The thermolysis of several N-(4-chloro-5H-1, 2, 3-dithiazol-5-ylidene) pyridin-n-amines (where n= 2, 3 and 4) gives a mixture of thiazolopyridine-2-carbonitriles in low to moderate yields. Introduction, by design, of a chlorine substituent at the C2 or C4 position of N-(4- chloro-5H-1, 2, 3-dithiazol-5-ylidene) pyridin-3-amine and other selected azines enables a BnEt3NI mediated ANRORC style ring transformation that provides fourteen heteroazine ...