THE SYNTHESIS OF 3,3-DIFLUOROALLYL DERIVATIVES OF SILICON BY AN ORGANOPHOSPHORUS ROUTE

Article abstract of DOI:10.1016/S0022-328X(00)82432-8

3,3-Difluoroallyl derivatives of silicon have been prepared by the reaction of difluorochloromethane with ylides of type Ph3P=CHCH2SiR3 (SiR3=SiMe3, SiMe2H, SiMe2OSiMe3, SiMe(OSiMe3)2).Also prepared by this procedure was Me3SiCH2C(CH3)=CF2, but Me3SiCH2C(C6H5)=CF2 could not be prepared in this way, probably because the ylide, Ph3P=C(C6H5)CH2SiMe3, was not sufficiently basic to deprotonate HCF2Cl.The thermal stability of Me3SiCH2CH=CF2 was assessed and a few of its reactions examined: addition of CCl2 and CBr2 (generated via the appropriate PhHgCX2Br) and addition-elimination reactions with phenyl- and n-butyllithium to give Me3SiCH2CH=C(R)F (R=Ph, n-Bu).