GB512940A - Improvements in sterols of the male sex hormone type - Google Patents

Abstract

512,940. Sex hormones. PARKE, DAVIS, & CO. March 4, 1938, No. 6839. Convention date, March 12, 1937. [Class 2 (iii)] A new sterioisomer of allopregnanediol which is designated as allo-pregnanediol-3#-20# is prepared by catalytically reducing allopregnanedione. The new diol may be used to prepare a new allo-pregnanol-20-one by diacylation, followed by partial saponification, oxidation, and saponification. From the allopregnanolone so produced there may be further prepared androstandione by dehydration and oxidation of the ethylene compound. The allopregnanedione which serves as the starting material for the process of the present invention is itself preferably prepared by oxidation by chromic anhydride of the mixture of pregnanediol and allo-pregnanediol obtained as neutral carbinol residue in the aqueous alkaliorganic solvent distribution method of Doisy from human pregnancy urine, andseparation from the oxidation mixture of the less soluble fraction. In an example, allo-pregnanedione prepared as above is reduced by shaking with hydrogen at 45 lbs. pressure for 75 minutes in glacial acetic acid solution in the presence of a platinum oxide catalyst. The allo-pregnanediol-3#-20# so produced is converted into its diacetate by treatment with acetic anhydride and then partially saponified by methyl alcoholic potash to give allo-pregnanediol-3#-20#- monoacetate 20. This compound is then oxidized with chromic oxide in acetic acid solution to 'the acetate of allo-pregnane-ol-20- one-3, which is saponified to the allo-pregnanolone by alcoholic potash. The dehydration of the allo-pregnanolone so produced is carried out by refluxing with freshly fused zinc chloride in acetic acid solution. The ethylene compound is isolated by extraction with chloroform, and decomposed with ozone to give androstanedione. Specification 431,833 is referred to.