有机环硅烷的有效合成方法及其波谱性质(英文)

AN EFFICIENT METHOD FOR SYNTHESIS OF ORGANIC CYCLOSILANES AND THEIR SPECTRAL PROPERTIES

有机基取代二氯硅烷与金属锂在有1,1,1—三甲基三苯基二硅烷存在的四氢呋喃溶液中发生还原偶联反应,合成并分离得到较高收率的具有热力学稳定结构的有机环硅烷,反应式和取得的化合物如下:nR^1R^2SiCl_2+2nLi Ph_3SiSiMe_3 THF→(R^1R^2Si)_n a n=6 b n=5化合物:1a R~=R^2=Me;2b R^1=R^2=P;3a R=Hex,R^2=Me;4a R^1=Ph,R^2=Me;5a R^1=p-tol,R^2=Me,6b R^1=o-tol,R^2=Me;7a R^1=PhCH_2,R^2=Me;8b R^1=Ph,R^2=Et;9a R^1=Ph,R^2=allyl 所有的环硅烷经氢核磁共振谱,红外光谱,紫外光谱等予以鉴定,对新化合物还测定了质谱,并讨论了它们的波谱性质。加入催化剂量的1,1,1—三甲基三苯基二硅烷是用来在溶液中产生三苯基硅基负离子,它可作为促进缩合反应和平衡化的催化剂。本方法特别有利于用来大量生产十二甲基环六硅烷和由烷基、芳基不对称取代的环硅烷。

Reductive coupling reaction of diorganodichlorosilanes with lithium metal in THF in the presence of 1,1,1-trimethyltri-phenyldisilane as catalyst has been used for preparation of organic cyclosilanes which either alkyl or aryl are in thermodynamically favored structures and higher yields.The reactions are described as follows: nR^1R^2SiCl_2+2nLi Ph_3SiSiMe_3/THF→(R^1R^2Si)_n a n=6 b n=5 Compounds:la R^1=R^2=Me;2b R^1=R^2=Ph;3a R^1=Hex,R=Me;4a R^1=Ph,R^2=Me;5a R^1=p-tol, R^2=Me;6b R^1=o-tol, R^2-Me;7a R^1= PhCH_2,R^2=Me;8b R^1=Ph,R^2=Et;9a R^1=Ph,R^2=allyl. All the compounds are identified by ~1H NMR,IR and UV,some new compounds also by MS.Their spectral properties are discussed.The catalytic amount of disilane serves as a source of triphenylsilyl anions which perform as condensing agent and equilibrating catalyst.This method is recommended particularly for the synthesis of dodecamethylcyclohexas- ilane on a large scale and asymmetrically disubstituted compounds (R^1R^2Si)_n,where R^1=aryl,R^2=alkyl.