Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 2, pp. 236−242.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © Kh.M. Alimardanov, O.A. Sadygov, N.I. Garibov, M.F. Abbasov, M.Ya. Abdullaeva, N.A. Dzhafarova, 2011, published in Zhurnal
Prikladnoi Khimii, 2011, Vol. 84, No. 2, pp. 240−246.
AND INDUSTRIAL ORGANIC CHEMISTRY
Liquid-Phase Catalytic Oxidation of C
into Carboxylic Acids in a Pseudohomogeneous System
Kh. M. Alimardanov, O. A. Sadygov, N. I. Garibov, M. F. Abbasov,
M. Ya. Abdullaeva, and N. A. Dzhafarova
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received April 16, 2010
Abstract—Liquid-phase oxidation of cyclohexene, methylcyclohexene isomers, and norbornene with a 30%
solution of hydrogen peroxide in a pseudohomogeneous system involving highly dispersed compounds of Group-
VIb and -VIIIb metals supported by nanosize carbon particles was studied.
Dicarboxylic acids are important monomers in
manufacture of synthetic ﬁ bers and plastics and also are
of interest as intermediates in syntheses of biologically
active compounds and pharmacological preparations
. These compounds are produced by oxidation
of unsaturated hydrocarbons and their functional
derivatives with various oxidizing agents, such as ozone
, potassium permanganate, manganese dioxide,
ruthenium dioxide (in combination with NaHlgO
where Hlg = Cl, Br), potassium persulfate, organic
hydroperoxides, peroxy acids [3–6], and nitric acid .
At present, dicarboxylic acids and, in particular, adipic
acid are industrially manufactured by the two-stage
scheme: oxidation of cyclohexane with atmospheric
oxygen into cyclohexanol and cyclohexanone, followed
by treatment of the resulting mixture with nitric
acid . This process yields, together with the main
product, also mono- and dicarboxylic acids (acetic,
oxalic, glutaric, and succinic) . In addition, use of
nitric acid as oxidizing agent results in that toxic gases,
nitrogen oxides, are evolved, which is ecologically and
There has been report in the literature that dicarboxylic
acids were produced by oxidation of cycloalkanes with
molecular oxygen in the presence of isoamyl nitrite
[10, 11]. The main reaction product at temperatures T ≤
120°C is a mixture of the corresponding cycloalkanol,
cycloalkanone, and dicarboxylic acid.
Oxidation of cyclohexene with hydrogen peroxide,
with compounds of bisquaternary ammonium and
sodium tungstate involved, gives, depending on reaction
conditions, cyclohexanone in 82% yield or adipic acid
It has been found that cyclohexene is oxidized by
hydrogen peroxide into adipic acid in the presence of
Ti-substituted aluminophosphate molecular sieves
(TAPO-5) without any organic solvent via stages in
which 1,2-cyclohexanediol is formed and the process
selectivity is determined by the speciﬁ c structural
feature of the intermediate .
It has also been suggested to oxidize cyclohexene
and cyclooctene into hexane-1,6- and octane-1,8-
dioic acids with peroxopolyoxo tungsten phosphate
complexes combined with quaternary ammonium
cations . A higher yield of adipic acid (89%) is
reached in oxidation of cyclohexene with 30% H
the presence of an oxodiperoxo tungsten complex and
a nitrogen-containing heterocycle . Cyclopentene
and cyclohexene can also be oxidized into, respectively,
glutaric and adipic acids in the presence of 50% H
peroxo complexes of tungsten [16, 17], H
 involved and oxalic, orthophosphoric,
and boric acids used as a complexing agent.