含二氮杂芴基的旋光环氧化合物的合成及聚合研究

Synthesis and Polymerization of Optically Active Epoxides with Diazafluorenyl Substituent

以1,10-邻菲罗啉(1)为原料制备4,5-二氮芴-9-酮(2),并合成4,5-二氮杂芴(3)和9-亚甲基-4,5-二氮杂芴(5),再利用正丁基锂(或甲基锂)与上述两种二氮杂芴反应得到相应的锂盐,在-50℃下与旋光的环氧氯丙烷(ee>98%)反应得到光学纯的含二氮杂芴基取代末端环氧化合物,它们的ee值均大于98%.将4,5-二氮芴-9-酮与乙基溴化镁(或苯基溴化镁)反应,得到相应的叔醇.叔醇在氢氧化钾和四丁基溴化铵存在下,与旋光的环氧氯丙烷反应,也得到光学纯的含二氮杂芴基取代末端环氧化合物,ee值均大于97%.将末端环氧化合物在不同条件下聚合,得到分子量分布很窄的含二氮杂芴基的聚醚.通过核磁共振、元素分析、凝胶渗透色谱等手段对产物进行了表征,对影响聚合的相关因素做了探讨.

4,5-Diazafluoren-9-one（2）, 4,5-diazafluorene（3） and 9-methylene-4,5-diazafluorene（5） were prepared by 1,10-Phenanthroline（1） as starting material. Using n-butyllithium to react with 3（or using methyllithium to react with 5）, the corresponding organic lithium salts could be given, and then, the optically active epichlorohydrin（ECH, ee〉98%） was added dropwise at-50 ℃, according to regular treatment, the optically pure terminal epoxides（4 and 6） with diazafluorenyl substituent were obtained. The ee values of epoxides are larger than 98%. Using ethylmagnesium bromide（or phenylmagnesium bromide） to react with 2 in the presence of potassium hydroxide and tetrabutylammonium bromide, the corresponding substituted epoxy compounds（8 a and 8 b） were produced. The ee values of epoxides（8 a and 8 b） are larger than 97%. The epoxides（4, 6, 8 a and 8 b） were polymerized using KOH as an initiator and the polyethers with narrow molecular weight distributions（M_w/M_n=1.04 to 1.10） were obtained. The products were analyzed by NMR, elemental analysis and GPC.