Synthesis, spectroscopic, theoretical and structural studies of new trihalomethyl sulphenyl derivatives of 5‐methyl‐1,3,4‐thiadiazole‐2‐thiol

Although 2‐mercapto‐5‐methyl‐1,3,4‐thiadiazole (mmtd) is commonly thought of as a thione tautomer, electrophilic substitution occurs on the thiol moiety. The tautomeric ability of mmtd allows a substitution reaction to take place at the sulphur; this is shown by reaction with Cl 3− n F n CSCI compounds ( n  = 0–2) to give perhalomethyldithio thiadiazole derivatives. Three novel perhalomethylsulphenyl compounds, which exhibit a wide range of potentially interesting applications, were obtained and characterized by x‐ray crystal diffraction, mass spectrometry, IR and Raman spectroscopy and density functional theory calculations. Copyright © 2002 John Wiley & Sons, Ltd.