Reaction of Styrene with Chlorine Dioxide

Article abstract of DOI:10.1134/S1070363218040308

Reaction of styrene with chlorine dioxide under various conditions selectively produces 1-phenyl- 2-chloroethanone, with 1-phenyl-2-chloroethanol, 2-hydroxy-1-phenylethanone, (1,2-dichloroethyl)benzene, (2-chloro-1-phenyl)ethene, and (1,2,2-trichloroethyl

Full text of DOI:10.1134/S1070363218040308

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 4, pp. 825–828. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © I.V. Loginova, I.Yu. Chukicheva, A.V. Kuchin, 2018, published in Zhurnal Obshchei Khimii, 2018, Vol. 88, No. 4, pp. 679–682.
LETTERS
TO THE EDITOR
Reaction of Styrene with Chlorine Dioxide
I. V. Loginova*, I. Yu. Chukicheva, and A. V. Kuchin
Institute of Chemistry, Komi Scientific Center, Ural Branch, Russian Academy of Sciences,
ul. Pervomaiskaya 48, Syktyvkar, Komi Republic, 167000 Russia
*
e-mail: loginova-iv@chemi.komisc.ru
Received November 2, 2017
Abstract—Reaction of styrene with chlorine dioxide under various conditions selectively produces 1-phenyl-
-chloroethanone, with 1-phenyl-2-chloroethanol, 2-hydroxy-1-phenylethanone, (1,2-dichloroethyl)benzene,
2-chloro-1-phenyl)ethene, and (1,2,2-trichloroethyl)benzene isolated as reaction byproducts.
2
(
Keywords: 1-phenyl-2-chloroethanone, 1-phenyl-2-chloroethanol, 2-hydroxy-1-phenylethanone, (1,2-dichloro-
ethyl)benzene, (2-chloro-1-phenyl)ethene, (1,2,2-trichloroethyl)benzene
DOI: 10.1134/S1070363218040308
Chloroketones and chlorohydrins are versatile
intermediate products in synthesis of bioactive
compounds [1]. Hydroxyketones are used for the
synthesis of pharmaceuticals and fragrances and also
are employed as fungicides, wood disinfectants,
stabilizers of proteins and polyhydroxy compounds,
reagents in analytical chemistry, etc. [2]. Similar
styrene derivatives also have found extensive
application. Chloroacetophenone is a toxic lacrimator
which is synthesized either by chlorination of
acetophenone or by the reaction of benzene with
chloroacetyl chloride in the presence of anhydrous
aluminum chloride [3]. Styrene chlorohydrin, a
semiproduct in industrial synthesis of a synthomycin,
is obtained by hydroxychlorination of styrene with
calcium hypochlorite or by passing gaseous chlorine
through an emulsion of styrene and water, whereby a
part of styrene is converted to 1-phenyl-1,2-dichloro-
ethane, difficultly separable from chlorohydrin [4].
The formation of 1-phenyl-1,2-dichloroethane can be
avoided by carrying out the reaction of bromobenzene
with anhydrous chloroacetaldehyde in the presence of
magnesium metal, followed by hydrolysis of mag-
nesium bromoalkoxide [5].
sulfoxides [11–13] and quinones [14–16]. There are
examples of using chlorine dioxide for oxidation of
unsaturated compounds, giving a complex mixture of
chlorination products [17, 18]. Chlorine dioxide was
found to epoxidize styrene in aqueous solutions [19].
The monochlorine monoxide thereby formed then
oxidized chlorine dioxide to chlorate and was reduced
to hypochlorous acid. The end products included styrene
oxide resulting from the reaction of hypochlorous acid
with styrene and compounds formed via epoxide ring
opening. Considerable amounts of styrene oxide were
obtained when the oxidation was carried out at pH 6.
Upon adding sulfamic acid the yields of the chlo-
rinated products decreased substantially.
When carrying out the reaction of styrene with
ClO we varied the technique of supplying ClO , the
2
2
styrene-ClO molar ratio (1 : 1, 1 : 2), and the catalyst
2
[
VO(acac) , FIBAN K-1 sulfonic cation-exchange
2
resin, KSF clay]. A ClO -air mixture was bubbled
2
through styrene or a solution of styrene in an organic
solvent (CH Cl or DMF), or, alternatively, a solution
2
2
of ClO in H O or in CH Cl was added dropwise to
2
2
2
2
styrene. The reaction was run at 20°C until complete
conversion of styrene was achieved; the reaction
products were separated by column chromatography.
Here we studied the reaction of styrene with chlorine
dioxide under various conditions. Chlorine dioxide is
used for oxidation of alcohols [6, 7], sulfur-containing
amino acids [8], and thiols and disulfides [9, 10], as
well as for the preparation of variously structured
Our results showed that, under the actual condi-
tions, the reaction of styrene with ClO gave a mixture
2
of compounds, chief among which are chloroketone 1
and chlorohydrin 2 (Scheme 1).
8
25

