摘要
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。
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 struc, tures of the intermediates and target product were characterized by IR, ^1HNMR, MS and elementary analysis.
出处
《精细化工》
EI
CAS
CSCD
北大核心
2007年第11期1112-1114,共3页
Fine Chemicals