorohydrin with alco-
hols, which in its first stage proceeds in the presence
of such acidic catalysts as: H2SO4 [1], HClO4 [2],
BF3 [3], and SnCl4 [4]. In the second stage, the inter-
The reaction of 1-chloro-2,3-epoxypropane (epi-
chlorohydrin) with phenols or alcohols leads to gly-
Correspondence to: J. Chlebicki
© 1997 John Wiley & Sons, Inc.
CCC 0538-8066/97/010073-07

74
CHLEBICKI ET AL.
mediate chlorohydrin is dehydrochlorinated by means
of Na2CO3 or NaOH solution. The synthesis of gly-
cidyl ethers formed as a result of catalytic reaction of
phase transfer using soda and a quaternary ammo-
nium salt is also presented [5]. Recently, a new sin-
gle-stage method of synthesizing those compounds in
the presence of heterogeneous catalysts of solid/liq-
uid type in alkaline solution was published [6].
The kinetics of the first stage of the reaction of al-
cohols with epichlorohydrin was examined in the
presence of BF3 catalyst and a remarkable excess of
alcohol [7]. It became evident that the reaction rate
was proportional to the concentration of both
epichlorohydrin and the catalyst. Similar relation-
ships were obtained for s-butanol and C2 9C5 ␣,
␻-diols [8].
The kinetics of the reaction of epichlorohydrin
with substituted phenols was examined in the pres-
ence of quaternary ammonium salts dissolved in
chlorobenzene [9]. The examination proved that the
effect of substituents in the aromatic ring on the reac-
tion rate can be described by a complex kinetic equa-
tion. The kinetics of the reaction of phenol, 2-naph-
tol, and hydroquinone with epichlorohydrin was also
investigated in the presence of triethylamine [10]. It
has been stated that under these conditions 1-chloro-
2-hydroxypropyl ethers of the phenols being exam-
ined are formed, and the reaction is of the first-order
in those reagents.
temperature programmable in the range from 50 to
250°C).
The basic series of measurements was carried out
at the temperature of 71°C and the following concen-
trations of reagents (in mol/dm3 ): p-cresol–7.8–8.5;
epichlorohydrin–0.910–Ϫ 1.830;
and
catalyst
(sodium p-cresolate)–0.550–1.200 or p-cresol–
7.8–8.5; epichlorohydrin–0.470–1.900; and catalyst
(quaternary ammonium salt)–0.047–0.164.
The concentration of ClϪ ions in a reaction mix-
ture was determined using the Volhard method [11].
Reagents
p-Cresol (POCh, Gliwice) and epichlorohydrin
(Fluka AG, Switzerland) were purified by means of
distillation in a Vigreux column containing a pack-
ing material. p-Cresolate added as a catalyst was
obtained by dissolving metallic sodium in p-cresol
immediately before the reaction. The quaternary am-
monium salts used as catalysts were as follows:
benzylhexadecyldimethylammonium chloride, ben-
zyldodecyldimethylammonium chloride, benzyldode-
cyldimethylammonium bromide, and benzylhexyl-
dimethylammonium chloride analytically pure (Fluka
AG, Switzerland).
Products
The aim of the article was to determine the rate
constants of the aryl glycidyl ether formation and to
propose the mechanism of those reactions. The reac-
tion of p-cresol with epichlorohydrin in the presence
of sodium p-cresolate or quaternary ammonium salts
as catalysts was a model kinetic reaction.
Individual compounds were isolated from the reac-
tion mixture using fractional distillation or prepara-
tive gas chromatography. Their chemical structure
was confirmed by elemental analysis (C, H, and Cl)
and infrared spectrums.
1-Chloro-3-(p-tolyloxy)-2-propanol (CTP): b.p. ϭ
140°C/12 mm Hg, nD20 ϭ 1.5380; anal.: calc.: C,
58.11; H, 9.20; Cl, 19.22; found: C, 58.05; H, 9.17;
Cl, 19.30%.
