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Xanthane hydride (5-Amino-3H-1,2,4-dithiazole-3-thione) reacts with primary amines (1 eq.) and HCHO (2 eq.) under harsh conditions (reflux in DMSO) to give a hitherto unknown heterocyclic system, 6,7-dihydro-3H,5H-[1,2,4]dithiazolo[4,3-a][1,3,5]triazine. The products were confirmed by NMR studies.

&lt;strong&gt;Synthesis of 6-R-6,7-dihydro-3&lt;em&gt;H&lt;/em&gt;,5&lt;em&gt;H&lt;/em&gt;-[1,2,4]dithiazolo[4,3-a][1,3,5]triazine-3-thiones by aminomethylation of xanthane hydride&lt;/strong&gt;