Bis(trimethylsilyl) Sulfide1

[3385-94-2]  · C6H18SSi2  · Bis(trimethylsilyl) Sulfide  · (MW 178.44)

(reduction of S, Se, and Te oxides;4 formation of thiocarbonyl derivatives under mild conditions;7 formation of allylsilanes from ketones or allylic alcohols13)

Alternate Name: TMS2S.

Physical Data: bp 164 °C; d 0.846 g cm-3.

Solubility: sol diethyl ether, THF, CH2Cl2, MeCN, and aromatic solvents.

Form Supplied in: colorless cloudy liquid, commercially available.

Handling, Storage, and Precautions: avoid strong oxidizing agents. The reagent is moisture sensitive, flammable, and decomposes to CO, CO2, H2S, and sulfur oxides. Stench, mucous membrane (lungs, eyes) and skin irritant. Store in cool dry place free of oxygen. Use in a fume hood.

Reducing Agent.

Bis(trimethylsilyl) sulfide (TMS2S) is used to reduce aromatic nitro groups2 to amines and the oxides of sulfur, selenium, and tellurium. Conditions for nitro group reduction (eq 1) are forcing; however, yields are good. Reactions of TMS2S with primary aliphatic nitro groups3 result in the formation of the thiohydroxamic acids (eq 2) which can be isolated or carried further to the nitrile. Secondary alkyl nitro derivatives provide oximes. Sulfoxides are reduced4 to sulfides, selenoxides to selenides, and telluroxides to tellurides. Conditions are mild and work well on both the aliphatic and aromatic oxides.

Sulfur Transfer Reagent.

Alkyl sulfides5 can be formed from the corresponding alkyl halides using TMS2S. Thioaldehydes,6 thioketones (eq 3),7 thioamides,8 thioacid anhydrides,9 thioacylsilanes,10 divinyl sulfides (eq 4),11 and thiranes (eq 5)12 are also produced from TMS2S and their respective carbonyl or alkenic compounds, in combination with the reagents shown.

Silicon Transfer Reagent.

Bis(trimethylsilyl) sulfide can transform1b alcohols, acids, and amines into their silylated counterparts. Enol silanes13 are also formed under the influence of this silyl transfer reagent.

1. (a) So, J.-H.; Boudjouk, P. Inorg. Synth. 1992, 29, 30. (b) Mizhiritskii, M. D.; Reikhsfel'd, V. O. RCR 1988, 57, 447. (c) Mizhiritskii, M. D.; Yuzhelevskii, Yu. A. RCR 1987, 56, 355. (d) Capozzi, G. PAC 1987, 59, 989.
2. Hwu, J. R.; Wong, F. F.; Shiao, M.-J. JOC 1992, 57, 5254.
3. Tsay, S.-C.; Gani, P.; Hwu, J. R. JCS(P1) 1991, 1493.
4. (a) Soysa, H. S. D.; Weber, W. P. TL 1978, 235. (b) Detty, M. R.; Seidler, M. D. JOC 1982, 47, 1354.
5. (a) Ando, W.; Furuhata, T.; Tsumaki, H.; Sekiguchi, A. SC 1982, 627. (b) Steliou, K.; Salama, P.; Corriveau, J. JOC 1985, 50, 4969.
6. (a) Capperucci, A.; Degl'Innocenti, A.; Ricci, A.; Mordini, A.; Reginato, G. JOC 1991, 56, 7323. (b) Segi, M.; Nakajima, T.; Suga, S.; Murai, S.; Ryu, I.; Ogawa, A.; Sonoda, N. JACS 1988, 110, 1976. (c) Lebedev, E. P.; Mizhiritskii, M. D.; Baburina, V. A.; Zaripov, Sh. I. JGU 1979, 49, 943.
7. (a) Degl'Innocenti, A.; Capperucci, A.; Mordini, A.; Reginato, G.; Ricci, A.; Cerreta, F. TL 1993, 34, 873. (b) Steliou, K.; Mrani, M. JACS 1982, 104, 3104.
8. Lin, P.-Y.; Ku, W. S.; Shiao, M.-J. S 1992, 1219.
9. Ando, W.; Furuhata, T.; Tsumaki, H.; Sekiguchi, A. CL 1982, 885.
10. Ricci, A.; Degl'Innocenti, A.; Capperucci, A.; Reginato, G. JOC 1989, 54, 19.
11. Aida, T.; Chan, T. H.; Harpp, D. N. TL 1981, 22, 1089.
12. Capozzi, F.; Capozzi, G.; Menichetti, S. TL 1988, 29, 4177.
13. Mizhiritskii, M. D.; Lebedev, E. P.; Fufaeva, A. N. JGU 1982, 52, 1862.

Mark A. Matulenko

University of Wisconsin at Madison, WI, USA

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