chlorides of certain noble metals. The ease of ethanolysis of the siliconsilicon bond and the course of the subsequent reactions of the cleavage fragments were dependent upon the nature of metals of catalysts. The ethanolysis of vinylpentamethyldisilane (I) in the presence of platinum salts mainly gave hydrosilation products (Me5Si2CH2CH2SiMe3 and EtOMe2SiCH2CH2SiMe2), whilst hydrogenation products (Me5Si2Et
发现在某些贵金属的氯化物存在下,乙硅烷的乙烯基衍生物非常容易发生硅键的亲核裂解。硅硅键的乙醇分解的难易程度和裂解片段随后的反应过程取决于催化剂金属的性质。乙烯基五五甲基乙硅烷(I)在铂盐存在下的乙醇化反应主要产生氢化硅烷化产物(Me 5 Si 2 CH 2 CH 2 SiMe 3和EtOMe 2 SiCH 2 CH 2 SiMe 2),而氢化产物(Me 5 Si 2 Et和EtOMe)由氯化钯(II)催化(I)的乙醇化反应,形成了2 SiEt)作为主要产物。烯丙基五甲基乙硅烷(XII)经历氯铂酸催化的乙醇分解反应比(I)慢得多,而顺式和反丙烯基戊甲基二硅烷(XIII)和(XIV)的溶解度与(I)一样容易。用氯化钯(II)作为催化剂,(XII)也很可能通过其初始异构化成(XIII)和(XIV)而很容易地裂解。针对这种类型的机制,人们提出了将硅硅键α轻松键合至烯烃键的这种亲核性裂解方法。
Nilolaev, G. A.; Mileshkevich, V. P.; Vainshtein, P. M., Journal of general chemistry of the USSR, 1982, vol. 52, p. 1867 - 1870
作者:Nilolaev, G. A.、Mileshkevich, V. P.、Vainshtein, P. M.、Shmeleva, O. A.
DOI:——
日期:——
Continuous Single-Stage Organomagnesium Synthesis of a Mixture of Ethylethoxysilanes and Dimethylethylethoxysilane
作者:Boris A. Klokov
DOI:10.1021/op990011g
日期:2000.3.1
Simultaneous synthesis of ethylethoxysilanes and dimethylethylethoxysilane from a mixture of ethyl chloride, tetraethoxysilane, and dimethyldichlorosilane with magnesium (supply rate 75-100 g h(-1)) was studied. Schemes of intermediate processes are proposed. Reactivity of dimethyldichlorosilane and diethyldichlorosilane relative to each other is evaluated. Various grades of magnesium are tested. To reduce the amount of regenerated solvent (toluene) its mixtures with oligodiethylsiloxanes are used. The mixture of ethyl-substituted silanes can be used in subsequent preparation of oligo-ethylsiloxane liquids modified with the terminal dimethylethylsiloxy groups, which are characterised by improved lubricating properties.