Synthetic methods are described for the preparation of 5H-[1,2,4]triazolo[5‘,1’:2,3][1,3]thiazino[4,5-b]quinolines 5, 5H-[1,2,4]triazolo[3',4’:2,3][1,3]thiazino[4,5-b]quinolines 6, 11 H-[1,2,4]triazolo[5‘, 1 ':2,3][1,3]thiazino[6,5-b]quinoline 13 and 11H-[1,2,4]triazolot[3',4’:2,3][1,3]thiazino[6,5-b]quinoline 14 starting from 2-chloro-3-chloromethylquinoline 1 and 1,2,4-triazole-5-thiols 2. Different reactivity of the chlorine atoms of 1 under different reaction conditions, and a new rearrangement were observed during elaboration of these methods. The structures of the products 5, 6,13,14 and the intermediates leading to them were confirmed by desulfurisation reactions, unequivocal syntheses and nmr spectroscopy.