8
26
LOGINOVA et al.
Scheme 1.
Cl
O
Cl
8
HO
7
1
ClO2
6
5
2
3
+
4
1
2
Cl
H
Cl
OH
Cl
O
Cl
H
H
Cl
H
Cl
Cl
3
4
5
6
The reaction run with the use of an aqueous
occur on its surface. VO(acac) is employed as a
2
solution of ClO at an equimolar ratio of the reactants
catalyst for epoxidation of allyl alcohols [22].
2
gave 1-phenyl-2-chloroethanone 1 in a maximum yield
of 69%, with up to 25% of 1-phenyl-2-chloroethanol 2
and up to 6% of 2-hydroxy-1-phenylethanone 3 formed
as well. As the molar ratio of the reactants increased,
the yield of 1 increased (81%), probably, due to
oxidation of the hydroxy group in 2 to ketone with an
excess of ClO2.
The use of the catalysts tested did not lead to
selective oxidation of styrene; in all cases the amounts
of chlorination products 4 and 5 increased. Also,
(
1,2,2-trichloroethyl)benzene 6 (1%) was isolated from
the reaction catalyzed by VO(acac) , unlike the
2
reaction run under other conditions.
The structures of 1–6 were confirmed by IR and
NMR spectroscopy; the characteristics of the com-
pounds synthesized corresponded to the published data
On changing the solvent from water to CH Cl the
2
2
yield of 1 did not exceed 55%, and that of 2, 5%. The
presence in the reaction mixture of (1,2-dichloroethyl)-
benzene 4 (23%) and of (2-chloro-1-phenyl)ethene 5
[23–27].
(
17%) is explained by the formation of chlorine
(
2-Chloro-1-phenyl)ethene 5 is a mixture of trans-
molecules from ClO decomposition in an aprotic
solvent. Bubbling ClO -air mixture through a solution
of styrene in CH Cl led to a similar set of reaction
products. In a DMF medium styrene was oxidized with
ClO predominantly to 1 with no formation of other
chlorination products. As the consumption of the
oxidant increased the yield of 1 increased to 75%.
Bubbling ClO directly through styrene led to the
2
(
5a) and cis-isomers (5b) which we could not separate
chromatographically. The ratio and yield of the
isomers formed were estimated from the integrated
2
2
2
7
intensities of the signals from methine protons at C
8
1
2
and C atoms in the H NMR spectrum at 6.68 and
.88 ppm for (trans-2-chloro-1-phenyl)ethene 5a and
at 6.33 and 6.73 ppm for (cis-2-chloro-1-phenyl)ethene
b. According to the NMR data, the cis- and trans-
6
2
5
formation of 1–3 in approximately equal amounts (20–
2
isomers were in a 1 : (4–8) ratio.
4%).
1
The H NMR spectrum of (1,2,2-trichloroethyl)-
benzene 6 exhibited signals from protons of two
methine groups appearing as doublets at 5.28 and
.07 ppm, as well as signals from phenyl protons
The catalysts tested in the reaction of styrene with
chlorine dioxide included VO(acac) , FIBAN K-1, and
KSF clay. FIBAN K-1 is a fibrous strongly acidic
cation-exchange resin with SO H functional group,
whose polymer base is formed by polypropylene fiber
with graft styrene-divinylbenzene copolymer. This is
an effective catalyst for olefin isomerization, alcohol
dehydration, and redox reactions [20, 21]. Mont-
morillonite KSF is a solid Lewis acid; H SO may
2
6
(
+
3
multiplet, δ 7.35–7.48 ppm).
Thus, the reaction of styrene with chlorine dioxide
allows selectively producing α-chloroacetophenone by
using an aqueous solution of ClO or by bubbling ClO
through a solution of styrene in DMF.
2
2
2
4
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 4 2018

