1~4

M.S. SAZ,U~HOVet al.

10. G. M. GAL'PERN, V. A. IL'INA, P. M. SHUMSKAYA and V. N. ALEgSANDROV,

Khlmlya i tekhnol, monomerov. Tr. Vses, n.-i. i proektn, in-t. monomerov 2, 129,
1970
11. A. M. IVANOV, L. N. KHAKALO and K. A. ~CHEItVINSKII, Neftel~hlmiya 8, 589,
1968
12. Ye. M. TOCHINA, L. M. POSTNIKOV and V. Ya. SHLYAPINTOKH, Izv. AN SSSR,
Ser. khlm. 71, 1968

OXIDATIVE CHLORINATION OF ETHYLBENZENE

AND ISOPROPYLBENZENE*
M. S. SAT,A~I~[OV,~V~.~~.GUSS]~I~OV,CH. A. CH~,A~IEV and D. K. ABD~LAYEV
Stungait Branch of the Institute of Petrochemical Processes Azerb. S.S.R. Academy of
Sciences
(Received 16 July, 1974)

C ~ o ~ x ~ . derivatives of ethyl and isopropylbenzene are obtained b y alkyiatiou

of chlorobenzene in the presence of Friedel-Crafts [1, 2] catalysts b y direct
chlorination of ethylbenzene [3-5] and isopropylbenzene [6, 7]. A1Cls, FeCIa,
ZnCI~, SnC14 and TiC14 are used as catalysts in chlorination of alkylbenzenes.
However, secondary reactions [5, 7] are undesirable in the catalytic process
of chlorination.
Investigations are being carried out in our laboratory in the field of oxidizing chlorination of alkyl-aromatic hydrocarbons [8]. There is no information
in the literature about this problem.
This article is concerned with explaining some relations which govern
the preparation of chlorine derivatives of ethyl- and isopropy!benzene b y oxidative chlorination (with a mixture o f hydrochloric acid and hydrogen perox i d e ) . .....
Experiments were carried out in a glass flask provided with a mechanical
atirrer, d r o p funnel and a thermometer. Reaction temperature was maintained
with an accuracy of 0 . 5 . Commercial hydrochloric acid, ethyl- and isopr0pylbenzene (pure) and a 30% aqueous solution of hydrogen peroxide were
used: for the investigation. The flask was filled with these in given proportions.
Hydrogen peroxide was added to the reaction mass from a drop funnel.
~ The react:ion mixture was analysed a t equal time intervals b y GLC using
an LKhM-7A device with a heat conductivity detector (detector current 90 mA).
* Neftekhlrnlya 15, No. 4, 601-605, 1975.

chlorination of e~hylbenzene

Oxidative

, 1~

Before chromatographic analysis the samples were washed o neutral reaction

a n d dried over calcium chloride. Chromatographic curves were obtained using
II~Z-600 brick modified with PEG-4000 at a carrier gas (nitrogen) velocity
of 60 ml/min. The length of the column was 3 m, analytical temperature 150.
Under these conditions the separation of products of the reaction mixture
is ensured. The peaks were assigned by comparing the retention times of individual compounds and those obtained. Results of chromatographic analysis
and IR spectra of products synthesized show that o-, 10-ehloroethyl- and o-,
ID-chloro-isopropylbenzenes are formed during the reaction.
%
/6

-I,

2oP ll

)
I

X /

100 ZOO

300
r'pm

tJ

10"c,he

400

500

Fze. 1. Effect of the intensity of agitation of the reaction mass on the yield (1-6) and
rate (7) of oxych]orination of ethy]benzene. Temperature 200, intensity of agitation,
rpm: 1--0; 2--100, 3--200; 4--300; 6--400; 6--600.

To find optimum conditions for oxychlorination, the.effects of the intensity

of stirring the reaction mass, the concentration of hydrochloric acid, hydrogen
peroxide feed rate, t h e molar ratio of reacting substances and temperature
on the yield of chlorine derivatives of ethyl- and isopropylbenzene were
examined.
RESULTS

In the initial stage of the experiment we determined the reaction range.

