A strategy was proposed for the synthesis of 5-(morpholin-4-yl)-N'-sulfonyl-1,2,3-thiadiazole-4-imidamides, as well as previously unknown 2-thiocarbamoy lacetimidamides. Their reactions with arylsulfonyl azides were studied. In the case of reactions between dimorpholine derivatives of 2-thiocarbamoylacetimidamides and arylsulfonyl azides, diazo transfer did not occur. Instead, a new process was observed, producing the target molecules in one synthetic step via the formation of triazene intermediate and the elimination of ammonia.