CuCl2 and PdCl2 catalysts for oxidative carbonylation of aniline with methanol

Synthesis of methyl-N-phenyl carbamate from the oxidative carbonylation of aniline with methanol has been studied over CuCl2-NaI, PdCl2-NaI, PdCl2-CuCl2-NaI, and PdCl2-CuCl2-HCl in an autoclave at 373/438 K and 0.13/3.79 MPa. Carbamate yields decreased in the order: CuCl2-NaI > PdCl2-NaI > PdCl2-CuCl2-NaI > PdCl2-CuCl2-HCl at 438 K and 3.79 MPa. Product distribution profiles showed that carbamate yield increased with reaction time and leveled off at43.5% over CuCl2-NaI after I h of batch reaction at 438 K and 3.79 MPa. The low cost and high activity Of CuCl2-NaI could provide a novel and cost-effective process for carbamate synthesis. (C) 2002 Elsevier Science B.V. All rights reserved.