REACTION OF STYRENE WITH CHLORINE DIOXIDE
827
Oxidation of styrene with chlorine dioxide (general
packed with 10% Carbowax 20M deposited on
Chromaton N-AW-DMCS; carrier gas argon; oven
temperature 50– 230°C at a rate of 6°C/min.
procedure). A mixture of air and ClO (dichloro-
2
methane extract from 263 mL of an aqueous solution,
c = 7–8 g/L) was bubbled through 2.920 g (28.1 mmol)
of styrene or a styrene solution in DMF or CH Cl , or,
Melting points were determined on a Sanyo
Gallenkamp apparatus with a digital thermometer. The
reaction products were separated by column chromato-
graphy (“wet” packing method) on Alfa Aesar 70/230μ
silica gel. Thin-layer chromatography was performed
on Sorbfil plates, with tert-butyl methyl ether as eluent
and 5% potassium permanganate solution as develop-
ing agent.
2
2
alternatively, 280 mL of a ClO solution in H O or in
2
2
CH Cl (c = 7–8 g/L) was added under stirring. The
2
2
reaction was run at 20°C until complete conversion of
styrene was achieved. The course of the reaction was
monitored by TLC on Sorbfil plates (eluent 1 : 1
benzene–petroleum ether). The reaction products were
extracted from the aqueous solution with chloroform
and separated by column chromatography on Alfa
Aesar 70/230μ silica gel (eluent chloroform, benzene-
petroleum ether). In a similar way the reaction was
carried out in the presence of a catalyst or with a ClO2
excess.
Solution of ClO
by extraction of ClO
8 g/L), followed by drying over MgSO
morillonite KSF [Acros Organics, surface area 15±
in dichloromethane was prepared
from an aqueous solution (c = 7–
. Mont-
2
2
4
2
10 m /g; chemical composition: SiO
(54.0%), Al O
2
2 3
(
17.0%), Fe O (5.2%), CaO (1.5%), MgO (2.5%),
2
3
1
-Phenyl-2-chloroethanone 1. Yield 14–69%, color-
Na O (0.4%), K O (1.5%); 8–12% free H SO ] was
–
1
2
2
2
4
less oily liquid. IR spectrum, ν, cm : 1732 (C=O), 692
C–Cl). H NMR, δ, ppm: 4.74 s (2H, C H ), 7.52 t
2H, C H + C H, J = 9.0 Hz), 7.62 t (1H, C H, J = 6.0
Hz), 7.99 d (2H, C H + C H, J = 9.0 Hz).
used without pretreatment. FIBAN K-1 catalyst was
made available by the Institute of Physical Organic
Chemistry, National Academy of Sciences of Belarus.
1
8
(
(
2
3
5
4
2
6
1
-Phenyl-2-chloroethanol 2. Yield 5–25%, light
ACKNOWLEDGMENTS
–
1
yellow oily liquid. IR spectrum, ν, cm : 3448 (O–H),
030 (C–H ), 698 (C–Cl).
3
The research done using the equipment of Center
for Collective Use “Khimiya” of Russian Academy of
Sciences, Ural Branch, Komi Science Centre, Institute
of Chemistry.
ar
2-Hydroxy-1-phenylethanone 3. Yield 6–22%, white
paste-like mass, mp 87°C (mp 88°C [26]). IR spec-
trum, ν, cm : 3433 (O–H), 3030 (C–H ), 1747 (C=O).
–
1
ar
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