ISSN 0965-5441, Petroleum Chemistry, 2007, Vol. 47, No. 3, pp. 225. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © A.V. Anisimov, A.V. Tarakanova, Fam Vin Tkhai, I.S. Kulikov, A.A. Seleznev, 2007, published in Neftekhimiya, 2007, Vol. 47, No. 3, p. 246.
SHORT COMMUNICATION
Oxidation of Organic Sulfur Compounds with Hydrogen
Peroxide in the Presence of Crown Ethers
A. V. Anisimov, A. V. Tarakanova, Fat Vin Tkhai, I. S. Kulikov, and A. A. Seleznev
Faculty of Chemistry, Moscow State University, Moscow, 199992 Russia
e-mail: anis@petrol.chem.msu.ru
Received, November 24, 2006
Abstract—-It was first shown that crown ethers catalyze the oxidation of organic sulfur compounds (methyl
phenyl sulfide to sulfoxide and sulfone, benzothiophene and dibenzothiophene to sulfones) with hydrogen per-
oxide.
DOI: 10.1134/S0965544107030127
Oxidation of sulfides to sulfoxides and sulfones are dant system is also confirmed by the conversion of ben-
important reactions in organic chemistry [1–3]. These zothiophene and dibenzothiophene, whose oxidation
reactions are used to manufacture selective extractants, presents significant difficulties during the oxidative
surfactants, pharmaceuticals, and other valuable prod- desulfurization of hydrocarbon fractions. The oxidation
ucts [4]. In addition, the sulfide oxidation reaction is of benzothiophene in the presence of dibenzo-18-
used in the oxidative desulfurization of hydrocarbon crown-6 for 18 h gave benzothiophene sulfone with a
feedstock [5]. Reported in the literature are several quantitative yield, and the yield of the corresponding
examples of the β-cyclodextrin-catalyzed oxidation of sulfone from dibenzothiophene was 11%.
alkyl aryl sulfides to corresponding sulfoxides and sul-
fones [6, 7]; however, there is no evidence for the par- for Basic Research, project no. 06-03-32367.
ticipation of macrocycles with a smaller size in these
reactions. We report that the oxidation of some organic
sulfur compounds, such as methyl phenyl sulfide, ben-
zothiophene, and dibenzothiophene, with hydrogen
peroxide is feasible in the presence of the two macrocy-
clic ethers benzo-18-crown-6 and dibenzo-18-crown-6.
This work was supported by the Russian Foundation
REFERENCES
1. Ji Hong-Bing, Hu Xiao-Fang, Shi Dong-Po, and
Li Zhong, Zh. Org. Khim. 42, 979 (2006).
2
3
. M. T. Reetz, F. Daligault, B. Brunner, et al., Angew.
Chem., Int. Ed. Engl. 43, 4078 (2004).
. J. Legros and C. Bolm, Angew. Chem., Int. Ed. Engl. 43,
4225 (2004).
4. M. C. Carreno, Chem. Rev. 95, 1717 (1995).
. F. M. Collins, A. R. Lucy, and C. Sharp, J. Mol. Catal., A
117, 397 (1997).
. H. Sakuraba, K. Natori, andY. Tanaka, J. Org. Chem. 56,
4124 (1991).
. D. M. Davies and M. E. Deary, J. Chem. Soc., Perkin
Trans. 2, 2423 (1996).
The reactions were conducted by heating a mixture
of a sulfur compound with 37% hydrogen peroxide in
ethanol at 45°C. At a reaction time of 8 h, the methyl
phenyl sulfide conversion in the presence of both crown
ethers was 100%, and the oxidation products were
methyl phenyl sulfoxide and methyl phenyl sulfone
with amounts in the reaction mixtures of 52 and 48%
for benzo-18-crown-6 and 30 and 70% for dibenzo-18-
crown-6, respectively. The high efficiency of this oxi-
5
6
7
2
25
Anisimov
