Hydrosilylation of cyclohexene, 1-methylcyclohexene, and isopropylidenecyclohexane
作者:O. G. Yarosh、L. V. Zhilitskaya、N. K. Yarosh、A. I. Albanov、M. G. Voronkov
DOI:10.1007/s11176-005-0114-4
日期:2004.12
Hydrosilylation of cyclohexene and isopropylidenecyclohexane with chloro(methyl)silanes Me3−n SiHCln (n = 1–3) gives rise to cyclohexyl- and chloro(2-cyclohexylpropyl)methylsilanes. Hydrosilylation of 1-methylcyclohexene with chlorodimethylsilane (n = 1) occurs anomalously and involves double-bond migration to form a mixture of seven compounds: the cis and trans isomers of 2-, 3-, 4-chlorodimethyl(methylcyclohexyl)silanes and chlorodimethyl(cyclohexylmethyl)silane. Chlorodimethylsilane (n = 2) adds to 1-methylcyclohexene to form a mixture of the cis and trans isomers of dichloro(methyl)(2-methylcyclohexyl)silane and dichloro(cyclohexylmethyl)methylsilane. With trichlorosilane (n = 3), no other products than trichloro(cyclohexylmethyl)silane are formed. The hydrosilylation products were reacted with ethynylmagnesium bromide to synthesize the corresponding ethynyl derivatives.
在氢硅化反应中,环己烯和异亚丙基环己烷与氯甲基硅烷Me3−n SiHCln(n = 1–3)反应,生成环己基和氯代(2-环己基丙基)甲基硅烷。1-甲基环己烯与氯二甲基硅烷(n = 1)的氢硅化反应异常,涉及双键迁移,生成七种化合物的混合物:2-、3-、4-氯二甲基(甲基环己基)硅烷的顺反异构体和氯二甲基(环己基甲基)硅烷。氯二甲基硅烷(n = 2)与1-甲基环己烯反应,生成二氯(甲基)(2-甲基环己基)硅烷和二氯(环己基甲基)甲基硅烷的顺反异构体混合物。在三氯硅烷(n = 3)存在下,仅生成三氯(环己基甲基)硅烷。氢硅化产物与乙炔镁溴反应,合成了相应的乙炔衍生物。