Reaction of some ketosteroids with thioglycolic acid

(1) Using thioglycolic acid, five mercaptols of 3-ketosteroids have been synthesized sine catalyst. Two of these mercaptols afforded crystalline methyl esters. (2) The reaction of 20-ketoseroids with thioglycolic acid has been investigated. Formation of 20-mercaptols ensues only when zinc chloride and sodium sulfate are employed as catalysts. (3) The date indicated that 17-ketosteroid compounds condense with thioglycolic acid when zinc chloride and sodium sulfate are present in the reaction mixture. (4) The addition of thioglycolic acid to the 5,6-double bond of dehydroepiandrosterone (XLIII) has been described. This reaction proceeds in a mode contrary to the rule of Markownikoff. The position of the thioether linkage in the addition product has been established by oxidation studies. The same reaction was applied to two other 5,6-unsaturated steroids. (5) The synthesis of ?5-3-carbomethoxymethylmercaptocholestene has been described. (6) The use of steroid mercaptols derived from thioglycolic acid as derivatives for characterization and separation purposes has been discussed.