EXPERIMENTAL
1-( p-tolyloxy)-2,3-epoxypropane (TEP): b.p. ϭ
117°C/15 mm Hg, nD20 ϭ 1.4829; anal.: calc.: C,
81.08; H, 7.30; found: C, 81.00; H, 7.21%.
1,3-di(p-tolyloxy)-2-propanol (DTP): anal.: calc.:
C, 84.95; H, 8.39; found: C, 84.86; H, 8.34%.
1,3-Dichloro-2-propanol (DCP): b.p. ϭ 174°C,
nD20 ϭ 1.4830; anal.: calc.: C, 28.12; H, 4.68; Cl,
54.69; found: C, 27.96; H, 4.73; Cl, 54.85%.
Apparatus and Procedure
The kinetics of the reaction was measured in a glass
reactor which was thermostatically controlled and
equipped with a thermometer, a stirrer, and a reflux
condenser closed up by means of a tube filled with a
drier and a tube for sample collecting. The tempera-
ture of reaction was kept constant with an accuracy of
Ϯ 0.2°C. The samples were collected using a mi-
cropipette and subjected to chromatographic analysis
(glc). Chromatographic analyses were carried out us-
ing Giede GCHF-18.3.4 chromatograph equipped
RESULTS AND DISCUSSION
with
a
flame-ionization detector (the column
length–Ϫ1 m, stationary phase–15% Silicon XE 60
on a Chromosorb W 60/80 mesh, and carrier gas–N2 ,
In this article, we continue our earlier investigations
of the kinetics and mechanism governing the reaction

1-CHLORO-2,3-EPOXYPROPANE AND p-CRESOL REACTION
75
k1
CH3C6H4OH ϩ CH29CHCH2Cl
O
CH3C6H4OCH2CHCH2Cl, (1)
OH
k2
CH3C6H4OCH2CHCH2Cl ϩ CH3C6H4OϪ
OH
CH3C6H4OCH2CH9CH2
O
ϩ CH3C6H4OH ϩ ClϪ, (2)
k3
ϩ CH3C6H4OH
CH3C6H4OCH2CH9CH2
O
Figure 1 Variations of epichlorohydrin concentration (C)
during the reaction with p-cresol at 71°C. Catalyst–sodium
p-cresolate: 1–1.200; 2–0.880; 3–0.760; and 4–0.650
mol/dm3.
(CH3C6H4OCH2)2CHOH. (3)
We did not take into account one more possible reac-
tion of a direct chlorine substitution in epichlorohy-
drin because the rate of this reaction is very low when
compared to those of the above reactions. We found
earlier that the rate of a direct chlorine substitution in
epichlorohydrin as a result of basic hydrolysis was by
two orders lower than the rate of the opening of the
epoxide ring [16].
In the series of consecutive reactions, the product
composition is determined by the ratio of the rate
constants of all elementary reactions. Reaction (1) is
the most important since it determines the rate of the
process. It is the reaction of nucleophilic p-cresol ad-
of oxiranes with the compounds with active hydrogen
ions, i.e., phenols [12], alcohols [13], and alkylothiols
[14]. It is commonly known that in those reactions
the normal or abnormal opening of the epoxide ring
can occur, depending on the kind of catalyst used. In
the case of epichlorohydrin, we always deal with the
normal opening of epoxide ring, therefore only one
type of adducts is formed, independently of the cata-
lyst applied [15].
The first part of the article is devoted to the kinet-
ics of the reaction of p-cresol with epichlorohydrin in
the presence of sodium p-cresolate catalyst. The reac-
tion products obtained were as follows: 1-chloro-3-
( p-tolyloxy)-2-propanol (CTP), 1-(p-tolyloxy)-2,3-
epoxypropane (TEP), and 1,3-di(p-tolyloxy)-2-
propanol (DTP). The concentrations of these com-
pounds increased over 60 min, which corresponded to
a 60–70% conversion of epichlorohydrin.
