GB1426353A - 15alpha,16alpha-methylene-5alpha-androstanes - Google Patents

Abstract

1426353 15,16-Methylene-androstane compounds SCHERING AG 12 Feb 1973 [11 Feb 1972] 6819/73 Heading C2U Novel steroids of the formula (wherein R is H, acyl, C 1-4 alkyl or an oxygencontaining heterocyclic group and C<SP>1</SP>-C<SP>2</SP> is a single or double bond between the 1- and 2- carbon atoms) are prepared by chemical or microbiological oxidation of the corresponding ring A-saturated 3#-hydroxy-steroids containing a protected 17#-hydroxy group, followed, if desired, by #<SP>1</SP>-dehydrogenation (for example by bromination and dehydrobromination) and/or, if desired or necessary, by conversion to a free 17#-ol which if desired may subsequently be esterified or etherified. 17# - Benzoyloxy - 15α,16α - methylene - 5α- androstan-3#-ol is prepared by oxygenating 3#- acetoxy - 5α - pregn - 16 - en - 20 - one to give 17α - hydroxy - 3# - acetoxy - 5α - pregn - 15- en - 20 - one, reducing this to the 20-ol. refluxing this in a solvent with a zinc-copple couple and methylene iodide to give 3#-acetoxy-15α,16α- methylene - 5α - pregnane - 17α,20# - diol, oxidizing this with periodic acid to give 3#-acetoxy- 15α,16α - methylene - 5α - androstan - 17 - one, reducing this to the 17#-ol, converting this to the 17-benzoate and hydrolysing the 3-acetoxy group. 17# - Tetrahydropyranyloxy - 15α,16α- methylene - 5α - androstan - 3# - ol is prepared by hydrolysis of 17#-tetrahydropyranyloxy-3#- acetoxy - 15α, 16α - methylene - 5α - androstane, in turn prepared by etherification of the corresponding 17#-ol. The novel steroids are androgenic and anabolic agents and may be made up into pharmaceutical compositions with suitable carriers.