A new approach for direct formylation of various amines has been disclosed using a novel formylating agent, formylhydrazine, to afford N-formylamines in significant yields with application in the gram-scale synthesis of chlorothiazide. This transformylation (transfer of a formyl group from hydrazine to amines) occurs via denitrogenation in the presence of K2S2O8 as the exclusive reagent with water as the solvent. Two reaction pathways involving extremely underexplored formyl or hemiaminal radicals have been postulated, which require further investigation.