Direct synthesis of organodichlorosilanes by the reaction of metallic silicon, hydrogen chloride and alkene/alkyne and by the reaction of metallic silicon and alkyl chloride

Dichloroethylsilane was synthesized by the reaction of metallic silicon, hy drogen chloride and ethylene using copper(I) chloride as the catalyst, the silicon conversion and the selectivity for dichloroethylsilane being 36 and 47%, respectively. At a lower reaction temperature or at a higher ratio of ethylene:hydrogen chloride a higher selectivity was obtained, however the silicon conversion was lower. The silicon-carbon bond formation is caused b y the reaction of a surface silylene intermediate with ethylene. The reacti on with propylene in place of ethylene gave dichloroisopropylsilane (22% se lectivity) and dichloro-n-propyl-silane (8% selectivity) together with chlo rosilanes. A part of the dichloroisopropylsilane is formed by the reaction of silicon, hydrogen chloride and isopropyl chloride formed by hydrochlorin ation of propylene. Use of acetylene instead of alkenes resulted in dichlor ovinylsilane formation with a 34% selectivity. Alkyldichlorosilanes were al so produced directly from silicon with alkyl chlorides, propyl and butyl ch lorides. During the reaction the alkyl chloride is dehydrochlorinated over the surface of copper originating from the catalyst to afford hydrogen chlo ride and alkene. The hydrogen chloride formed participates in the formation of the silicon-hydrogen bond in alkyldichlorosilane, and the reaction of s ilicon, hydrogen chloride and alkene also causes alkyldichlorosilane format ion. The reaction with isopropyl chloride gave a very high selectivity (85% ) for dichloroisopropylsilane, the silicon conversion being 86%.