Russian Journal of General Chemistry, Vol. 73, No. 8, 2003, p. 1323. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 8, 2003, p. 1399.
Original Russian Text Copyright
2003 by Potapov, Amosova, Belozerova, Yarosh, Gendin, Voronkov.
LETTERS
TO THE EDITOR
Thermal Addition of Diphenyl Disulfide
to Ethynyltrimethylsilane in the Presence of Dimethyl Diselenide
V. V. Potapov, S. V. Amosova, O. V. Belozerova, O. G.Yarosh,
D. V. Gendin, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Irkutsk State Technical University, Irkutsk, Russia
Received July 15, 2002
It is known that the radical reaction of the system
diphenyl disulfide diphenyl diselenide with acetylene
derivatives occurs under UV irradiation and gives rise
to thioselenation products, i.e. 1-phenylthio-2-phenyl-
selenoethene [1]. Heating of dimethyl diselenide with
alkynes yields 1,2-bis(methylseleno)ethenes [2].
GC MS and confirmed by alkaline hydrolysis. The
1,2-bis(phenylthio)ethene [3] formed by hydrolysis
has the same Z:E ratio as the starting compound.
The spectral and physicochemical characteristics
of 1,2-bis(phenylthio)-1-trimethylsilylethene and 1,2-
bis(phenylthio)ethene are consistent with published
data [3, 4].
We showed that thermal dithiylation of ethynyltri-
methylsilane is strongly accelerated in the presence of
equimolar or catalytic amounts of dimethyl diselenide.
The reaction of diphenyl disulfide with ethynyltri-
methylsilane in the presence of dimethyl diselenide
(10 mol%) at 150 C provides 1,2-bis(phenylthio)-1-
trimethylsilylethene in 60% yield (1:2 E:Z mixture).
The yield of 1,2-bis(phenylthio)-1-trimethylsilylethene
in similar conditions in the absence of dimethyl
diselenide is as low as 7%.
1
The H NMR spectra were measured on a Bruker
DPX-400 instrument (400 MHz) in CDCl3, internal
reference HMDS. The mass spectra were obtained at
70 eV.
REFERENCES
1. Ogawa, A., Obayashi, R., Ine, H., Tsuboi, Y., Sono-
da, N., and Hirao, T., J. Org. Chem., 1997, vol. 63,
no. 3, p. 881.
SiMe3
<
MeSeSeMe
>
2. Potapov, V.A., Amosova, S.V., Starkova, A.A., Zhni-
kin, A.R., Doron’kina, I.V., Beletskaya, I.P., and
Hevesi, L., Sulfur Lett., 2000, vol. 23, no. 5, p. 229.
PhSSPh + Me3SiC CH
>
<
SPh
PhS
It can be assumed that the catalytic effect of di-
methyl diselenide consists of formation of an inter-
mediate thioselenation product which then converts
into the thermodynamically more stable 1,2-bis-
(phenylthio)-1-trimethylsilylethene.
3. Trofimov, B.A., Gusarova, N.K., Atavin, A.S., Amoso-
va, S.V., Gusarov, A.V., Kazantseva, N.I., and Kala-
bin, G.A., Zh. Org. Khim., 1973, vol. 9, no. 1, p. 8.
4. Kuniyasu, H., Ogawa, A., Miyazaki, S.-I., Ryu, I.,
Kambe, N., and Sonoda, N., J. Am. Chem. Soc., 1991,
vol. 113, no. 26, p. 9796.
The isomeric composition of 1,2-bis(phenylthio)-1-
1
trimethylsilylethene was determined by H NMR and
1070-3632/03/7308-1323$25.00 2003 MAIK Nauka/Interperiodica
Potapov
