PREPARATION OF CHLOROTOLUENE BY OXIDIZING

CHLORINATION OF TOLUENE*

M. S. SALAKHOV,M. M. GUSEII~OV,CH. A. CHALABIYEVand D. K. ABDULLAYEV

Sumgait Branch of the Yu. G. Mamedaliyev Institute of Petrochemical
Processes
(Received 13 February 1973)

WE HAVE previously shown [1] t h a t it is possible to obtain alkyl monoehloro-

benzenes by oxychlorination of benzene and its homologues, using a mixture
of hydrochloric acid and hydrogen peroxide as a source of oxygen. The possi-
bility of using commercial hydrochloric acid and perhydrol of different con-
centrations enables us to use this reaction as an effective process for obtaining
mono-, di- and polychloro-derivatives of aromatic hydrocarbons which are of
considerable national economic significance [2].
I t is of interest to prepare chlorotoluene by oxy-ehlorination of toluene.
Existing methods of preparing this compound by vapour phase chlorination
[2] and oxy-ehlorination [3] of toluene do not ensure process selectivity. I t was
shown [3] t h a t in high temperature oxy-ehlorination of toluene using copper
chloride with the mixture of hydrogen chloride, substitution takes place both
in the side chain and in the nucleus. I t becomes necessary therefore to sepa-
rate chlorotoluenes from products of chlorination in the side chain. On the
other hand, high temperature oxy-chlorination of hydrocarbons requires special
catalysts to maintain activity during the reaction.
The development of a more selective method of preparing alkylchloroben-
zenes without catalysts remains an important problem. It appears to us t h a t
selective oxy-ehlorination of toluene to chlorotoluenes (with a chlorine atom
in the nucleus) is a satisfactory preparatory method for the synthesis of these
compounds and m a y subsequently form the basis of an industrial process;
1) the method does not depend greatly on purity and concentration of hydro-
chloric acid and hydrogen peroxide; 2) the reaction takes place at room tem-
perature without catalyst; 3) high selectivity of chlorination on the nucleus
is ensured.
This paper describes results of investigating oxy-ehlorination of toluene
using hydrochloric acid (36%) and hydrogen peroxide (30%) and examines
the effect of process parameters on intermediate product yield.

* ~qeftekhimiya 14, No. 3, 471-474, 1974.

113
114 M.S. SALAKHOVet al.
EXPERIMENTAL
Calculated amounts of hydrochloric acid and toluene are placed in a three-
necked flask provided with a mechanical stirrer, thermometer and drop funnel
followed by a dropwise addition of a 30% aqueous solution of hydrogen per-
oxide at a given temperature. The reaction was controlled by measuring the
amount of chlorotoluene forme(l with an LKhM-TA chromatograph.

a c

J
I I I L- L ~ 1 I I I I
5"5 3"5 1.5 0 30 25 20 15 700 800 ern "~
Yield time, rain Y/eM time, rain

FIG. 1. Chromatographic c u r v e s (a, b) a~td IR spectrum (c) of reaction products of oxy-

chlorination of toluene, a: 1 - - o - and p-chlorotoluenes; 2. 3---dichlorotoluenes; b: 1--
o-chlorotoluene; 2--p-chlorotoluene.

PEG-4000 on INZ-600 brick was used as adsorbent, carrier-gas (nitrogen)

velocity being 60 ml/min, column length 3 m, and column temperature 150 °.
Under these conditions chlorotoluenes were separated (overall) from toluene
and dichlorotoluenes (Fig. 1¢~). After the reaction the hydrocarbon layer was
separated from the aqueous layer, neutralized with weak soda solution, dried
with calcium chloride and rectified. The isomer composition of the chloro-
toluene fraction (159-161°; u~ 1.5249; d~° 1.0732) was established chroma-
tographically (Fig. lb) using as adsorbent, carbon black graphitized by heat,
column length being 2 m, temperature 150 + and carrier-ainu (nitrogen) velocity
60 ml/min. Analysis of this fraction indicated that it consists of a 63.4 : 36.6°/i)
mixture of o- and p-ehlorotoluenes. The peaks were identified by comparing
individual samples. Absorption bands were tbund in the I g spectrum of this
sample (Fig. lc) in the region of 746 and 806 cm ~, typical of o and p-disubsti-
tuted benzene, respectively [4].
To find optimum conditions for preparing ehlorotoluenes, a study was made
of the effect of temperature and molar proportions of reacting components on
reaction product yield. The effect of variation of the molar proportion of hyd-
 Preparation of chlorotoluene 115

rochloric acid on the yield o f mono- and dichlorotoluenes was e x a m i n e d using

a n .equimoleeular p r o p o r t i o n of toluene a n d h y d r o g e n peroxide. E x p e r i m e n t a l
results are shown in Fig. 2. An increase in the molecular q u a n t i t y o f h y d r o -
chloric acid f r o m 1 to 6 (Fig. 2, curve 1) increases the yield of chlorotoluenes

%
% I. log - !

