Tertiary alcoholysis of chlorosilanes via tetracoordinate silylated quaternary ammonium intermediates
作者:H.K. Chu、M.D. Johnson、C.L. Frye
DOI:10.1016/0022-328x(84)85186-4
日期:1984.8
only if the additional assumption is made that the slow and rate-determining steps involve ionic quaternary ammonium chloride intermediates in which the nitrogen bears a tetracoordinate silicon substituent. The proposed tetracoordinate-silylated quaternary ammonium intermediates derive further credibility from a number of stable species reported previously and reviewed herein.
研究了叔胺-HCl受体对ROH(R = ViMe 2 C)对Ph 2 SiCl 2和Ph 2 Si(OR)Cl的醇解作用的增速作用。相对速率大于10 6用于pH 2的SiCl 2和10 4用于pH 2已经观察到Si(OR)Cl。这些显着提高的速率与胺的碱度差异没有任何关系,但与胺的亲核倾向相关。但是,只有在另外作出以下假设的情况下,这才是正确的:确定速度和速率的步骤涉及离子性的季铵氯化物中间体,其中的氮带有一个四配位的硅取代基。所提出的四配位甲硅烷基化的季铵中间体从先前报道并在本文中综述的许多稳定物种中获得了进一步的可信度。