SYNTHESIS OF (15E)-3-BETA-HYDROXYANDROST-5-ENE-15,17-DIONE 15-(O-CARBOXYMETHYL)OXIME - THE NEW HAPTEN FOR 3-BETA-HYDROXYANDROST-5-EN-17-ONE(DEHYDROEPIANDROSTERONE, DHEA)
J. Fajkos et al., SYNTHESIS OF (15E)-3-BETA-HYDROXYANDROST-5-ENE-15,17-DIONE 15-(O-CARBOXYMETHYL)OXIME - THE NEW HAPTEN FOR 3-BETA-HYDROXYANDROST-5-EN-17-ONE(DEHYDROEPIANDROSTERONE, DHEA), Collection of Czechoslovak Chemical Communications, 61(11), 1996, pp. 1647-1654
From 17 beta-hydroxy-15 beta-[(4-methoxyphenyl)methoxy]androst-5-en-3
beta-yl acetate (1) by acetylation, removal of (4-methoxyphenyl)methyl
group, and oxidation with Jones reagent, 15-oxoandrost-5-ene-3 beta,1
7 beta-diyl 3,17-diacetate (4) was prepared. (O-Carboxymethyl)hydroxyl
amine treatment and subsequent diazomethane methylation gave methyl es
ter of corresponding 15-(O-carboxymethyl)oxime derivative. Partial aci
d hydrolysis gave 3-acetate as a minor product, therefore the major 17
-acetate was transformed in two steps into the 3-benzoate. Oxidation a
t position 17 and subsequent deprotection gave for both products final
(15E)-3 beta-hydroxyandrost-5-ene-15,17-dione 15-(O-carboxymethyl)oxi
me (14), but for 3-acetyl derivative the whole synthesis is shorter an
d gave higher yield.