The kinetics data is presented in Figure 1. The
changes are represented by a straight line which
proves that the reaction is of the first-order in
epichlorohydrin. Based on data from the literature we
could have expected that for sodium p-cresolate this
reaction would also be of the first-order. It should be
stressed, however, that the dependence of the initial
reaction rate on the catalyst concentration is not lin-
ear (see Fig. 2) which proves that the reaction is
rather complex.
The process, which proceeds in the presence of
p-cresolate catalyst, can be schematically presented
in the form of the following consecutive reactions:
Figure 2 Effect of catalyst concentration upon the initial
rate constant (r0 ) of epichlorohydrin reaction with p-cresol
at 71°C.

76
CHLEBICKI ET AL.
dition to the epoxide ring. This reaction probably
proceeds according to a two-stage mechanism. In
the first stage, the oxygen atom in epichlorohydrin
undergoes protonation and a bimolecular complex
with a p-cresol molecule is formed. In the second
stage, a carbon atom in the ring with a partial posi-
tive charge is subjected to nucleophilic attack. Thus,
the opening of the epoxide ring and formation of a
CTP product occur in consequence of the simultane-
ous action of the proton donor and the nucleophilic
reagent. The rate of this reaction can be expressed as
follows:
where
k3 ϭ kЉ[CH3C6H4OH].
Investigation of the process kinetics allowed us to
collect data which is indispensable in calculating the
rate constants of the three consecutive reactions. The
calculations were done using the least-square method.
The values of the reaction rate constants are the
following:
k1 ϭ 0.030 Ϯ 0.009 dm3/molиmin,
k1 /k2 ϭ 0.019 Ϯ 0.002,
r1 ϭ k1 [Epi] [CH3C6H4OϪ ]
k3 ϭ 0.033 Ϯ 0.005 dm3/molиmin,
n ϭ 2.10 Ϯ 0.01
where
The results obtained prove that the proposed kinetic
model allowing satisfactory description of experi-
mental data is correct. The curves calculated on the
basis of the kinetic model and experimental points are
presented in Figure 3. The rate of reaction (1) has a
decisive influence on the rate of the whole process.
This rate is by ca. two orders lower than the rate con-
stant k2 ϭ 1.58 dm3/molиmin.
The second part of the article is devoted to the ki-
netics of the reaction of p-cresol with epichlorohydrin
in the presence of quaternary ammonium salt as a cat-
alyst. The composition of the products of reaction
proceeding in the presence of that catalyst differs sig-
nificantly from those described earlier.
k1 ϭ kЈ[CH3C6H4OH].
Also the second reaction of aryl glycidyl ether (TEP)
formation probably proceeds in two intermediate
stages. In the first slow stage, the CTP molecule ex-
changes its proton with a p-cresolate ion which re-
sults in the formation of a free p-cresol molecule and
a respective anion. In the second rapid stage, a TEP
ether is formed and a chlorine anion is released. The
rate of this reaction is considerably affected by the al-
kalinity of the medium. Numerous researchers re-
ported that in the reactions of dehydrochlorination or
isomerization, they had observed a substantial in-
crease in the initial rate of the reaction with the in-
crease in the base concentration [17,18].
In our investigations, we also observed a similar
effect of sodium p-cresolate concentration on the re-
action rate. Probably for that reason, the dependence
of the initial reaction rate on p-cresolate concentra-
tion, determined on the basis of the degree of
epichlorohydrin conversion, is not linear (see Fig. 2).
The rate of reaction (2) can be expressed by the fol-
lowing equation:
r2 ϭ k2 [CTP] [CH3C6H4OϪ ]n.
The reaction (3) of diether (DTP) formation probably
proceeds according to the mechanism of nucleophilic
addition of the p-cresolate anion to aryl glycidyl ether
(TEP) and a subsequent rapid transition of a proton
from p-cresol to a complex molecule and the repro-
duction of the p-cresolate anion.
