氧雄龙的合成

以甲基表雄醇为起始原料,环保高效地合成了氧雄龙。首先采用环保的温和氧化剂2-iodoxybenzoicacid(IBX)在65～70℃,氧化甲基表雄醇直接合成α,β-不饱和羰基甾体-17α-甲基-1-睾酮;经-30～-40℃臭氧化后,用氢氧化钠溶液碱性水解得到17β-羟基-17α-甲基-1-氧代-1,2-开环-A-失碳-5α-雄甾-2-含氧羧酸;最后在0～10℃,经硼氢化钠碱性条件下还原后,调节pH=1～2,内酯化反应合成了目的物。3步操作的产率分别为72%、69%及86%。中间体和目的物经红外光谱、核磁共振氢谱、质谱及元素分析确证了其化学结构。

Synthesis of Oxandrolone

Oxandrolone was eco-friendly and efficiently synthesized from 17α-methyl-androstan-3β,17β-diol.Firstly,the α,β-unsaturated carbonyl steroid intermediate 17α-methyl-1-testosterone was synthesized from 17α-methyl-androstan-3β,17β-diol with a recyclable and elegant oxidant 2-iodoxybenzoic acid (IBX) at 65～70 ℃.Next,17β-hydroxyl-17α-methyl-1-oxo-1,2-seco-A-nor-5α-andro-2-oic acid was given through the ozonization of 17α-methyl-1-testosterone with ozone at -30～-40 ℃ followed by hydrolysis under alkaline condition.Finally,the target oxandrolone was obtained through reduction with sodium borohydride under alkaline condition at 0～10 ℃ and proceeding with lactonization in acidic aqueous solution(pH=1～2).The yields at three stages were 72%,69% and 86%,respectively.The chemical structures of the intermediates and target product were characterized by IR,1HNMR,MS and elementary analysis.