A various new dithi‐ocarbamides were synthesized from heterocyclic six‐membered 1,3‐dicarbonyl systems, such as 4‐hydroxy‐2,5‐pyranopyridines, 4‐hydroxy‐2‐pyridones, 4‐Hydroxy‐2‐quinolones, 4‐hydroxy‐coumarins, and 4‐hydroxy‐1‐methyl‐2‐quinolones. The dicarbonyl compounds in the presence of anhydrous potassium carbonate in dimethyformamide react with tetraalkylthiuram disulfides to yield 3‐dialkylaminothiocarbonylthio derivatives through a simple, convenient one‐pot reaction. The structures were confirmed by using IR, NMR, and elemental analysis.