Synthesis of D-norprogesterone

✍ Scribed by Alfred Hassner; A.W. Coulter; W.S. Seese

• Book ID: 104212209
• Publisher: Elsevier Science
• Year: 1962
• Tongue: French
• Weight: 106 KB
• Volume: 3
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)70514-4

✦ Synopsis

MODIFIED steroids have recently received considerable attention3 owing to the interesting biological properties that many of them exhibit. D-Norsteroids merit additional interest for stereochemical reasons since they contain a six-and four-membered fused ring system. A recent report4 on the synthesis of D-norsteroids , prompts us to communicate our findings to date. Dehydroepiandrosterone (I) can be transformed to D-norprogesterone (XI) by the following route. Nitrosation of I to II5 followed by reaction with chloramine gave 16-diazc-5-androstene-3E-ol-17-one (III),6 m.p. 196-197', in 72 per cent yield. Ultraviolet light irradiation of the latter in tetrahydrofuran-methanol gave upon chromatography 16-carbomethoxy-D-nor-5androstene-38-01 (IV), m.p. 163-16&O, in 40 per cent yield (reported41! m.p. 164-165'). When the irradiation of III was carried out in the presence of water instead of methanol an acid, m.p. 175-1?7', was isolated (65 per cent) which proved to be a mixture of two acids, m.p. 212-214' and m.p.