Photoinduced molecular rearrangements. The photochemistry of 1,2,4-oxadiazoles in the presence of sulphur nucleophiles. Synthesis of 1,2,4-thiadiazoles

Abstract

The photochemistry of some 1,2,4-oxadiazoles in the presence of sulphur nucleophiles has been investigated. Irradiation of the 5-amino-3-phenyl- and 3,5-diphenyl-1,2,4-oxadiazole at γ = 254 nm in methanol in the presence of sodium hydrogen sulphide or thiols gave a photo-induced redox reaction at the ring ON bond, leading to the corresponding N-substituted benzamidines. By contrast, irradiation of the 5-amino-3-phenyl-1,2,4-oxadiazole in the presence of thioureas or thiocarbamates, essentially gave 3-phenyl-5-substituted 1,2,4-thiadiazoles, which presume an NS bond formation between the ring-photolytic species and the sulphur nucleophile. In turn, irradiation of the same 5-amino-3-phenyl-1,2,4-oxadiazole in the presence of thioamides again afforded the redox reaction; in addition, amounts of 3-phenyl-5-substituted-1,2,4-thiadiazoles were also formed. Some mechanistic considerations are reported, and synthetic methodologies leading to 1,2,4-thiadiazoles are emphasized.