Collect. Czech. Chem. Commun. 1979, 44, 742-749

Hydrosilylation of dialkenyl sulphides

Michail G. Voronkova, Václav Chvalovskýb, Svetlana V. Kirpichenkoa, Natalia N. Vlasovaa, Sergei T. Bolshakova, Gabriela Kuncováb, Vladimir V. Keikoa and Elena O. Tsetlinaa

a Institute of Organic Chemistry, Siberian Division of the Academy of Sciences of the U.S.S.R., 664033 Irkutsk, U.S.S.R.
b Institute of Chemical Process Fundamentals, Czechoslovak Academy of Sciences, 165 02 Prague 6-Suchdol, Czechoslovakia


Hydrosilylation of divinyl and diallyl sulphide by triethyl- and triethoxysilane catalyzed by H2PtCl6.6 H2O and [RhCl{P(C6H5)3}3] has been studied. With divinyl sulphide the addition of X3SiH (X = C2H5 or OC2H5) across the double bond proceeded to a negligible extent, the main reaction route being the cleavage of the =CH-S bond. The course of the reaction of diallyl sulphide depended strongly upon the catalyst and the starting silicon hydride. In the presence of both catalysts triethoxysilane adds to diallyl sulphide to form a mixture of both isomeric monoadducts (β and γ) in relative amounts depending upon the catalyst. Contrary to this, the γ-adduct is formed solely in the chloroplatinic acid catalyzed hydrosilylation of the above compound by triethylsilane whereas the cleavage of the C-S bond is predominant reaction in the presence of the rhodium catalyst. Some further side reactions are also reported.