用二茂锆配合物一锅法合成1,1′-二取代联烯  

One Pot Synthesis of 1,1′-Disubstituted Allenes using Zirconocene Complexes

作　　者：任申勇[1] 李连涛[1] 张熠点 郭巧霞[2] 申宝剑[1] Ren Shenyong;Li Liantao;Zhang Yidian;Guo Qiaoxia;Shen Baojian(College of Chemical Engineering and Environment,China University of Petroleum,Beijing,102249;College of Science,China University of Petroleum,Beijing,102249)

机构地区：[1]中国石油大学(北京)化学工程与环境学院,北京102249 [2]中国石油大学(北京)理学院,北京102249

出　　处：《化学通报》2021年第10期1080-1085,共6页Chemistry

基　　金：中国石油大学(北京)科研基金项目(2462015YQ0313)资助。

摘　　要：二氯二茂锆(Cp_(2)ZrCl_(2))与乙基溴化镁(EtMgBr)反应生成二乙基二茂锆(Cp_(2)ZrEt_(2)),再与1,4-二烷氧基-2-丁炔反应形成锆杂环戊烯,经过烷氧基在锆原子上的消除直接得到1,1′-二取代联烯(端联烯)。或者Cp_(2)ZrCl_(2)与正丁基锂(n-BuLi)反应生成二丁基二茂锆(Cp_(2)ZrBu_(2)),再与α-烯烃反应形成锆杂环戊烷,然后与1,4-二烷氧基-2-丁炔反应形成锆杂环戊烯,经过烷氧基在锆原子上的消除得到端联烯。上述反应合成端联烯的收率都比较高,这为构造端联烯衍生物提供了一种简单实用的方法。The reaction of zirconocene dichloride(Cp_(2)ZrCl_(2)) with ethyl magnesium bromide(EtMgBr) afforded zirconocene diethyl(Cp_(2)ZrEt_(2)), which reacted with 1,4-dialkoxy-2-butyne to form zirconacyclopentene, after alkoxy group elimination on Zr 1,1′-disubstituted allene(terminal allene) derivative was obtained directly. Moreover the reaction of Cp_(2)ZrCl_(2) with butyl lithium(n-BuLi) afforded zirconocene dibutyl(Cp_(2)ZrBu_(2)), which reacted with ɑ-olefin to form zirconacyclopentane, then with 1,4-dialkoxy-2-butyne to form zirconacyclopentene, after alkoxy group elimination on Zr terminal allene was also obtained directly. The reactions gave terminal allenes in good yields which provided a simple and useful method to construct terminal allene derivatives.

关 键 词：1 1′-二取代联烯 二氯二茂锆 1 4-二烷氧基-2-丁炔 锆杂环戊烯 烷氧基消除 

分 类 号：TQ221.22[化学工程—有机化工]