Since initial a~omatic hydrocarbons (and chloroalkylaromatic compounds)
do, not dissolve in hydrochloric acid it was assumed that reaction rate might
b e a~ected by difl~usion factors. In fact, results of experiments (Fig/ I ) s h o w
that the intensity of sirring the reaction mixture has a marked effect on the
field of monochloroethylbenzene and the rate of oxyehlorination.::: ThUs,
without agitation (curve 1, Fig. 1) t h e m a x i m u m yield Of ehloroethylbenzene

'!156

M.S.

SAT.A~OV ~ a/.

does not exceed 18%, while an increase in the intensity of agitation to 400
rev/min (curve 5) increases yield to 91/o. A further increase of agitation
intensity to 600 rev/min has no effect on the yield of chlo~oethylbenzene.
To obtain comparable results by a di~erential method, initial reaction rates
were calculated at dii~erent intensities of agitation.
A marked increase in reaction rate in the interval of 200-400 rev/min
(Fig. 1, curve 7), apparently, points to a transition of the reaction from the
diffusion (<200 rev/mi'n) into the kinetic range (>400 rev/min).
Oxychlorination of aromatic hydrocarbons consists of two step-by-step
reactions: interaction of hydrogen peroxide with hydl'ogen chloride takes
place in the first stage to form chlorine
2HCI~-H20= -+ CI~-2tt20,

(1)

in the second stage of the process the chlorine separated reacts with hydroca2o
bon by the system

(2)

CI,+ ~ - R - - ~ - R + H C I
C1

Consequently, the yield and rate of chlorine formation depend on the

concentration of hydrochloric acid.

%
100~
54

////
3

5
T, h r

Ill/~
7

~o. 2

"c~ hr
Fzo. 3

F I o . 2. Effect of t h e concentration of hydroohloric acid on the yield of ehloroethyl.

benzene. Temperature 20C, intensity of agitation 400 rev/rnln~ (~0]~jCt]~l : H t O a ~ 1 : 1.
Concentration o f hydrochloric acid, % wt.: 1--12; 2--10; 3--20; 4--20; 5--30.
FIG. 3. Effect of t h e feed rate of hydrogen peroxide on the yield of ohloroethylbenzene.
C+H,C~H, : HCI : H = O , ~ 1 : 6 : 1; feed r~te: 1 - - simultaueotm Rllln~; 2--30; 3--15; 4 - - 1 0

g/hr.

157,

Oxidative chlorination of ethylbenzene

Results of Fig. 2 indicate t h a t the yield of ehloroethylbenzene and t h e

rate of its formation depend on the concentration of hydrochloric acid and the
reaction does not take place in practice if acid concentration is lower t h a n
12~o. An increase in He1 concentration to 36% increases the yield of chloroethylbenzene to 91% in 2 hr.
Oxidative chlorination of aromatic hydrocarbons depends both on reaction
(1) and reaction (2). I f the rate of reaction (2) is equal to, or considerably higher
than, the rate of reaction (1) the separation of free chlorine m a y be excluded.
I t was established t h a t without aromatic compounds reaction (1) takes place
at a high rate and it m a y be adjusted b y the rate of hydrogen peroxide supply.
Consequently, it was essential to select conditions under which the chlorine
separated in the first stage fully reacted with aromatic hydrocarbons. Results
in Fig. 3 indicate t h a t a feed rate of hydrogen peroxide of 10 g/hr is optimum;
at this rate a 98-99~/o yield of chloroethylbenzene is ensured in terms of t h e
hydrogen peroxide taken. The Figure shows that with the simultaneous supply
of all reacting substances the rate of oxidative chlorination is higher t h a n
with the gradual feed of Hz0~, b u t the yield of chlorine derivatives is only
790/0, i.e. part of chlorine is not used up in the reaction.
T A B L E 1. E F F E C T OF ~:J~JS A M O U N T OF H Y D R O G E N C H L O R I D E ON T~lJ~ ~2"J[ELD OF CHLORO"~.~t"Y'L- A N D CHLOROISOPROP~irLBENZ]ENE8

