X-射线单晶衍射法研究双炔失碳醇α-差向异构体的构型  

X-RAY DIFFRACTION STUDIES ON THE CONFIGURATION OF 2ξ, 17α-DIETHYNYL-2ξ, 17β-DIHYDROXY-A-NOR-5α-ANDROSTANEα-EPIMER

作　　者：李麟[1] 李正化[1] 

机构地区：[1]华西医科大学新药设计研究室,成都610041

出　　处：《药学学报》1990年第6期435-437,共3页Acta Pharmaceutica Sinica

摘　　要：本文报道有抗生育作用和雌激素活性的双炔失碳醇α-差向异构体的构型研究。采用重结晶法、低压硅胶柱色谱与HPLC相结合的方法,制得单晶纯品。经HPLC,IR,MS,~1HNMR证实。经Ⅹ-射线单晶衍射法测定,晶体属正交晶系,空问群为P222_1,晶胞参数为a=6.777(2),b=12.125(4),c=25.292(8),V=2078.5(1.2)。晶体结构采用直接法和Fourier技术得到,经最小二乘法修正,最后的偏离因子R=0.039。结构表明:其相对构型中,C_2,C^(17)之乙炔基为α-型,结合合成原料构型推定C_2为R型,C_(17)为R型。X-ray diffraction studies on the configuration of 2ξ, 17α-diethynyl-2ξ, 17β-dihydroxy-A-nor-5α-androstane 'α-epimer' that possessed antifertility effect and estrogen activity were reported Pure α-epimer was obtained by recrystallization and low pressure silica gel column chromatography combined with HPLC method. Its structure was identified by IR, MS, ~1HNMR. The configuration was determined by single crystal X-ray diffraction analysis. The crystal of α-epimer belonged to orthorhombic, the space group was P222,, with the following crystallographic parameters: a=6.777 (2), b = 12.125 (4), c =25.292 (8),V=2078.5 (1. 2)~3, Z=4. One thousand two hundred and thirty-five independent reflections with Ⅰ≥3σ (Ⅰ)were collected on a Nicolet R3M/E four-circle diffractometer by means of MoK α radiation. The structure was solved by direct method and refined by least square technique to a final discrepancy factor of R = 0.039. The molecule was shown to consist of the α-configuration of C_2 and C_(17) ethynyl groups.The absolute configuration was deduced by the absolute configuration of synthetic raw material, conformation analysis and the study of ~1HNMR. The absolute configuration of asymmetric centers were 2R, 5S, 8R,9S, 10S, 13S ,14S,17R.

关 键 词：双炔失碳醇 晶体结构 差向异构体 

分 类 号：R962[医药卫生—药理学]