螺甾内酯(Spiroenone)中间体的合成  

Synthesis of the Intermediate of Spiroenone

作　　者：刘丰良[1] 阳卫军[2] 周康根[3] 章晓骅[1] 

机构地区：[1]中南大学化学化工学院,湖南长沙410083 [2]湖南大学化学化工学院,湖南长沙410082 [3]中南大学冶金科学与工程学院,湖南长沙410083

出　　处：《湖南大学学报（自然科学版）》2003年第6期34-36,共3页Journal of Hunan University:Natural Sciences

基　　金：教育部优秀青年教师基金(No.1357)

摘　　要：3β 乙酰氧基雄甾 5,15 二烯 17 酮(2)与甲基硫氧叶立德(3)通过亲核加成反应得到螺甾内酯(Spiroenone)重要中间体3β 乙酰氧基 15β,16β 亚甲基雄甾 5 烯 17 酮(1),产物经重结晶法分离,收率达80.5%.讨论了反应的主要影响因素,找到了优化条件,即反应温度为12℃,n((CH3)3S+OI-)∶n(NaH)∶n(2)=1.1∶1.05∶1,溶剂为二甲亚砜和四氢呋喃(体积比为4∶1)时,加料方式为叶立德溶液加入到甾体溶液中.实验表明:低温有利于15β,16β 亚甲基产物的形成.测试了产物的物理常数;并用IR,MS,1HNMR等波谱分析手段对产物进行了表征.3β-acetoxyandrosta-5,15-dien-17-one(1)- the intermediate of spiroenone - was prepared by nucleophilic addition reaction of 3β-acetoxyandrosta-5,15-dien-17-one (2) and dimethyloxosulfonium methylide(3) with 80.5% yield. The article also discussed the influence of the ratio of reactants, the reaction temperature , the selection of solvents and the addition ways of reactants . The optimum conditions are as follows ,n((CH_3)_3S^+OI^- )∶n(NaH)∶n(2)=1.1∶1.05∶1, the temperature is 12 ℃, the volume fraction of DMSO:THF is 4∶1,and the addition way is from (3) to (2) .The result shows that low temperature is favorable to the formation of 15β,16β-methylene product seperated by recrystallization. Moreover, (1) was characterized by IR, MS and ()~1HNMR.

关 键 词：合成 3β-乙酰氧基雄甾-5 15-二烯-17-酮 甲基硫氧叶立德 螺甾内酯中间体 

分 类 号：O629.222.1[理学—有机化学]