期刊论文

Sun Yunkai;Zhang Jin

中文

有机化学

0253-2786

2018

38

1

253-258

10.6023/cjoc201708052

* Corresponding authors. E-mail: sunyunkai1983@163.com; zhangjin@xtu.edu.cn Received August 24, 2017; revised September 17, 2017; published online October 20, 2017. Dedicated to Professor Yangjie Wu on the occasion of his 90th birthday. Project supported by the National Science Foundation of China (Nos. 11305086, 11375084) and the Science Foundation of Hunan Province (No. 14JJ6021). 国家自然科学基金(Nos. 11305086, 11375084)及湖南省自然科学基金(No. 14JJ6021)资助项目.

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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...

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 9...