An Efficient Method for the Oxidation of Organic Sulfides to Sulfones
________________________________________________________________________________ PROCEDURES/DATA
_
the reaction. Thin-layer chromatography of the crude solid
and reaction mixture indicated that oxidation of sulfide 1 is
quantitative, and intermediate sulfoxides were not observed.
On the other hand, if UHP was replaced by 30% H O , the
yield of the reaction product was markedly lower and in some
cases no reaction occurs.
The optimum ratio substrate 1 to UHP in the case of oxida-
tion of dialkyl sulfides was found to be 1:4, and in the case of
oxidation of alkyl-aryl- and diaryl sulfides 1:8.
Several examples illustrating this novel and efficient proce-
dure for the oxidation of organic sulfides 1 to the correspond-
ing sulfones 2 are presented in Table 1.
[2] W. E. Truce, T. C. Klinger, W. W. Brand, “Sulfones and Sul-
foximines” in: Organic Chemistry of Sulfur, S. Oae (ed.),
Plenum Press, New York, 1977, Chapter 10
[
3] E. Block, “Oxidation and Reduction of Sulfides” in: The
2
2
Chemistry of Functional Groups, Suppl. E, Part 1, S. Patai
(
ed.), Wiley, New York, 1980, Chapter 13
[
4] K. Schank, “The Chemistry of Sulfones and Sulfoxides”, S.
Patai, Z. Rappoport, C. J. M. Stirling (eds.), Wiley, New York,
1
988, Chapter7
[5] M. Hirano, J. Tomaru, T. Morimoto, Chem. Lett. 1991, 523
[6] S. W. Kaldor, M. Hammond, Tetrahedron Lett. 1991, 32, 5043
[7] K. S. Kim, H. J. Hwang, C. S. Cheong, C. S. Hahn, Tetrahe-
dron Lett. 1190, 31, 2893
[
[
8] B. M. Trost, D. P. Curran, Tetrahedron Lett. 1981, 22, 1287
9] H. Z. Schultz, H. B. Fryemuth, S. R. Buc, J. Org. Chem.
In conclusion, this new method for converting sulfides to
the corresponding sulfones offers the following advantage:
1
963, 28, 140
10] G. W. Gokel, H. M. Gerdes, D. M. Disbong, J. Org. Chem.
980, 45, 3634
11] S. Wolfe, C. F. Ingold, J. Am. Chem. Soc. 1983, 45, 7755
(a) safe and cheap oxidizing reagent is used; (b) the oxidation
[
[
is mild and fast giving exclusively sulfones in quantitative
yields; (c) the method is efficient also for the oxidation of
sulfides containing bulky groups (entry 1c) and electron with-
drawing substituents (entries 1i, 1k); (d) the procedure is very
facile, and sulfones precipitate from the reaction mixture.
1
[12] C. Lu, E. W. Hughes, P. A. Giguere, J. Am. Chem. Soc. 1941,
63, 1507
[13] M. S. Cooper, H. Heaney, A. J. Newbold, W. P. Sanderson,
Synlett 1990, 533
[
[
[
[
[
14] H. Heaney, Aldrichchimica Acta 1993, 2, 35
15] R. Balicki, Synthesis, in print
16] C. W. Fenton, C. K. Ingold, J. Chem. Soc. 1929, 2341
17] H. J. Reich, F. Chow, S. L. Peake, Synthesis 1978, 299
18] W. Su, Tetrahedron Lett. 1994, 35, 4955
Experimental
All reagents are commercially available and were used with-
out purification. TLC analyses were run on plates covered
with silica gel, eluted with benzene-methanol (8:1, v/v).
[19] C. M. Suter, The Organic Chemistry of Sulfur, Wiley, New
York 1944, 688
[
[
20] L. Field, R. D. Clark, Org. Synth., Coll. 4, N. Rabjohn (ed.),
963, p. 674
1
Oxidation of Organic Sulfides (General Procedure)
21] F. E. Hardy, P. R. H. Speakman, P. Robson, J. Chem. Soc.
The corresponding substrate 1 (3 mmol for dialkyl- and 1.5
mmol for alkyl-aryl- or diaryl sulfides) is introduced to the
solution of UHP (12 mmol) in formic acid (10 ml) at room
temperature with stirring. A white precipitate is formed dur-
ing reaction. After 1–4 h, the reaction is complete (TLC anal-
ysis). Water (20 ml) and ether (20 ml) are added. After sepa-
ration, the ether layer is washed successively with saturated
sodium bicarbonate and sodium chloride solutions. Drying
over magnesium sulfate, filtration through a pad of silica gel
and concentration give chromatographically pure sulfone 2.
(C) 1969, 2334
[22] C. G. Venier, T. G. Squires, Y. Y. Chen, G. P. Hussmann, J.
C. Shei, B. F. Smith, J. Org. Chem. 1982, 47, 3773
23] B. M. Graybill, J. Org. Chem. 1967, 32, 2931
[
[
24] F. Ullmann, G. Pasdermadjian, Ber. Dtsch. Chem. Ges. 1901,
3
4, 1154
[
[
25] C. Graebe, Justus Liebigs Ann. Chem. 1974, 174, 188
26] B. Camps, Ber. Dtsch. Chem. Ges. 1882, 25, 256
Address for correspondence:
Prof. Dr. Roman Balicki
Pharmaceutical Research Institute
References
8, Rydygiera Str
[
1] N. S. Simpkins, “Sulfones in Organic Synthesis” in: Tetra-
hedron Organic Chemistry Series Vol. 10, J. E. Baldwin and
P. D. Magnus (ed.), Pergamon Press, Oxford 1993
01–793 Warszawa, Poland
Fax: Intern. code 22 633-82-96
E-mail: Kaczmarek@stratus.ifarm.waw.pl
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