A phosgene-free route for the synthesis of methyl N-phenyl carbamate (MPC) by the reaction of aniline with methyl carbamate in the presence of methanol was studied. Effects of catalysts, reaction temperature, reaction time, and catalyst content, the molar ratio of reactants and the content of water on the reaction were investigated. The results demonstrated that an aniline conversion of 90.1% and MPC selectivity of 99.7% were achieved when the reaction was carried out at 433 K for 4 h using ZnCl2 as a catalyst. A possible reaction mechanism was proposed based on the product distribution. (C) 2003 Elsevier B.V. All rights reserved.