The reaction of gem-dichloroallyllithium with halides of silicon, germanium, tin and mercury, and with triphenylborane. Equilibrium vs. kinetic control of regioselectivity
作者:Dietmar Seyferth、Gerald J. Murphy、Robert A. Woodruff
DOI:10.1016/s0022-328x(00)90668-5
日期:1977.11
The reactions of gem-dichloroallyllithium, which was prepared by the low temperature reactions of n-butyllithium with 3,3,3-trichloropropene or with 3,3-dichloroallyltriphenyllead, with trimethylchlorosilane, trimethylchlorogermane, trimethyltin bromide, mercuric chloride and iodomethane were examined. With trimethylchlorosilane and iodomethane, 1,l-dichloroallyl products were obtained exclusively
考察了通过正丁基锂与3,3,3-三氯丙烯或3,3-二氯烯丙基三苯基铅的低温反应与三甲基氯硅烷,三甲基氯锗烷,溴化三甲基锡,氯化汞和碘甲烷的反应制备的宝石-二氯烯丙基锂的反应。用三甲基氯硅烷和碘甲烷仅能得到1,1-二氯烯丙基产物,而用三甲基溴化锡和氯化汞只能得到3,3-二氯烯丙基产物。与trimethylchlorogermane(等摩尔量)的反应得到的Me 5.7 / 1的混合物3 GeCCl 2 CHCH 2和Me 3 GeCH 2 CHCC1 2。当使用不足的三甲基氯锗烷时,该比率降低至0.65,这是因为对照实验证实,宝石-二氯烯丙基锂与Me 3 GeCC1 2 CH = CH 2平衡形成Me 3 GeCH 2 CH = CCl 2。宝石-二氯烯丙基锂与结构为Li [Ph 3 BCH 2 CH = CCl 2 ]的三苯基硼烷形成加合物,其水解(酸性介质)得到HCCl 2 CH = CH