Acid-catalysed rearrangement of bis-5,6-dihydro-4H-1,3-thiazin-2-yl and other disulphides and related reactions

Abstract

Some dithiocarbamates, thiocarbamates, and thiourea derivatives have been oxidised to the disulphides [R¹X(R²N)C]₂S₂ with iodine. In the presence of trifluoroacetic acid, these lost sulphur giving the thiocarbonyl derivatives R¹X(R₂N)C–N(R²)CSR¹(R¹, R², X =[CH₂]₃, S; [CH₂]₂, S; Me, Me, S; Et, PhCH₂, O; 5α-cholestan-3β-yl, Et, O; and Me, Ph, NMe). These rearrangements were most plausibly intramolecular, but proceeded by varying extents of intermolecular scrambling.