SYNTHESIS OF HIGHLY STERICALLY HINDERED ORGANOSILICON COMPOUNDS AND REACTIONS OF THEM WITH ALCOHOLIC SODIUM ALKOXIDES

Abstract

The Compounds TsiSiXX′X″ [Tsi˭(Me₃Si)₃,C; X˭X′˭X″=Br X=(C₆H₄OMe-p), X′=X″˭Cl X=Bu, X′=X″=Cl; X′=Me, X″=F) synthesised and reacted with boiling NaOR/ROH (R=Me, Et, ⁱPr) have been shown to give the products of type (Me₃,Si)₂CHSiYZOR(Y=OR, X Z=OR, X′). It is suggested that the reaction proceeds through an elimination, analogous to E2 elimination of alkyl halides, involving cynchronous attack of RO⁻ at an SiMe,₃ group, libration of X⁻, and formation of (Me₃Si)₂C˭SiYZ. The compound TsiSiBr₃ reacts with 0.1 M NaOR/ROH to give the substitution and elimination products, TsiSiBr₂(OR), TsiSiBr(OR)₂, and (Me₃Si)₂CHSi(OR)₃. The compounds TsiSi(C₆H₄OMe-p)Cl₂, TsiSiBuCl₂. and TsiSi(C₆H₄OMe-p)MeF react analogouly to give (Me₃Si)₂CHSi-(C₆H₄OMe-p)(OR)₂, (Me₃Si)₂CHSi(C₆H₄OMe-p)OG(OR), (Me₃Si)₂CHSi Bu(OR)₂, (Me₃Si)CH₂SiBu(OR₂) and (Me₃Si)₂CHSi(C₆H₄OMe-p)MeOR

Key Words:

• alkoxide
• organosilicon
• trisyl
• fragmentation