The rate of reaction (3) may be presented as
follows:
Figure 3 Computation of kinetic curves and experimental
points of the reaction in the presence of sodium p-cresolate:
1–epichlorohydrin; 2–1-( p-tolyloxy)-2,3-epoxypropane;
and 3–1-chloro-3-(tolyloxy)-2-propanol.
r3 ϭ k3 [TEP] [CH3C6H4OϪ ]

1-CHLORO-2,3-EPOXYPROPANE AND p-CRESOL REACTION
77
In the products, we found ether (CTP), aryl gly-
cidyl ether (TEP), and 1,3-dichloro-2-propanol
(DCP). Therefore, except reactions (1) and (2) pre-
sented earlier, we can propose other elementary reac-
tions proceeding in the presence of quaternary ammo-
nium salt:
In order to establish the reaction order in epi-
chlorohydrin and the catalyst, we conducted a series
of experiments in which their initial concentrations
were changed. We found that under these conditions
the reaction was also of the first-order in both epi-
chlorohydrin and quaternary ammonium salt which
was confirmed by a straight line in Figure 5.
The system of four differential equations was pro-
posed to describe mathematically the experimental
data. They are as follows:
k4
CH3C6H4OH ϩ CH29CHCH2Cl ϩ ClϪ
kϪ4
O
ClCH2CHCH2Cl ϩ CH3C6H4OϪ, (4)
d[Epi]
OH
ϭ Ϫ k1 [Epi] [CH3C6H4OϪ]
k5
dt
Ϫ k4 [Epi] ([Kat] Ϫ [CH3C6H4OϪ]) ϩ
ϩ ClϪ
CH3C6H4OCH2CH9CH2
ϩ kϪ4 [Epi] [CH3C6H4OϪ]n,
O
CH3C6H4OCH2CHCH2Cl ϩ CH3C6H4OϪ. (5)
d[CTP]
ϭ k1 [Epi] [CH3C6H4OϪ]
dt
ϩ k5 [CTP] ([Kat] Ϫ [CH3C6H4OϪ]) Ϫ
OH
Ϫ k2 [CTP] [CH3C6H4OϪ]n,
Reactions (4) and (5) are the reactions of nucleophilic
addition of ClϪ ion to epichlorohydrin or aryl gly-
cidyl ether; moreover, reaction (5) is the opposite of
reaction (2). In the presence of sodium p-cresolate,
however, reaction (5) cannot proceed because ClϪ an-
ion reacts with Naϩ cation to give sodium chloride
which is insoluble in the reaction mixture and precip-
itates. During kinetic measurements the quantitative
composition of the products was also determined
chromatographically. During the course of the reac-
tion, the concentration of ClϪ ions varied. This con-
centration was determined according to the Volhard
method using AgNO3 solution. The changes in the
ClϪ ion concentrations at two catalyst concentrations
are depicted in Figure 4.
d[TEP]
ϭ k2 [CTP] [CH3C6H4OϪ]n
dt
Ϫ k5 [TEP] ([Kat] Ϫ [CH3C6H4OϪ]),
d[DCP]
ϭ k4 [Epi] ([Kat] Ϫ [CH3C6H4OϪ])
dt
Ϫ kϪ4 [DCP] [CH3C6H4OϪ],
where
[Kat] ϭ [CH3C6H4OϪ] ϩ [ClϪ].
Also the ratios of the reaction-rate constants calcu-
lated earlier were applied to the solution of the above
system of differential equations. The calculations
were also done by means of the least-square method.
The following results were obtained: the rate constant
Figure 5 Variation of epichlorohydrin concentration (C)
during the reaction with p-cresol at 71°C in the presence of
[C16H33Nϩ(CH3 )2CH2C6H5 ]ClϪ as catalyst.
Figure 4 Variation of chloride ion concentration (C) dur-
ing the reaction of epichlorohydrin with p-cresol in the
presence of quaternary ammonium salts.

