Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 4, pp. 661−665.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.E. Meshechkina, L.V. Mel’nik, G.V. Rybina, S.S. Srednev, A.S. Shevchuk, 2012, published in Zhurnal Prikladnoi Khimii, 2012,
Vol. 85, No. 4, pp. 646−650.
AND INDUSTRIAL ORGANIC CHEMISTRY
Efﬁ ciency of Phase-Transfer Catalysis in Cyclopentene
Epoxidation with Hydrogen Peroxide
A. E. Meshechkina, L. V. Mel’nik, G. V. Rybina, S. S. Srednev, and A. S. Shevchuk
Yaroslavl State Technical University, Yaroslavl, Russia
Received October 4, 2011
Abstract—The effect of the structure and amount of the phase-transfer catalyst (quaternary ammonium salts) and
the solvent effect on cyclopentene oxidation with an aqueous hydrogen peroxide solution in the liquid–liquid two-
phase system was studied. The phase-transfer catalyst and solvent ensuring high reaction rate and high selectivity
with respect to target products were chosen.
Today there is increasing interest in use of aque-
ous solutions of hydrogen peroxide instead of organic
hydroperoxides and per acids as agents for oxidation of
unsaturated compounds [1, 2], because 30% hydrogen
peroxide solution is readily available, cheap, stable in
transportation, and environmentally safe; furthermore,
hydrogen peroxide has high relative content of available
oxygen. These advantages make hydorgen peroxide
promising as agent for various processes.
Analysis of procedures for preparing 1,2-epoxy-
cyclopentane by oxidation of cyclopentene (CP) with
isopropylbenzene hydroperoxide and aqueous solution of
hydrogen peroxide (HP), made in , revealed technical
and economical advantages of hydrogen peroxide.
Processes used for oxidation of unsaturated substrates
with aqueous hydrogen peroxide solutions can be con-
ventionally classed with respect to implementation, in ac-
cordance with the catalysts used. The ﬁ rst group includes
oxidation processes performed on heterogeneous catalysts
(titanium silicalite, zeolites), with alcohols, mainly meth-
anol, used as solvent [3, 4]. The second group includes
oxidation processes performed with soluble catalysts,
compounds of Group V and VI metals (W, Mo, V) .
Among them, particular place is occupied by reactions
performed in two-phase water–organic solvent systems.
The catalytic complex is formed directly in the reac-
tion medium from sodium tungstate, phosphoric acid,
hydrogen peroxide, and phase-transfer catalyst (PTC).
Depending on the reaction temperature and pH of the
aqueous phase, the process can be directed to synthesis
of either 1,2-epoxycyclopentane (1,2-ECP) or 1,2-cyclo-
pentanediol (1,2-CD) .
In this study we examined how the structure and
amount of PTC and the nature of the solvent affect the
efﬁ ciency of oxygen (peroxy group) transfer from the
aqueous phase to the organic phase in which cyclopentene
Cyclopentene isolated from the С
fraction of pyroly-
sis was puriﬁ ed by fractional distillation to 98% purity.
The solvents (chemically or analytically pure grade) were
additionally puriﬁ ed by fractional distillation. Hydrogen
peroxide (35% aqueous solution), sodium tungstate dihy-
drate, phosphoric acid (80%), and phase-transfer catalysts
(Table 1) of chemically or analytically pure grade were
used without any pretreatment.
A temperature-controlled glass reactor equipped
with a reﬂ ux condenser, a thermometer, and a sampling
neck was charged with the aqueous (sodium tungstate,
phosphoric acid, hydrogen peroxide, water) and organic
(phase-transfer catalyst, solvent, cyclopentene) phases,
prepared in advance separately. The mixture was vigor-