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具有激素活性的19-失碳-16-次甲基-17α-乙酰氧基黄体酮(10)可从3β-乙酰氧基-16β-甲基-16α,17α-环氧孕甾-5-烯-20-酮(1)经九步反应合成。1先与HOCl加成得5α-氯-6β-羟基衍生物(2),后者再与四醋酸铅及碘在苯中反应而成6β,19-环氧化物3;16α,17α-环氧结构破环后生成16-次甲基衍生物5,在碳酸氢钾-甲醇溶液中3β-乙酰氧基被选择性水解为3β-羟基衍生物6,6经Jones氧化并除去HCl成7,后者用锌及醋酸还原成19-羟基化合物8α;8α经Jones氧化成19-羧酸衍生物9,最后脱羧便得目的物10。8α用四氯苯醌脱氢成Δ~6衍生物11α,再经氧化、脱羧便得Δ~6-19-失碳-16-次甲基-17α-乙酰氧基黄体酮(13)。
The 19-nor-16-methylethyl-17α-acetoxy progesterone (10) having a hormonal activity can be obtained from 3β-acetoxy-16β-methyl-16α, 17α-epoxypregn-5-ene (1) synthesized in nine steps. 1 first added with HOCl 5α-chloro-6β-hydroxy derivative (2), the latter with lead tetraacetate and iodine in the reaction of 6β, 19-epoxide 3; 16α, 17α-epoxy structure Disruption of the 16-methine derivative 5 results in the selective hydrolysis of the 3β-acetoxy group to the 3β-hydroxy derivative 6,6 in potassium bicarbonate-methanol solution and oxidation by Jones and removal of HCl to 7, the latter Zinc and acetic acid was reduced to 19-hydroxy compound 8α; 8α by Jones oxidation of 19-carboxylic acid derivative 9, the final decarboxylation will give the desired object 10.8α with tetrachlorobenzoquinone dehydrogenation Δ ~ 6 derivative 11α, and then After oxidation, decarboxylation will be Δ 6-19 - carbon-16-methymethyl-17α-acetoxy progesterone (13).