7172
In summary, this reaction allows an easy one-step conversion of disul®des to higher polysul®des.
It should allow easy one-step access to some higher polysul®des unavailable by other methods.
Acknowledgements
This work was supported by the Natural Sciences and Engineering Research Council of
Canada and by a McGill University Fellowship for A.Z.R. Dr. Anne-Marie Lebuis solved and
re®ned the crystal structure.
References
1. (a) Litaudon, M.; Guyot, M. Tetrahedron Lett. 1991, 32, 911±914; (b) Chenard, B. L.; Harlow, R. L.; Johnson,
A. L.; Vladuchick, S. A. J. Am. Chem. Soc. 1985, 107, 3871±3879; (c) Ford, P. W.; Narbut, M. R.; Belli, J.;
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3. (a) Westphal, U.; Steudel, R. Phosphorus, Sulfur, and Silicon and Rel. El. 1992, 65, 151±155; (b) Steudel, R.;
Kustos, M.; Munchow, V.; Westphal, U. Chem. Ber. 1997, 130, 757±764.
4. Williams, C. R.; Britten, J. F.; Harpp, D. N. J. Org. Chem. 1994, 59, 806±812.
5. (a) Pickering, T. L.; Saunders, K. J.; Tobolsky, A. V. J. Am. Chem. Soc. 1967, 89, 2364±2367; (b) Musorin, G. K.;
Sedunova, O. V.; Gendin, D. V. Russ. Chem. Bull. 1998, 47, 363±364; (c) Steliou, K. Sulfur Transfer Reagents.
M.Sc. Thesis, McGill University, 1975; (d) the product was positively identi®ed by comparison with p-tolyl
tetrasul®de separately prepared following a procedure from: Saville, R. W. J. Chem. Soc. 1958, 2880±2888;
(e) Dodson, R. M.; Srinivasan, V.; Sharma, K. S.; Sauers, R. F. J. Org. Chem. 1972, 37, 2367±2372; (f) Williams,
1
C. R.; Harpp, D. N. Tetrahedron Lett. 1991, 7651±7654; (g) H NMR (CDCl3) ꢀ=4.42 (s, 4H), 7.1 (m, 10H); 13
C
NMR (CDCl3) ꢀ=40.33, 127.24, 128.18, 128.63, 140,32, 141.26; m.p. 149±151ꢀC. Crystal data for 16: C16H14S6,
Mr=398.63, crystal dimensions 0.65Â0.20Â0.17 mm, monoclinic, space group P21/n, a=21.020(8), b=5.698(2),
c=14.769(4) A, ꢁ=93.37(3)ꢀ, V=1765.9(10) A3, ꢂcalc=1.499 g/cm^3, T=293(2) K, Z=4, F(000)=824, l
(CuKa)=1.54056 A (graphite monochromated), 2ꢃmax=69.82ꢀ, 3329 measured re¯ections of which 2865 with
I>2ꢄ(I) were used for re®nement; Rint=0.031, R1=0.0269, wR2=0.072, GOF=1.026; (h) Bartlett, P. D.; Ghosh,
T. J. Org. Chem. 1987, 52, 4937±4934.
6. The picture of 16 was printed from the cif ®le with Ortep-3 for Windows v. 1.06 created by: Farrugia, L. J. J. Appl.
Cryst. 1997, 30, 565.
7. (a) Fachinetti, G.; Floriani, C. J. Chem. Soc., Dalton Trans. 1974, 2433±2436; (b) Pietra, F.; Vitali, D. J. Chem.
Soc. (B) 1970, 623±625; (c) Moore, C. G.; Porter, M. J. Chem. Soc. (D), 1958, 2890±2892.
8. A typical procedure: A solution of trityl thiosulfenyl chloride (1), 1 mmol (342 mg) in methylene chloride, was
added rapidly into a solution of 1 mmol (122 mg) of diethyl disul®de (6) in a mixture of acetic acid and methylene
chloride (disul®de was dissolved ®rst in CH2Cl2; this is important when solid disul®des are used; slow-reacting
disul®des were treated with 1.1 equiv. of 1). The reaction time was usually shorter than 30 min except for 15 and
17 where at least 12 h was required for completion. The solvent was evaporated when the reaction mixture became
colourless. Separation by column chromatography followed (the residue was loaded with minimum amount of
benzene and eluted with hexanes). The product (160 mg) was analyzed by NMR revealing the presence of starting
disul®de (2%) and hexasul®de (9%). The yield of Et2S4 was calculated as 75% based on starting disul®de.
1
9. Properties of 21: H NMR (CDCl3) ꢀ=2.3 (s, 3H), 7.35 (m, 15H); 13C NMR (CDCl3) ꢀ=23.35, 73.15, 127.13,
127.84, 130.37, 143.48; m.p. 51±53ꢀC; MS (EI) m/z 243 [M+^MeS3] (100).
10. Brintzinger, H.; Pfannstiel, K.; Koddebush, H.; Kling, K. Chem. Ber. 1950, 83, 87±90.