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.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
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
关键词
环氧氯丙烷
手性
环硫化合物
不对称合成
epichlorohydrin
chirality
ring-sulfured compounds
asymmetric synthesis
