Description:
<jats:p><jats:bold>Rearrangement of 3‐Thioxo‐Δ<jats:sup>1,4</jats:sup>‐steroids, a New Approach of Steroid Thiols</jats:bold></jats:p><jats:p>3‐Thioxoandrosta‐1,4‐dien‐17‐one <jats:bold>(1)</jats:bold> is subjected to a dienthion‐thiophenol rearrangement in aprotic and protic solvents in the presence of an acid catalyst resulting in the formation of 1‐(acetylthio)‐4‐methylestra‐1,3,5(10)‐trien‐17‐one <jats:bold>(2)</jats:bold>. 1‐mercapto‐4‐methylestra‐1,3,5(10)‐trien‐17‐one <jats:bold>(3)</jats:bold>, and the dimer 1,1′‐(dithio)bis[4‐methylestra‐1,3,5(10)‐trien‐17‐one] <jats:bold>(4)</jats:bold> as the reaction products. The mercapto compound 3 tends to be autoxidized to the sulfide <jats:bold>4</jats:bold>.</jats:p>