GB1152128A - Process and Intermediates for the Manufacture of 19-Hydroxycholestanes - Google Patents

Abstract

1,152,128. 6#,19 - Oxido - cholestanes and 19-hydroxy-cholestanes. G. D. SEARLE & CO. 19 Oct., 1967, No. 47571/67. Addition to 1,000,890. Heading C2U. Novel steroids of the formula (wherein Z is carbonyl, #-hydroxymethylene or #-alkanoyloxymethylene, the alkanoyl radical containing 1 to 7 carbon atoms; and R is H or C 2 H 5 ) are prepared by contacting the corresponding 3# - alkanoyloxy - 5α - acetoxy - 6#- hydroxy steroids with a heavy metal acetate oxidizing agent to give the required products wherein Z is #-alkanoyloxymethylene, hydrolysing these to the required 3#-ols, and oxidizing these to the required 3-ones; and the 3-ones are converted to the valuable 19-hydroxycholest-4- en-3-one and 24-ethyl-19-hydroxycholest-4-en- 3-one by contacting with zinc in the presence of a Lewis acid. The 3# - alkanoyloxy - 5α - acetoxy - 6# - hydroxy steroid starting materials are prepared by epoxidizing the corresponding 3#-alkanoyloxy- #<SP>5</SP> - 6 - unsubstituted steroids to give the 5,6- epoxides, cleaving these with an inorganic acid to give the corresponding 3#,5α,6#-triol 3-alkanoates, acetylating these to give the triesters, selectively hydrolysing these to the 3#,5α,6#- triol 5-acetates and esterifying these.