Temperature 20C; molar ratio of alkylbenzene : H,O~----1 : 1

HC1,
mole
1
2
4
6
8
10

C,HsC,H,C1
overall I o-I p28
57
85
91
91
91

17
35
52
55
i 55
56

11
22
33
36
36
35

Yield, %
CsH~C6H,C1
C~IIC,HsC1,
veraU I " I P"
0
2
4
7
7.5
8

23
51
7O
80
81
82

11 112
25
26
34.5 35.5
39.5 40.5
40 i 41
40"5 I 41.5

CsH,CeH,CI~

2.5
5
8
11
11

The effect of the amount of hydrochloric acid in the initial mixture on

the yield of chloroalkylbenzenes is shown in Table 1. Investigations were
carried out at an intensity of agitation of the reaction mixture of 400-450
rev/min and a rate of hydrogen peroxide feed of 10 g/hr. An increase in t h e
molar concentration of hydrochloric acid from 1 to 6 moles pet mole hydrogen
peroxide increases the yields of monochloroethylbenzene and monochlorois0propylbenzene from 28 to 91% and from 23 to 80%, respectively.
The relatively low yield of monochloro-isopropylbenzene, particularly
o-isomers is probably due to the sterie effect of the isopropyl radical (Tables
1 and 2). A further increase in the content of hydrochloric acid increases tho

1~. S. SAT.Alg'Frovet a~=

158

formation of dicMoroderivatives of aromatic compounds, the yields of which

v a r y between 8 and 11 ~ .
A study of the effect of temperature on the yields of chloroaromatic hydrocarbons in the temperature range of 0-40 at a rate of hydrogen peroxide feed
of 10 g/hr (Fig. 4a, b) indicates that an increase in temperature accelerates
oxychlorination of ethyl- and isopropylbenzenes. The time to achieve a maxim u m yield of the intermediate product at 40 decreases from 9 to 3 hr, this
yield, however, is lower than at 0 . This dependence of the yield of ehloroethylbenzene on temperature is due to the. acceleration of subsequent chlorination
of t h e chloroethylbenzene formed to dichloroethylbenzenes. In fact, it follows
from curves 2'-5' (Fig. 4a) that with an increase of temperature from 10 to
40 , diehloroethylbenzene yield varies between 4 and 18~o and at 0 the latter
is not formed at all. Consequently, to achieve selective oxychlorination,
the process should be carried out at low temperature (20 and lower) or at
high temperatures with a duration of up to 3 hr.
a/a /

100

r,hr

FIG. 4. Dependence of the yields of chloroaromatic hydrocarbons on reaction t i m e :

a - - chloroethyl (1-5) and dichloroethylbenzene (2'-5"); b -- chloroisopropyl (1-4) and
dichloroisopropyl benzene (1'-4'). Molar ratio of C6HsAI HC1 : H=O----1 : 6 : 1; tempera
ture, C: 1--0; 2, 2'--10; 3, 3'--20; 4, 4'--30; 5, 5'--40.
Similar results were obtained for oxychlorination of isopropylbenzene (Fig.
4b). In this case with an increase of temperature the yield of monochloroisopropylbenzene decreases and the content of dichloroisopropylbenzene increases.
Results in Fig. 4 indicate that the formation of dichloroderivatives of
ethyl- and isopropylbenzenes begins after a 4 5 ~ conversion of initial alkylaromatic compounds. Therefore, in order to increase process selectivity,
a s t u d y was made of the effect of molar quantitites of ethyl- and isopropylbenzenes in the reaction mixture (Table 2).

