Chinese Journal of Organic Chemistry >
Synthesis and Polymerization of Optically Active Epoxides with Diazafluorenyl Substituent
Received date: 2017-08-24
Revised date: 2017-09-17
Online published: 2017-10-20
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
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
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