GB889311A - Androstenol derivatives - Google Patents

Abstract

The invention comprises compounds of the general formulae <FORM:0889311/IV (b)/1> <FORM:0889311/IV (b)/2> wherein X represents fluorine, bromine or chlorine, Z represents a carbonyl or hydroxymethylene radical, Z1 represents a carbonyl radical or represents a hydroxymethylene radical when Z represents a hydroxymethylene radical, and M represents hydrogen, an alkali metal or ammonium radical. The 9a -bromo-11b -hydroxy compounds of the above general formulae may be prepared by reacting the corresponding D 9(11)-compounds with N-bromoacetamide. The 9a -fluoro and chloro-11b -hydroxy compounds of the above general formulae are prepared by treating the corresponding 9,11-epoxides with hydrogen fluoride and hydrogen chloride, respectively. The 11-keto compounds of the above general formulae may be prepared by a mild oxidation of the corresponding 11b -hydroxy compounds, e.g. by means of chromium trioxide in pyridine. The 3-hydroxy compounds of the above general formulae may be be prepared by reducing the corresponding 3-keto-compounds with sodium borohydride. The salts of the second general formula above may be obtained from the lactones of the first general formula by reaction with aqueous alkali, and the corresponding free acids may be obtained from the salts by a brief exposure to a proton source. Detailed examples are given. 17a - (2 - carboxyethyl) - 17b - hydroxy - 4,9(1I)-androstadien-3-one lactone is prepared by treating 17a - (2 - carboxyethyl) - 17b - hydroxy - 4 - androsten-3-one lactone with oxygenating substances produced by growing the microorganisms Rhizopus sp. (A.T.C.C. 13,429) to form 17a -(2-carboxyethyl) - 11a , 17b - dihydroxy - 4 - andros - ten-3-one lactone, treating this compound with methane sulphonyl chloride to form the corresponding 11a -methyl-sulphonyloxy compound, and treating the latter compound with sodium acetate and glacial acetic acid. Specification 889,310 is referred to.