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 condi...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.展开更多
The title compound VII, 2-fluoro-4-methyl-3-oxo-4-aza-5α-androst-1-ene-17β-carboxylic acid methyl ester （C21H30FNO3, Mr = 363.46）, was prepared through a seven-step reaction from pregnenolone, and characterized by...The title compound VII, 2-fluoro-4-methyl-3-oxo-4-aza-5α-androst-1-ene-17β-carboxylic acid methyl ester （C21H30FNO3, Mr = 363.46）, was prepared through a seven-step reaction from pregnenolone, and characterized by elemental and single-crystal X-ray diffraction analyses as well as IR, MS and 1H-NMR spectra. It is of monoclinic system, space group P21/c with a = 6.3882（7）, b = 9.9033（11）, c = 15.4925（17） , β = 91.923（2）°, V = 979.57（19） 3, Z = 2, Dc = 1.232 mg/m3, μ = 0.088 mm-1, F（000）= 392, R = 0.0465, wR = 0.0989 and λ（MoKα） = 0.71073 . The structure indicates that the four cycles （A： C（1）–C（2）–C（3）–N（1）–C（5）–C（10）, B： C（5）–C（6）–C（7）– C（8）–C（9）–C（10）, C： C（8）–C（14）–C（13）–C（12）–C（11）–C（9）, D： C（14）–C（15）–C（16）–C（17）–C（13）） are in chairand trans-configurations. The results of crystal structure determination show that there exist weak intra-molecular hydrogen bonds, resulting in a two-dimensional supramolecular frame-work of the title compound.展开更多
基金supported by the Young Science Fund of Key Laboratory of Advanced Textile Materials and Manufacturing Technology,Ministry of Education
文摘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.
基金supported by Young Science Fund of Key Laboratory of Advanced Textile Materials and Manufacturing Technology (Zhejiang Sci-Tech. University),Ministry of Education
文摘The title compound VII, 2-fluoro-4-methyl-3-oxo-4-aza-5α-androst-1-ene-17β-carboxylic acid methyl ester （C21H30FNO3, Mr = 363.46）, was prepared through a seven-step reaction from pregnenolone, and characterized by elemental and single-crystal X-ray diffraction analyses as well as IR, MS and 1H-NMR spectra. It is of monoclinic system, space group P21/c with a = 6.3882（7）, b = 9.9033（11）, c = 15.4925（17） , β = 91.923（2）°, V = 979.57（19） 3, Z = 2, Dc = 1.232 mg/m3, μ = 0.088 mm-1, F（000）= 392, R = 0.0465, wR = 0.0989 and λ（MoKα） = 0.71073 . The structure indicates that the four cycles （A： C（1）–C（2）–C（3）–N（1）–C（5）–C（10）, B： C（5）–C（6）–C（7）– C（8）–C（9）–C（10）, C： C（8）–C（14）–C（13）–C（12）–C（11）–C（9）, D： C（14）–C（15）–C（16）–C（17）–C（13）） are in chairand trans-configurations. The results of crystal structure determination show that there exist weak intra-molecular hydrogen bonds, resulting in a two-dimensional supramolecular frame-work of the title compound.
