225 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. Oxidation of sulfides to sulfoxides and sulfones are important reactions in organic chemistry [1–3]. These reactions are used to manufacture selective extractants, surfactants, pharmaceuticals, and other valuable products [4]. In addition, the sulfide oxidation reaction is used in the oxidative desulfurization of hydrocarbon feedstock [5]. Reported in the literature are several examples of the β-cyclodextrin-catalyzed oxidation of alkyl aryl sulfides to corresponding sulfoxides and sulfones [6, 7]; however, there is no evidence for the par- 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, benzothiophene, 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. 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- dant system is also confirmed by the conversion of benzothiophene and dibenzothiophene, whose oxidation presents significant difficulties during the oxidative desulfurization of hydrocarbon fractions. The oxidation of benzothiophene in the presence of dibenzo-18- crown-6 for 18 h gave benzothiophene sulfone with a quantitative yield, and the yield of the corresponding sulfone from dibenzothiophene was 11%. This work was supported by the Russian Foundation for Basic Research, project no. 06-03-32367. REFERENCES 1. Ji Hong-Bing, Hu Xiao-Fang, Shi Dong-Po, and Li Zhong, Zh. Org. Khim. 42, 979 (2006). 2. M. T. Reetz, F. Daligault, B. Brunner, et al., Angew. Chem., Int. Ed. Engl. 43, 4078 (2004). 3. J. Legros and C. Bolm, Angew. Chem., Int. Ed. Engl. 43, 4225 (2004). 4. M. C. Carreno, Chem. Rev. 95, 1717 (1995). 5. F. M. Collins, A. R. Lucy, and C. Sharp, J. Mol. Catal., A 117, 397 (1997). 6. H. Sakuraba, K. Natori, and Y. Tanaka, J. Org. Chem. 56, 4124 (1991). 7. D. M. Davies and M. E. Deary, J. Chem. Soc., Perkin Trans. 2, 2423 (1996). 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: [email protected] 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 peroxide. DOI: 10.1134/S0965544107030127 SHORT COMMUNICATION

Oxidation of organic sulfur compounds with hydrogen peroxide in the presence of crown ethers

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Page 1: Oxidation of organic sulfur compounds with hydrogen peroxide in the presence of crown ethers

225

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.

Oxidation of sulfides to sulfoxides and sulfones areimportant reactions in organic chemistry [1–3]. Thesereactions are used to manufacture selective extractants,surfactants, pharmaceuticals, and other valuable prod-ucts [4]. In addition, the sulfide oxidation reaction isused in the oxidative desulfurization of hydrocarbonfeedstock [5]. Reported in the literature are severalexamples of the

-cyclodextrin-catalyzed oxidation ofalkyl aryl sulfides to corresponding sulfoxides and sul-fones [6, 7]; however, there is no evidence for the par-ticipation of macrocycles with a smaller size in thesereactions. We report that the oxidation of some organicsulfur compounds, such as methyl phenyl sulfide, ben-zothiophene, and dibenzothiophene, with hydrogenperoxide is feasible in the presence of the two macrocy-clic ethers benzo-18-crown-6 and dibenzo-18-crown-6.

The reactions were conducted by heating a mixtureof a sulfur compound with 37% hydrogen peroxide inethanol at

45°

C. At a reaction time of 8 h, the methylphenyl sulfide conversion in the presence of both crownethers was 100%, and the oxidation products weremethyl phenyl sulfoxide and methyl phenyl sulfonewith 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-

dant system is also confirmed by the conversion of ben-zothiophene and dibenzothiophene, whose oxidationpresents significant difficulties during the oxidativedesulfurization of hydrocarbon fractions. The oxidationof benzothiophene in the presence of dibenzo-18-crown-6 for 18 h gave benzothiophene sulfone with aquantitative yield, and the yield of the correspondingsulfone from dibenzothiophene was 11%.

This work was supported by the Russian Foundationfor Basic Research, project no. 06-03-32367.

REFERENCES

1. Ji Hong-Bing, Hu Xiao-Fang, Shi Dong-Po, andLi Zhong,

Zh. Org. Khim.

, 979 (2006).2. M. T. Reetz, F. Daligault, B. Brunner, et al., Angew.

Chem., Int. Ed. Engl.

, 4078 (2004).3. J. Legros and C. Bolm, Angew. Chem., Int. Ed. Engl.

,4225 (2004).

4. M. C. Carreno, Chem. Rev.

, 1717 (1995).5. F. M. Collins, A. R. Lucy, and C. Sharp, J. Mol. Catal., A

117

, 397 (1997).6. H. Sakuraba, K. Natori, and Y. Tanaka, J. Org. Chem.

,4124 (1991).

7. D. M. Davies and M. E. Deary, J. Chem. Soc., PerkinTrans. 2, 2423 (1996).

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 Russiae-mail: [email protected]

Received, November 24, 2006

Abstract

—-It was first shown that crown ethers catalyze the oxidation of organic sulfur compounds (methylphenyl sulfide to sulfoxide and sulfone, benzothiophene and dibenzothiophene to sulfones) with hydrogen per-oxide.

DOI:

10.1134/S0965544107030127

SHORT COMMUNICATION