Organosilicon compounds. Part XLI. The reaction of bis(trimethylsilyl)mercury with some ethers

Abstract

Anisole is cleaved by bis(trimethylsilyl)mercury at 185°; some dimethylmercury is formed, and the major organic product is phenoxytrimethylsilane, which may be formed in a four-centre process in which a Me–Hg bond is simultaneously produced. Little, if any, attack on anisole by trimethylsilyl radicals occurs.

Corresponding reactions, involving the cleavage of C₆H₁₁–O and Me–O bonds occur with methoxycyclohexane, the major organic products being the compounds Me₃SiOMe and Me₃SiOC₆H₁₁, in roughly 3 : 1 ratio, and cyclohexane, the latter presumably coming from cyclohexyl radicals formed by dissociation of C₆H₁₁–Hg bonds. Analogous cleavages occur with ethoxybenzene, methoxytrimethylsilane, and cyclohexoxytrimethylsilane, but with diphenyl ether the greatly dominant reaction is the decomposition of the mercurial to hexamethyldisilane.

The results with anisole indicate that radical processes may be less important than has been suggested, and molecular reactions correspondingly more important, in reactions of the mercurial with other aromatic compounds such as chloro- and bromo-benzene.