描述了由氯乙烯制备有机甲硅烷基乙炔的一般方法。对称的双(三烷基甲硅烷基)乙炔可以在-80°C下于四氢呋喃中从四氯乙烯,锂和三烷基卤代硅烷获得高收率。当锂和四氯乙烯被类似地在-80至反应°,然后与有机硅卤化物,(氯乙炔基)三有机硅烷,R猝灭3 SiCCCl,生产。这些可以与锂和氯硅烷偶联以得到不对称取代的双(有机甲硅烷基)乙炔。三氯乙烯,锂和三烷基氯硅烷可得到适当的乙炔基三烷基硅烷R 3 SiC fairCH。对称的双(有机甲硅烷基)乙炔也可以由顺式或反式制备-1,2-二氯乙烯,烷基锂化合物和氯硅烷。
A new substitution reaction of acetylenic hydrogen with silyl radicals
作者:Hideki Sakurai、Mineo Yamagata
DOI:10.1039/c29700001144
日期:——
Di-t-butyl peroxide-catalysed reaction of pentamethyldisilane with pentamethyldisilanylacetylene afforded cis- and trans-bis(pentamethyldisilanyl)ethylene and bis(pentamethyldislanyl)acetylene, the latter being formed by a novel hydrogen-abstraction process from an intermediate vinyl radical.
The Reaction of Disilylacetylenes with Cyclopentadienyl Manganese. Formation of Vinylidene Complexes by 1,2-Silyl Shift
作者:Hideki Sakurai、Takeaki Fujii、Kenkichi Sakamoto
DOI:10.1246/cl.1992.339
日期:1992.2
Both cyclic and acyclic acetylenes substituted by two silyl groups on each end undergo facile 1,2-silyl shift in the reaction with cyclopentadienyltricarbonylmanganese under photochemical conditions to give 2,2-disilylvinylidene complexes. Several interesting reactions of the novel complexes are described.