有机化学 ›› 2018, Vol. 38 ›› Issue (1): 253-258.DOI: 10.6023/cjoc201708052 上一篇    下一篇

所属专题: 庆祝吴养洁院士九十华诞专辑

研究简报

含二氮杂芴基的旋光环氧化合物的合成及聚合研究

孙允凯a, 张劲b, 刘慧君a, 王小峰a   

  1. a 南华大学化学化工学院 衡阳 421001;
    b 湘潭大学化学学院 湘潭 411105
  • 收稿日期:2017-08-24 修回日期:2017-09-17 出版日期:2018-01-25 发布日期:2017-10-20
  • 通讯作者: 孙允凯, 张劲 E-mail:sunyunkai1983@163.com;zhangjin@xtu.edu.cn
  • 基金资助:

    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.

Synthesis and Polymerization of Optically Active Epoxides with Diazafluorenyl Substituent

Sun Yunkaia, Zhang Jinb, Liu Huijuna, Wang Xiaofenga   

  1. a College of Chemistry and Chemical Engineering, University of South China, Hengyang 421001;
    b College of Chemistry, Xiangtan University, Xiangtan 411105
  • Received:2017-08-24 Revised:2017-09-17 Online:2018-01-25 Published:2017-10-20
  • Contact: 10.6023/cjoc201708052 E-mail:sunyunkai1983@163.com;zhangjin@xtu.edu.cn
  • Supported by:

    Project supported by the National Science Foundation of China (Nos. 11305086, 11375084) and the Science Foundation of Hunan Province (No. 14JJ6021).

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.

关键词: 环氧化合物, 手性, 不对称合成, 聚合

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 (8a and 8b) were produced. The ee values of epoxides (8a and 8b) are larger than 97%. The epoxides (4, 6, 8a and 8b) were polymerized using KOH as an initiator and the polyethers with narrow molecular weight distributions (Mw/Mn=1.04 to 1.10) were obtained. The products were analyzed by NMR, elemental analysis and GPC.

Key words: epoxide, chirality, asymmetric synthesis, polymerization