含芴基的旋光末端环氧和环硫化合物的合成  

Synthesis of the Optically Pure Epoxy and Ring-sulfured Compounds with Fluorenyl Substituent

作　　者：孙允凯[1] 张劲[1] 曹靖[1] 欧阳昆冰[1] 阳年发[1] 

机构地区：[1]湘潭大学化学学院环境友好化学与应用省部共建教育部重点实验室,湘潭411105

出　　处：《化学学报》2010年第20期2086-2090,共5页Acta Chimica Sinica

基　　金：国家自然科学基金(No.20772102);教育部博士点专向科研基金(No.20060530002)资助项目

摘　　要：先利用芴与乙醇钠反应或者三苯甲醇与浓磷酸反应,制备相应的9-烃基芴,再利用正丁基锂与9-烃基芴反应得到相应的锂盐,然后在-70℃下滴加旋光的环氧氯丙烷,滴加完毕后在室温搅拌几小时,得到光学纯的含芴基取代末端环氧化合物,它们的ee值均大于98%.将环氧化合物用四氢呋喃溶解,加入NH4SCN,室温搅拌反应24h,过柱分离后,得到光学纯的芴基取代的末端环硫化合物,ee值也均大于97%.通过元素分析、NMR对产物的结构进行了表征,也利用旋光仪等测定了产物的旋光度,并且对反应机理进行了探讨.It has been found that the optically active epoxide （R）-4,4,4-triphenyl-1-butene oxide [or its （S） isomer],which bears bulky pendant,can polymerize to form helical polyether.In our study,optically active epoxides and ring-sulfured compounds with fluorenyl substituent are necessary.Using fluorene and its derivatives to react with n-butyl lithium,the corresponding organic lithium salts can be given,and then,the optically active epichlorohydrin was added dropwise at-70 ℃,stirring to room temperature for several hours.According to regular treatment,the optically pure terminal epoxides with fluorenyl substituent were obtained.The ee values of epoxides are larger than 98%.To a solution of epoxy compounds in THF,was added NH4SCN with stirring,and stirred for 24 h at room temperature.The solvent was evaporated in vacuo and the residue was separated by column chromatography.Optically pure ring-sulfured compounds were obtained and their ee values are greater than 97%.The products were analyzed by NMR,elemental analysis and polarimeter,and mechanism of the reaction was discussed.

关 键 词：环氧氯丙烷 手性 环硫化合物 不对称合成 

分 类 号：O621.3[理学—有机化学]