Collect. Czech. Chem. Commun. 1996, 61, 1647-1654

Synthesis of (15E)-3β-Hydroxyandrost-5-ene-15,17-dione 15-(O-Carboxymethyl)oxime; The New Hapten for 3β-Hydroxyandrost-5-en-17-one (Dehydroepiandrosterone, DHEA)

Jan Fajkoš, Vladimír Pouzar and Ivan Černý

Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague 6, Czech Republic


From 17β-hydroxy-15β-[(4-methoxyphenyl)methoxy]androst-5-en-3β-yl acetate (1) by acetylation, removal of (4-methoxyphenyl)methyl group, and oxidation with Jones reagent, 15-oxoandrost-5-ene-3β,17β-diyl 3,17-diacetate (4) was prepared. (O-Carboxymethyl)hydroxylamine treatment and subsequent diazomethane methylation gave methyl ester of corresponding 15-(O-carboxymethyl)oxime derivative. Partial acid hydrolysis gave 3-acetate as a minor product, therefore the major 17-acetate was transformed in two steps into the 3-benzoate. Oxidation at position 17 and subsequent deprotection gave for both products final (15E)-3β-hydroxyandrost-5-ene-15,17-dione 15-(O-carboxymethyl)oxime (14), but for 3-acetyl derivative the whole synthesis is shorter and gave higher yield.

Keywords: Dehydroepiandrosterone; Hapten; Oxime.