78
CHLEBICKI ET AL.
ably [14]. The values of analogous rate constants
determined for the reaction of n-hexyl alcohol with
methyloxirane at the temperature of 80°C and in
the presence of various tertiary amine catalysts
were as follows: for triethylamine–0.384, for tri-
propylamine–0.126, for tributylamine–0.138, and
for dimethylcyclohexylamine–1.050 dm3/molиmin
[19]. In the case of the reaction of p-cresol with epi-
chlorohydrin at the temperature of 80.5°C, the con-
stant k1 equals 0.303 dm3/molиmin. The ratio of the
rate constants k4 /k1 , which for the reaction of nucle-
ophilic addition is equal to 0.63, may also be ex-
plained by the lower nucleophilicity of the ClϪ ion
compared to the CH3C6H4OϪ ion (EN(Cl ) ϭ 1.21,
Ϫ
EN(CH
) ϭ 1.46). The ratio k5 /k4 of the rate
Ϫ
H O
C
3
6
constants 4is also dependent on the ratio of nucle-
ophilicity of anions bonded to the epoxide ring; in
this case, however, we deal with the reactions of vari-
ous epoxide compounds catalyzed by ClϪ ions.
Figure 6 Computation of kinetic curves and experimental
points of the reaction in the presence of quaternary ammo-
nium salt: 1–epichlorohydrin; 2–1-chloro-3-(p-tolyloxy)-
2-propanol; 3–1,3-dichloro-2-propanol; and 4–1-(p-toly-
loxy)-2,3-epoxypropane.
As we mentioned earlier, protonation of the oxy-
gen atom in the epoxide ring plays an important part
in nucleophilic addition of a proton to oxiranes. The
higher the concentration of oxirane subjected to pro-
tonation, the greater the reaction rate. Therefore those
substituents, which cause an increase in the value of
the partial negative charge, facilitate protonation and
thus make the reaction rate faster. The correctness of
the rate constants calculated can be verified on the
k1 ϭ 0.130 Ϯ 0.030 dm3/molиmin and the ratios of
the other rate constants k2 /kϪ4 ϭ 1.5 Ϯ 0.2, k5 /k4 ϭ
20 Ϯ 5.0 and k4 /k1 ϭ 0.63 Ϯ 0.07.
x
grounds of Taft’s constants (␴ x). The value of ␴ for
ClϪ ion is 2.92, and for the p-cresolate ion the value
The calculations obtained prove that the kinetic
model proposed is correct; it also describes satisfac-
torily the data produced experimentally. In Figure 6,
the curves calculated according to the kinetic model
proposed and the experimental points are shown.
The value of the constant k1 for the reaction pro-
ceeding in the presence of quaternary ammonium salt
is more than four times higher than the value of that
constant for the reaction carried out in the presence of
sodium p-cresolate. The rise in the value of the con-
stant k1 can be explained by the increase in nucle-
ophilicity of p-cresolate anion in the presence of qua-
ternary ammonium salt. Similar phenomena were
observed earlier when the radius of a cation of the
catalyst used in experiments increased notice-
was calculated from the equation ␴ x ϭ 6.2 ␴ which
I
represents the characteristics of the inductive effect of
a substituent in the p-position in the phenyl ring and
is equal to Ϫ 0.496 [20].
The kinetic measurements conducted at various
temperatures allowed the activation parameters to be
determined from the Arrhenius equation. The results
obtained are presented in Table I. Moreover, the ki-
netic data obtained at various temperatures and
processed similarly as previously described enabled
us to state that the ratio of the rate constants of all el-
ementary reactions did not change. Such a statement
leads to the conclusion that reaction selectivity is not
dependent on temperature.
