An Unusual Occurrence in the Reaction of 4-Azasteroid Derivatives with N-Fluorodi-benzenesulfonimide and Lithium Diisopropylamide  

作　　者：江银枝 梁大伟 项卓 张连群 

机构地区：[1]Department of Applied Chemistry,Zhejiang Sci-Tech.University

出　　处：《Chinese Journal of Structural Chemistry》2010年第8期1236-1240,共5页结构化学（英文）

基　　金：supported by the Young Science Fund of Key Laboratory of Advanced Textile Materials and Manufacturing Technology,Ministry of Education

摘　　要：The reaction of N,N-diethyl-3-oxo-4-methyl-4-aza-5-androstane-17β-carboxamide（1） with N-fluorodibenzenesulfonimide（NFA） and lithium diisopropylamide（LDA） was studied.Under absolute anhydrous and anaerobic conditions,the formation of 5（2α-fluoro-4-methyl-3-oxo-4-aza-5α-androstane-17β-carboxylic acid methyl ester） can be rationalized by participating in the expected nucleophilic substitution reaction.Not in absolute anhydrous and anaerobic conditions,the formation of 10（N-di-isopropyl-N＇-aryl-sulfonamides（C12H20N2O2S） and 11（N-diethyl-3-oxo-4-methyl-4-aza-5-androstene-17β-carboxamide） can be rationalized by assuming that the situ genera-ted carbanion 2 followed by a single electron transfer mechanism.5,10 and 11 were characterized.10 was a new compound and determined by X-ray single-crystal diffraction.Crystal data for 10：space group C2/c with a = 14.783（2）,b = 7.6193（11）,c = 24.663（3） ,β = 98.688（3）o,V = 2746.1（7） nm3,Mr = 256.36,Z = 8,Dc = 1.240 g/cm3,μ = 0.229 mm-1,F（000） = 1104,R = 0.0511 and wR = 0.1268.There exist intramolecular H-bonds which result in a supramolecular framework of the title compound.The formation mechanisms of 10 and 11 were also discussed briefly.The reaction of N,N-diethyl-3-oxo-4-methyl-4-aza-5-androstane-17β-carboxamide（1） with N-fluorodibenzenesulfonimide（NFA） and lithium diisopropylamide（LDA） was studied.Under absolute anhydrous and anaerobic conditions,the formation of 5（2α-fluoro-4-methyl-3-oxo-4-aza-5α-androstane-17β-carboxylic acid methyl ester） can be rationalized by participating in the expected nucleophilic substitution reaction.Not in absolute anhydrous and anaerobic conditions,the formation of 10（N-di-isopropyl-N＇-aryl-sulfonamides（C12H20N2O2S） and 11（N-diethyl-3-oxo-4-methyl-4-aza-5-androstene-17β-carboxamide） can be rationalized by assuming that the situ genera-ted carbanion 2 followed by a single electron transfer mechanism.5,10 and 11 were characterized.10 was a new compound and determined by X-ray single-crystal diffraction.Crystal data for 10：space group C2/c with a = 14.783（2）,b = 7.6193（11）,c = 24.663（3） ,β = 98.688（3）o,V = 2746.1（7） nm3,Mr = 256.36,Z = 8,Dc = 1.240 g/cm3,μ = 0.229 mm-1,F（000） = 1104,R = 0.0511 and wR = 0.1268.There exist intramolecular H-bonds which result in a supramolecular framework of the title compound.The formation mechanisms of 10 and 11 were also discussed briefly.

关 键 词：4-azasteroid synthesis crystal structure SULFONAMIDES mechanism 

分 类 号：O621.25[理学—有机化学]