Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (1): 253-258.DOI: 10.6023/cjoc201708052 Previous Articles     Next Articles

Special Issue: 庆祝吴养洁院士九十华诞专辑



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 发布日期:2017-10-20
  • 通讯作者: 孙允凯, 张劲;
  • 基金资助:


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 Published:2017-10-20
  • Contact: 10.6023/cjoc201708052;
  • Supported by:

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

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