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Reactions of functionalized [CN, CO2Et, C(O)NHR, C(S)NR1R2] derivatives of thiomalonic acid and 2‐arylthioacetamides with sulfonyl azides were shown to give active‐methylene N‐sulfonylamidines in 62–98 % yields. Various procedures for the reactions, including the use of pyridine, boiling ethanol, and water, or running the reactions in the absence of a base and solvent at 80 °C, were carried out and...