Oxidative chlorination of ethylbenzene

159

I t was f o u n d t h a t w i t h a n e q u i m o l e c u l a r r a t i o of a r o m a t i c h y d r o c a r b o n s
a n d h y d r o g e n p e r o x i d e u p to 7-8~/o d i c h l o r o d e r i v a t i v e s are f o r m e d .
T~BLE 2. EFFECT OF ~ ' ~ M O ~
' ~

YIELD

OF

PROPORTION OF ETJ~t~Jb-ANDISOPROPYI,BEN~ENES ON
MONO-

AND

DICH~LOROA_I.~YI,BENZENES

Temperature 20C hydroperoxide feed rate 10 g/hr; molar ratio of H C I : H I O s

=6:1
CIHsC,H~C1
Alkylbenzene,
overall
opmole
1
2
4
6
8
10

91

55

36

93
95
96
96
97

57
58
58
58
59

37
37
38
38
38

CaHTCeH,C1
I C,H6C,HaC1.

overall

o-

p-

80
94
95
96
97
97

39.5
46-5
47
47.5
48
48

40"5
47"5
48
48"5
49
49

CsHTC,HaCII

On increasing t h e m o l a r r a t i o o f a l k y l b e n e z e n e : h y d r o g e n p e r o x i d e t o
10 : 1, t h e c o n t e n t s o f d i c h l o r o - d e r i v a t i v e s decreases to 1.0~/o a n d t h e yield
o f m o n o c h l o r o - a l k y l b e n z e n e s increases to 97.0%.
SUMMARY

l. A s t u d y was m a d e of o x y c h l o r i n a t i o n of e t h y l - a n d i s o p r o p y l b e n z e n e
w i t h a m i x t u r e of h y d r o g e n p e r o x i d e a n d h y d r o c h l o r i c acid. I t was s h o w n
t h a t w i t h v i g o r o u s s t i r r i n g (over 400 r e v / m i n ) t h e r e a c t i o n t a k e s p l a c e in t h o
k i n e t i c range.
2. On using 36~/o h y d r o c h l o r i c acid a n d a m o l a r r a t i o o f A r : HCI : H 2 0 a
of 1:1:1,
yields o f c h l o r e t h y l - a n d c h l o r i s o p r o p y l b e n z e n e s are 28 a n d 23
a n d w i t h a r a t i o o f 1 : 6 : 1 t h e y increase to 91 a n d 80~/o, r e s p e c t i v e l y . A n
increase in t h e c o n c e n t r a t i o n of t h e a r o m a t i c c o m p o u n d to 10 m o l e results
in t h e f o r m a t i o n of ortho- a n d para-isomers.
REFERENCES

1.
2.
3.
4.
5.
6.
7.
8.

Yu. G. MAMEDALIYEV and Sh. V. VEIAYEV, Dokl. AN SSSR 92, 325, 1953 ~
M. B. TUROVA-POLYAK and M. A. MASLOVA, Zh. obshch, khimii 27, 897, 1957
S. N. USHAKOV and P. A. MATUZOV, Zh. obshch, khimii 14, 120, 1944
Yu. G. MAMEDALIYEV, M. M. GUSEINOV, D. Ye. MISHIYEV, R. S. AT.E~IARDANOV
and P. A. PETROSYAN, Azerb. khim. zh. No. 4, 9, 1962
Yu. S. KROPANEV, V. G. PLYUSNIN, N. I. PLOTKINA and L. P. UL'YANOVA,
Neftckl~imlya 9, 591, 1969
Yu. G. MAMEDALIYEV, Izbrannyye proizvcdcniya (Selected Works), Izd. AN Azerb.
SSR 1, 1964
Yu. S. KROPANEV, V. G. PLYUSNIN and P. I. PLOTKINA, Ncftebhimiya 7, 398,
1967
Auth. Cert. U.S.S.R. 386891, 18. 10. 1972. Otkr. isobr., prom. obr. i toy. znaki, No. 27,
59, 1973