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)

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 majo r 15 beta isomer was separated. Borohydride reduction gave 17 beta-hyd roxy derivative which was protected as methoxymethyl ether. Oxidative cleavage of protecting group at position 15 and the subsequent Jones o xidation afforded corresponding 15-ketone. Its oximation with O-(carbo xymethyl)hydroxylamine, deacetylation and methylation with diazomethan e gave protected O-(carboxymethyl)oxime derivative with free hydroxy g roup at position 3. Its oxidation afforded dihydrotestosterone derivat ive and successive deprotection of position 17 and of carboxy group le d to final (15E)-17 beta-hydroxy-5 alpha-androstane-3,15-dione 15-[O-( carboxymethyl)]oxime. The title compound was designed as dihydrotestos terone hapten for heterologous radioimmunoassays.