2
3
5q
80 2 '~ 80

qO ~.
~0

gO
5!
4'
J'
121 lq! 181 181 1101
C7 H8: HCt : H~O2 , rno/e:mo/e: mole 1 3 5 7 thp

FIG. 2 Fie. 3
Fie. 2. Relationship between the yield of ehlorotoluene (1) and dichloroto]uone (2)
and the molar quantity of hydrogen chloride. Temperature 20°; reaction time 5 hr; rate
of passing hydrogen peroxide 10 g/hr.
FIe. 3. Relationship between the yield of mono- (1-5) and diehlorotoluenes (2"-5") and
reaction time at different temperatures: C ~ H s : H C I : H , O = = I : 6 : I , rate of passing
hydrogen peroxide 10 g/hr; temperature °C: 1--0; 2, 2'--10; 3, 3'--20; 4, 4'--30; 5, 5"--40.

f r o m 30 to 88% a n d a f u r t h e r increase in the p r o p o r t i o n of hydrochloric acid

h a r d l y affects yield. I t follows from the diagram t h a t to p r e p a r e monochloro-
toluene with a high yield, a molar ratio of reacting components,
C7Hs : HC1 : H202-~ 1 : 6 : 1 and a t e m p e r a t u r e of 20 ° are required for t h e
reaction.
I t should be n o t e d t h a t dichlorotoluene is also f o r m e d (Fig. 2, curve 2), t h e
c o n t e n t of which, according to the a m o u n t of hydrochloric acid, varies b e t w e e n
0 a n d 8~/o, resulting from f u r t h e r chlorination o f the chlorotoluene formed.
To s t u d y process selectivity, the effect of the molecular c o n c e n t r a t i o n o f
toluene ranging f r o m 1 to 10 mole on m o n o c h l o r o t o h i e n e yield was studied.
Results o f these e x p e r i m e n t s are shown in Table 1. W i t h a n increase in toluene
c o n c e n t r a t i o n from 1 to 10 mole, chlorotoluene yield increases f r o m 88.0 to
98~/o a n d the contents o f dichloro-derivatives decreases f r o m 8 to 0.7%,
respectively.
A s t u d y was s u b s e q u e n t l y m a d e of the effect o f t e m p e r a t u r e on the r a t e of
f o r m a t i o n a n d the yield of chlorotoluenes. I t follows f r o m Fig. 3 t h a t an in-
 116 M . S . SALAKHOV et al.

crease in temperature from 0 to 40 ° accelerates oxy-chlorination. A t high

temperatures, however, e.g. at 40 ° the yield of chlorotoluene is lower t h a n at
0% In addition, the a m o u n t of dichlorotoluene at 40 ° reaches 18% while at 0 °
it is hardly formed at all which confirms t h a t oxy-chlorination of toluenes
is accelerated at high temperatures (Table 2).

TABLE 1. E F F E C T OF T H E M O L A R R A T I O OF R E A C T I N G C O M P O N E N T S
ON T H E Y I E L I ) OF MOkNO- A N D D I C H L O R O T O L U E N E ~

Temperature 20°; reaction time 9 hr; rate of passing hydrogen

peroxide 10 g/hr

Yield, mole (~,

Molar ratio of
of monochloro- of diehloro-
CTHs : HC1 : H:O2
toluenes tohlene

1:6:1 88.0 12.0

2:6:1 94-5 4.5
4:6:I 95.7 2.6
6:6:1 96.4 1-7
8:6:1 97.0 1.3
10:6:1 98-0 0.7

It should be noted that process s e l e c t i v i t y is a f f e c t e d b y t h e d u r a t i o n o f

oxy-chlorination. As shown by Fig. 3, a t 40 ° t h e y i e l d o f m o n o c h l o r o t o l u e n e s
reaches 90% in 3 hr, while further continuation of the reaction reduces the
yield to 80% with a corresponding increase in dichlorotoluene content from
7 to 1 8 o

TABLE 2. EFFECT OF TEMPERATURE ON THE Y1ELI)

OF Me:NO- AND DICHLOROTOLUENES
C v H s : H C I : H , O , ~ I : 6 : 1; duration 9 hr; rate of
passing hydrogen peroxide: 10 g/hr

Yield, mole o/~

Temperaturo, °C of monochlo- of dichh)ro-
rotoluenes toluene

0 95.0 0.5
10 91.5 8.0
20 87-5 12.0
30 84.0 15.0
40 80.0 18.0

Investigations thus indicate that in low temperature liquid-phase oxy-chlori-

n a t i o n t h e p r o c e s s o f c h l o r i n a t i o n o f t o l u e n e s u n d e r o p t i m u m c o n d i t i o n s is
s e l e c t i v e a n d m a x i m u m y i e l d o f c h l o r o t o l u e n e s ( 9 8 % in t e r m s o f h y d r o g e n
p e r o x i d e ) is e n s u r e d .
 Preparation of chlorotoluene 117

SUMMARY
1. A s t u d y was m a d e o f oxidizing chlorination o f toluene in h y d r o c h l o r i c
acid w i t h h y d r o g e n p e r o x i d e as t h e source of o x y g e n . T h e chlorotoluenes ob-
t a i n e d c o n t a i n o- a n d T-isomers.
2. An increase o f t h e m o l a r p r o p o r t i o n o f h y d r o c h l o r i c acid f r o m 1 to 6 a t a
t e m p e r a t u r e of 20 ° increases chlorotoluene yield f r o m 30 to 92~/o.
3. A r e d u c t i o n o f t e m p e r a t u r e f r o m 40 to 0 ° reduces the yield o f dichloro-
toluenes to 0.5%, which results in a selective process w i t h t h e f o r m a t i o n of
chlorotoluene.

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No. 27, 1973
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(Principles of Synthesis of Intermediate Products and Dyes). Goskhhnizdat, Moscow,
1950
3. A. B. SOLOMONOV, P. P. (~ERTSEN and A. K. KETOV, Zh. prikl, khimii, 1~o. 6, 1418,
1969
4. A. BELLAMI, Infrakrasnye spektry slozhnykh molekul (IR Spectra of Complex
Molecules). Izd. inostr, lit., Moscow, 1963