Heterocyclic synthesis with nitriles: Synthesis of some new thiocyanato-substituted heterocycles from alkylidene malononitrile^†

α-(Thiocyanatomethyl)benzylidenemalononitrile undergoes bromination with N-bromo succinimide to afford α-(bromothiocyanatomethyl)benzylidenemalononitrile. This bromo derivative undergoes reactions with sodium hydrogen sulfide, thioglycollic acid, hydroxylamine hydrochloride, phenylhydrazine, and hydrazine hydrate to afford thiophene, 4H-thiopyran, 4H-oxazine, pyridazine, and bis(thiazol-2-ylidene)azine derivatives, respectively. Mechanistic explanations as well as structure elucidations are discussed.