Organic Process Research & Development 2006, 10, 876−880
Full Papers
Epoxidation of Allyl Chloride to Epichlorohydrin by a Reversible Supported
Catalyst with H2O2 under Solvent-Free Conditions
Jun Li, Gongda Zhao, Shuang Gao,* Ying Lv, Jian Li, and Zuwei Xi*
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, People’s
Republic of China
Abstract:
years, many researchers2-14 have shown interest in the
epoxidation of olefins with hydrogen peroxide. Epoxidation
of olefins is an electrophilic reaction; the strong electron-
withdrawing effect of chloride atoms in allyl chloride
molecules makes it more difficult to epoxidize than non-
functional terminal olefins. Only a few examples of epoxi-
dation of allyl chloride have been reported so far.
The epoxidation of allyl chloride by TS-1 zeolite with
H2O2 was reported by Clerici group and Gao.15,16 The
reaction was carried out at 45 °C for 30 min in the presence
of methanol solvent. The selectivity for epichlorohydrin is
92% based on H2O2, and the conversion of H2O2 is 98%.15
Presently, this method has not yet been commercialized.
Venturello and co-workers had reported a homogeneous
catalytic system for allyl chloride epoxidation with [(C8H17)3-
NCH3]3[PO4[W(O)(O2)2]4] catalyst and aqueous H2O2.17,18
The reaction mixture was refluxed for 2.5 h in the benzene/
water biphasic system to give epichlorohydrin in the yield
of 85%. Sun et al. had tried to epoxidize allyl chloride with
H2O2 generated in situ through an anthraquinone route and
[π-C5H5NC16H33]3[PW4O16] catalyst in toluene and tributyl
phosphate mixed solvents at 75 °C for 1.5 h to give
epichlorohydrin in the yield of 80.5%.19 Not only do
heterogeneous catalytic systems need a large amount of
solvents, but also the homogeneous catalytic systems men-
Allyl chloride was epoxidized to epichlorohydrin with H2O2
under solvent-free conditions in 94% selectivity using a new
reversible supported catalyst, heteropolyphosphatotungstate/
silanized silica gel. By the action of H2O2 the heteropolyphos-
phatotungstate dissolves from the carrier surface and forms
an active homogeneous reagent. When all H2O2 is consumed,
the reduced catalyst redeposits on the support carrier. The
supported catalyst retains the character of a homogeneous
catalyst during reaction but exhibits heterogeneous properties
upon work-up. The solid-supported catalyst is easily isolated
and can be reused. The reaction system for synthesis of
epichlorohydrin therefore avoids the serious pollution issues
known from the commercialized chlorohydrin methods. Some
other olefins can also be epoxidized by this catalytic system
under neat conditions.
Introduction
Epichlorohydrin is an important petrochemical used in
the manufacture of epoxy resins, synthetic glycerol, etc. Its
worldwide production capacity in 2003 was around 1.24
million tons, and there is continual increase in market
demand. The industrial methods for the production of
epichlorohydrin are the chlorohydrin method and the allyl
alcohol method.1 Both methods use Ca(OH)2 and produce
CaCl2 as a by-product. The chlorohydrin method entails
serious environmental pollution issues. The allyl alcohol
method imposes fewer threats to the environment, but the
process is more complicated, thus leading to higher invest-
ment costs. More than 90% of epichlorohydrin in the world
is still manufactured today using the chlorohydrin method.
Owing to environmental concerns in recent years, there is a
strong need for the development of an environmentally
friendly process for the production of epichlorohydrin. Direct
epoxidation of allyl chloride with hydrogen peroxide is an
ideal method.
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Hydrogen peroxide is a relatively cheap, environmental
friendly oxidant with an atom efficiency of 47%. In recent
* Corresponding authors. Telephone: 86-411-84379248. Fax: 86-411-
84379248. E-mail: (Z.X.) zwxi@dicp.ac.cn; (S.G.) sgao@dicp.ac.cn.
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Vol. 10, No. 5, 2006 / Organic Process Research & Development
10.1021/op060108k CCC: $33.50 © 2006 American Chemical Society
Published on Web 07/18/2006