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Citation: Sun Yunkai, Zhang Jin, Liu Huijun, Wang Xiaofeng. Synthesis and Polymerization of Optically Active Epoxides with Diazafluorenyl Substituent[J]. Chinese Journal of Organic Chemistry, ;2018, 38(1): 253-258. doi: 10.6023/cjoc201708052 shu

Synthesis and Polymerization of Optically Active Epoxides with Diazafluorenyl Substituent

Sun Yunkai ^a,, ,
Zhang Jin ^b,, ,
Liu Huijun ^a ,
Wang Xiaofeng ^a

a.
College of Chemistry and Chemical Engineering, University of South China, Hengyang 421001
b.
College of Chemistry, Xiangtan University, Xiangtan 411105

Corresponding author: Sun Yunkai, sunyunkai1983@163.com Zhang Jin, zhangjin@xtu.edu.cn
Received Date: 24 August 2017
Revised Date: 17 September 2017
Available Online: 20 January 2017
Fund Project: the Science Foundation of Hunan Province 14JJ6021Project supported by the National Science Foundation of China (Nos. 11305086, 11375084) and the Science Foundation of Hunan Province (No. 14JJ6021)the National Science Foundation of China 11305086the National Science Foundation of China 11375084

Figures(2)

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 (M_w/M_n＝1.04 to 1.10) were obtained. The products were analyzed by NMR, elemental analysis and GPC.
- epoxide,
- chirality,
- asymmetric synthesis,
- polymerization
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