SYNTHESIS OF (15E)-17-BETA-HYDROXY-5-ALPHA-ANDROSTANE-3,15-DIONE 15-[O-(CARBOXYMETHYL)]OXIME, NEW HAPTEN FOR DIHYDROTESTOSTERONE (17-BETA-HYDROXY-5-ALPHA-ANDROSTAN-3-ONE)

摘要

Addition of 4-methoxybenzyl alcohol to 3 beta-hydroxy-5 alpha-androst-15-en-17-one gave the mixture of isomeric 15-(4-methoxyphenyl)methoxy derivatives from which, after acetylation and chromatography, the major 15 beta isomer was separated. Borohydride reduction gave 17 beta-hydroxy derivative which was protected as methoxymethyl ether. Oxidative cleavage of protecting group at position 15 and the subsequent Jones oxidation afforded corresponding 15-ketone. Its oximation with O-(carboxymethyl)hydroxylamine, deacetylation and methylation with diazomethane gave protected O-(carboxymethyl)oxime derivative with free hydroxy group at position 3. Its oxidation afforded dihydrotestosterone derivative and successive deprotection of position 17 and of carboxy group led to final (15E)-17 beta-hydroxy-5 alpha-androstane-3,15-dione 15-[O-(carboxymethyl)]oxime. The title compound was designed as dihydrotestosterone hapten for heterologous radioimmunoassays. [References: 6]