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This invention discloses a method for synthesizing cefotiam, using 7-aminocephalosporanic acid (7-ACA) as the parent nucleus and introducing a 4-dimethylaminopyridine-dimethyl carbonate composite catalytic system. The reaction is carried out in a one-pot process involving 3-position nucleophilic substitution, 7-position amidation, and simultaneous deprotection in a green mixed solvent of ionic liquid [BMIM]BF₄-water with 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazole and compound I. This method simplifies the process, improves selectivity, produces a high-purity product with stable yield, and is suitable for industrial production.