GB736412A - Manufacture of unsaturated compounds of the androstane series - Google Patents

Abstract

D 7-Androstenes containing in the 3-position an acyloxy or Oxo radical and in the 17-position an acyloxy, Oxo or esterified carboxyl radical are prepared by treating aliphatic sulphonic acid esters of 7 - hydroxy - androstanes containing the required radicals in the 3- and 17-positions with an inorganic or organic base. The preferred ester reactants are the esters of 3 : 17-diacyloxy - 7 - hydroxy - androstanes, e.g. aliphatic sulphonic acid esters of 3 : 17-diacetoxy-, 3 : 17 - dipropionyloxy- and 3 : 17-dibenzoyloxy - 7 - hydroxy - androstanes and 3 - keto - 7 - hydroxy - aetiocholanic acid esters. The aliphatic sulphonic acid ester radical may be derived from an alkane sulphonic acid such as methane-, ethane- and propane-sulphonic acid. Suitable inorganic and organic bases are the hydroxides and carbonates of alkali and alkaline earth metals, pyridine, 2 : 4 : 6-collidine, dimethylaniline and piperidine. In p the examples, D 7 - 3b : 17b - diacetoxy - androstene is prepared from the corresponding 7a -mesyloxy- and 7a - propanesulphonyloxy - androstanes, D 7 - 3a - acetoxy - aetiocholenic acid methyl ester is prepared from 3a -acetoxy-7a -mesyloxyaetiocholanic acid methyl ester, D 7-3 : 17-diketo-androstene is prepared from 3 : 17-diketo-7a - mesyloxy - androstane, D 7 - 3b : 17b - dibenzoyloxy - androstene is prepared from 3b : 17b - dibenzoyloxy - 7a - ethanesulphonyloxy - androstane, D 7 - 3b - acetoxy - 17 - keto-androstene is prepared from 3b -acetoxy-7a -mesyloxy - 17 - keto - androstane and D 7-3b : 17b - dipropionyloxy - androstene is prepared from 3b : 17b -dipropionyloxy-7a -mesyloxy-androstane and is hydrolysed with methanolic potassium hydroxide to form D 7-3b : 17b -dihydroxy-androstene. Aliphatic sulphonic acid esters of 7-hydroxyandrostanes which are further substituted in the 3-position by an acyloxy or Oxo radical and in the 17-position by an acyloxy, Oxo or esterified carboxyl radical are prepared by oxidizing a D 5-androstene compound with tertiary butyl chromate, the double bond of the resultant D 5-7-keto-androstene is saturated with hydrogen advantageously by means of catalytically activated hydrogen in the presence of an inert organic solvent, e.g. ethyl acetate, the 7-keto-androstane obtained is reduced to the 7-hydroxy-androstane forming the 7a -hydroxy compound as the main product which is then esterified with an aliphatic sulphonic acid. 3b : 17b - Diacetoxy - 7a - mesyloxy - androstane is prepared from D 5-3b : 17b -diacetoxyandrostene by the above procedure each intermediate compound being isolated.