PREPARATION AND REACTIONS OF ALPHA, BETA-UNSATURATED AND CROSS-CONJUGATED DIENE THIONES

.DELTA.1,4-Kiene-3-thiones were prepared from corticosterone-1,4-dien-3-ones and phosphorus pentasulfide. Reaction with diphenyldiazomethane or 2-nitrobenzenesulphenyl chloride gave, respectively, the derived 3-diphenylmethylene-.DELTA.1,5-dienes and 3-(2-nitrobenzenesulphenylthio)-.DELTA.1,3,5-trienes. The less stable steroid .DELTA.4-ene-3-thiones were trapped with 2-nitrobenzenesulphenyl chloride as 3-(2-nitrobenzenesulphenylthio)-.DELTA.3,5-dienes. Subsequent thiol exchange gave 3-ethane- and 3-benzene-sulphenylthio-.DELTA.3,5-dienes. Warfarin and cyclocumarol were thionated with P4S10 giving mono- and dithio-derivatives. Griseofulvin gave a stable enethione and then, with diphenyldiazomethane, the diphenylmethylene derivative. [The .DELTA.1,4-dien-3-one unit of the corticosteroids is a structural feature of paramount importance for biological activity.].