3β-乙酰氧基-15β,16β-亚甲基雄甾-5-烯-17-酮的合成

来源期刊：中南大学学报(自然科学版)2003年第6期

论文作者：刘丰良 周康根 刘佳佳

文章页码：637 - 640

关键词：3β-乙酰氧基雄甾-5,15-二烯-17-酮;甲基硫氧叶立德; 3β-乙酰氧基-15β,16β-亚甲基雄甾-5-烯-17-酮;合成

Key words：3β-acetoxyandrosta-5 ,15-dien-17-one; dimethyl sulfoxonium methylide ;3β-acetoxy-15β,16β-methylenean-drosta-5-en-17-one; synthesis

摘    要：在二甲亚砜、四氢呋喃或1,4—二氧杂环己烷溶剂中,当温度为12~30℃时,碘化三甲氧硫锤钅翁((CH3)3S⁺OI^-)与氢化钠(NaH)作用1 h生成甲基硫氧叶立德,再与3β-乙酰氧基雄甾-5,15-二烯-17-酮(Ⅱ)反应,产物经分离得到环丙化产物3β-乙酰氧基-15β,16β-亚甲基雄甾-5-烯-17-酮;探讨了反应物配比、反应温度、溶剂种类、加料方式对环丙化反应的影响.当反应温度为12℃,n((CH₃)₃S⁺OI^-)∶n(NaH)∶n(Ⅱ) =1.10∶1.05∶1.00,加料方式为叶立德溶液加入到甾体溶液中,溶剂为二甲亚砜和四氢呋喃(体积比为4∶1)时,用重结晶法分离得产物,产率为80.5%.测试了产物的比位移值Rf、熔点、旋光度,并采用IR,MS和1HNMR等对产物进行了表征.

Abstract: The title compound(Ⅰ) was prepared by nucleophilic addition reaction of 3β-acetoxyandrosta-5,15-dien-17-one (Ⅱ) at 12~30℃. Thus,interaction of trimethylsulfoxonium iodide and sodium hydride gave dimethyl sulfoxonium methylide (Ⅲ) which transferred methylene to (Ⅱ) to form (Ⅰ). The influence of the ratio of reactants, the reaction temperature, the selection of solvents and the addition ways of reactants are discussed. The optimum condition is as follows,n((CH₃)₃S⁺OI^-)∶n(NaH)∶n(Ⅱ)=1.10∶1.05∶1.00, the temperature is at 12℃, the volume fraction of DMSO∶THF is 4∶1, and the addition way is from (Ⅲ) to (Ⅱ). The product is seperated by recrystallization and fair yields (e.g. 80.5%) and stereoselectivity are obtained. The compound (Ⅰ) is characterized by IR, MS and ¹HNMR.