15 beta-hydroxysteroids (Part VI). steroids of the human perinatal period: the preparation and reactions of 3 beta-hydroxy-5,15-androstadien-17-one. The synthesis of 3 beta,15 beta-dihydroxy-5-androsten-17-one and derivatives.
A successful approach to the synthesis of 3 beta,15 beta-dihydroxy-5-androsten-17-one (14d) has been developed using trichloroethoxy ethers as intermediates in the synthesis of the corresponding alcohols. 3 beta-Methoxymethoxy-5,15-androstadien-17-one (10c) was prepared by a selenation/dehydroselenation strategy from 3 beta-methoxymethoxy-5-androsten-17-one (14c). Base-catalyzed reaction of trichloroethanol with 10c gave 3 beta-methoxymethoxy-15 beta-trichloroethoxy-5-androsten-17-one (14g). Under the same conditions, 3 beta-acetoxy-5,15-androstadien-17-one (10b) gave 3 beta-hydroxy-15 beta-trichloroethoxy-5-androsten-17-one (14f) which was characterized after conversion to 14g. Cleavage of the trichloroethoxy group in 14f with zinc or zinc/copper couple gave 14d. The acid-catalyzed hydrolysis of 17,17-ethylenedioxy-5,15-androstadien-3 beta-ol (15) gave 3 beta-hydroxy-5,15-androstadien-17-one (10a) as the major product along with 14d. However, addition of water to 10a in the presence of acid gave the desired product 14d in poor yield (15%).
Reeder
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Department of Metabolic Mass Spectrometry, Royal Prince Alfred Hospital, New South Wales, Sydney, Australia.
Joannou
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GE
D000730:Androstadienes / Q000737:chemistry*; D000734:Androstenediols; D000736:Androstenes / Q000138:chemical synthesis*; D005260:Female; D006801:Humans; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry / Q000379:methods; D011247:Pregnancy
C003561:3,15-dihydroxy-5-androst-en-17-one; C103441:3-hydroxy-5,15-androstadien-17-one; D000730:Androstadienes; D000734:Androstenediols; D000736:Androstenes