The reaction of 1-alkyl-or 1-arylsulfonyl-3-alkylthioureas (I) with carbonyl chloride or phosphorus pentachloride afforded the previously unreported sulfonylcarbodiimides. When the reaction was conducted at room temperature, the intermediate 1-alkyl-or 1-arylsulfonyl-3- alkylchloroformamidines (III) were isolable.