Über 11, 18‐dioxygenierte 17α‐Hydroxy‐progesterone. Über Steroide, 153. Mitteilung

A 17α‐hydroxyl group has been introduced into 11, 18‐dioxygenated pregnene compounds via the 16, 17α‐epoxide, both by reaction with hydrogen bromide and reductive debromination and by lithium aluminum hydride reduction. Thus, the (18→11)‐lactone of d, l‐11β,17α‐dihydroxy‐progesterone‐18‐acid (X), and presumably d, l‐11β,17α‐dihydroxy‐18‐acetoxy‐progesterone (XIIb) have been prepared. The OPPENAUER oxidation of an 11β,18‐dihydroxy compound gave mainly the 11‐oxo‐18‐hydroxy‐derivative, from which d, l‐11‐oxo‐17α,18‐dihydroxy‐progesterone (XVI) was obtained, and only small amounts of the 11β‐hydroxy‐18‐oxo‐derivative. The structure of the main product was established by conversion into d, l‐18‐acetoxy‐adrenosterone (XIV) which was also synthesised by an independent route.