Organic Process Research & Development 2004, 8, 879−882
Synthesis of Methyl Phenyl Glyoxylate via Clean Oxidation of Methyl Mandelate
over a Nanocatalyst Based on Heteropolyacid Supported on Clay
Ganapati D. Yadav* and Ramesh D. Bhagat
Department of Chemical Engineering, UniVersity Institute of Chemical Technology, UniVersity of Mumbai,
Matunga, Mumbai-400 019 India
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Abstract:
sulphonamide, 1-chlorobenzotriazole, N-bromosaccharin,
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12
Oxidation is an important class of reaction from both industrial
and academic points of view. In recent years, a large number
of oxidizing agents have been used for a variety of industrial
reactions, but many of them are polluting, giving poor yields.
Mandelates have played an important role in organic synthesis
and are used in artificial flavoring and perfumes. Methyl phenyl
glyoxylate, which contains two carbonyl groups, is an important
intermediate used in fine chemical industry. Oxidation of methyl
mandelate was carried out to prepare methyl phenyl glyoxylate,
with 85% selectivity, by using hydrogen peroxide in the
bromate, and N-bromophthalimide. In the past few years,
the oxidation of R-hydroxyl compounds has been reported
by using catalytic amounts of chromium oxide in conjunction
with tert-butylhydroperoxide
Oxidation is also reported with the catalytic amounts of
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3,14
14,15
or hydrogen peroxide.
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3
VOCl in acetonitrile under an oxygen atmosphere. Phenyl
glyoxylic acid esters were prepared by treating a Grignard
reagent phenylmagnesium bromide with diethyl oxalate.16
Oxidation of phenylacetylene derivatives can also be utilized
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for the synthesis of R-keto ester. Methyl phenylglyoxylate
presence of a novel catalyst, namely, 20% w/w Cs2.5
H
0.5PW12
O
40
/
was synthesized via ozonolysis of 1-bromophenylacetylene
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K-10 catalyst, which is partly substituted dodecatungstophos-
phoric acid supported on clay. The catalyst is a nano material
and reusable. The workup is easy.
followed by reaction with potassium iodide, whereas the
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oxidation was improved by treatment of trimethylsilyl
phenylacetylenes with osmium tetroxide and tert-butyl hy-
droperoxide in methanol to get methyl phenyl glyoxylate. It
is also reported that ammonium chlorochromate adsorbed
on alumina was used for the preparation of phenyl glyoxylic
Introduction
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esters. The use of heterogeneous catalysts with a clean
oxidizing agent is necessary for the synthesis of methyl
phenyl glyoxylate, and this work is concerned with that
aspect.
Carbonyl compounds are a prominent class in synthetic
organic chemistry having several applications as solvents and
precursors to several products such as alcohols, acids, and
heterocyclic compounds.1 Methyl phenyl glyoxylate, which
contains two carbonyl groups, is an important intermediate
used in fine chemical industry. R-Dicarbonyl compounds are
obtained by the oxidation of R-hydroxylcarbonyl precursors.
Due to the sensitivity of the R-dicarbonyl compounds, special
reagents and reaction conditions are required to prevent side
-3
Heteropolyacids are a very important class of acid and
redox catalysts. The novelty of clay-supported heteropoly-
acids as reusable benign catalysts was reported by us20 for
the first time, and a series of commercially important
21-27
reactions were studied.
We have also developed a novel
nanocatalyst by using partially substituted dodecatungsto-
phosphoric acid (DTP) with cesium and supporting it on acid-
1
reactions during the oxidation of R-hydroxycarbonyls.
Although a number of methods have been developed to
achieve this transformation, most of them suffer from the
use of corrosive acids or toxic metallic compounds that
generate undesirable waste materials. There are several
methods available in the literature on the oxidation of
R-hydroxyl compounds by oxidizing agents such as N-
activated clay. Thus, nanoparticles of 20% w/w Cs2.5
0.5
H -
PW12O40 were created in the pore network of acid treated
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bromosuccinimide, N-bromoacetamide, trichloroisocyanuric
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acid, N-bromobenzene sulphonamide, N-chlorobenzene
*
To whom correspondence should be addressed. E-mail: gdyadav@yahoo.com,
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gdyadav@udct.org. Telefax: 91-22-2410-2121. Fax: 91-22-2414-5614.
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(
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0.1021/op049858p CCC: $27.50 © 2004 American Chemical Society
Vol. 8, No. 6, 2004 / Organic Process Research & Development
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Published on Web 10/28/2004