Table I Rate Constant of p-Cresol Reaction with Epichlorohydrin in the Presence of
[C16H33Nϩ(CH3 )2CH2C6H5 ]ClϪ as Catalyst
Temperature
°C
k1
ln A
dm3/mol min
E
dm3/mol min
kJ/mol
80.5
91.5
100.0
0.303 Ϯ 0.007
0.700 Ϯ 0.010
1.100 Ϯ 0.080
25.74 Ϯ 1.39
84.6 Ϯ 1.98

1-CHLORO-2,3-EPOXYPROPANE AND p-CRESOL REACTION
79
Table II Rate Constant of p-Cresol Reaction with
Epichlorohydrin in the Presence of Various Quaternary
Ammonium Salts at 71°C
tion of reaction products, therefore they may be use-
ful in the formulation of a mathematical model.
k1
dm3/mol min
BIBLIOGRAPHY
Catalyst
[C6H13Nϩ(CH3 )2CH2C6H5 ]ClϪ
[C12H25Nϩ(CH3 )2CH2C6H5 ]ClϪ
[C12H25Nϩ(CH3 )2CH2C6H5 ]BrϪ
[C16H33Nϩ(CH3 )2CH2C6H5 ]ClϪ
0.084 Ϯ 0.002
0.113 Ϯ 0.010
0.132 Ϯ 0.015
0.130 Ϯ 0.020
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9. Yu. O. Golubok, K. A. Vyunov, and O. A. Podzolkova,
Zh. Org. Khim., 15, 2106 (1979).
The influence of various ammonium salts on ele-
mentary reaction–rate constants was also investi-
gated. The values of the constant k1 shown in Table II
prove that they are only in a very small degree depen-
dent on the lengths of alkyl groups and ammonium
salt anion. In this case, the ratios of rate constants of
the other elementary reactions were constant.
10. A. V. Ragimov, B. A. Mamedov, Ch. O. Istailova,
M. A. Seiidov, and S. Sh. Verdieva, Kinet. Katal., 26,
75 (1985).
CONCLUSION
11. W. J. Williams, Handbook of Anion Determination,
Butterworth and Co., Ltd., London, 1979.
12. V. F. Shvets and V. V. Lebedev, Kinet. Katal., 6, 782
(1965).
13. J. Chlebicki, Rocz. Chem. Ann. Soc. Chim. Pol., 49,
925 (1975).
The kinetic investigations proved that epichlorohy-
drin reacts with p-cresol in the presence of sodium
p-cresolate to give glycide monoether TEP as the
main product because the rate of its formation is by
ca. 50 times greater than the rate of CTP formation.
Therefore, the rate of the whole process is limited by
the rate of CTP formation.
14. J. Chlebicki and Z. Cichacz, Inter. J. Chem. Kinet., 20,
387 (1988).
Quaternary ammonium salt used as a catalyst al-
lows us to obtain CTP as a main product since it is
formed in two reactions ((2) and (5)). Both reactions
follow the mechanism of nucleophilic addition of ei-
ther p-cresolate ion to epichlorohydrin or ClϪ ion to
aryl glycidyl ether TEP. The changes of ClϪ ion con-
centrations in the course of reaction enabled explana-
tion of catalytic activity of quaternary ammonium
salts.
15. H. Kwart and A. L. Goodman, J. Am. Chem. Soc., 82,
1947 (1960).
16. L. V. Aleksanyan and V. F. Shvets, Arm. Khim. Zh., 25,
986 (1972).
17. L. V. Istomin, N. N. Lebedev, E. B. Sokolova, M. P.
Shebanova, and M. V. Korotkova, Osnov. Organ. Sintez
i Neftekhimiya, Yaroslavl, 17, 32 (1983).
18. M. Halpern, Y. Sasson, and M. Rabinovitz, J. Org.
Chem., 48, 1022 (1983).
19. J. Chlebicki, Scientific Papers of Institute of Organic
and Polymer Technology, Wroclaw Technical Univ.,
No. 21, 1975.
The kinetic models proposed in the form of the
system of differential equations satisfactorily describe
the process, i.e., qualitative and quantitative composi-
20. R. W. Taft, J. Am. Chem. Soc., 79, 1045 (1953).