Synthesis of Organofunctional Silicon Hydride Halides from Methylchlorosilane

The organofunctional silicon hydride halides R(CH 3 )SiHCl were prepared in high yields from CH 3 SiHCl 2, employing CH 3 SiH 2 Cl as an intermediate. CH 3 SiHCl 2 was converted to CH 3 SiH 2 Cl by chloride−hydride redistribution in 41% yield (based on Si−H). The chloride substituent in CH 3 SiH 2 Cl reacted selectively with the Grignard reagent RMgX to form the corresponding dihydride R(CH 3 )SiH 2, where R = H 2 C═CH−, H 2 C═C(CH 3 )−, H 2 C═CHCH 2 −, (CH 3 ) 2 CH−, H 2 C═CHCH 2 CH 2 −, c-C 5 H 9 −, PhCH 2 −, and p -Cl(C 6 H 4 )−. Cl(CH 2 ) 3 (CH 3 )SiH 2 was also prepared by reduction of the corresponding dichloride. Monohalogenation of R(CH 3 )SiH 2 with CuCl 2 /CuI in THF then gave CH 3 RSiHCl in 60−88% overall yield (starting from CH 3 SiH 2 Cl).