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Reaction of a-bromobenzyl cyanide and ethyl xanthamidate, NH,*CS*OEt, in benzene or without a solvent yields a-carbamylthiobenzyl cyanide (VI), whereas in alcohol the ethyl xanthamidate is isomerized to ethyl thiolcarbamate (IV). The reaction in benzene in the presence of sodium acetate gives 2 : 5-di-(2-ethoxy-5-phenyl-4-thiazolylimino)-3 : 4-diphenylpyrroline (VIII), a brilliant red pigment, of which the structure has been proved by hydrolysis. The synthesis of similar pigments also occurs when methyl and n-butyl xanthamidates are used.