A reaction coupling system of transesterification and methoxycarbonylation with methyl phenyl carbonate (MPC) as intermediate was established to efficiently prepare 1,6-hexamethylene diurethane (HDU) from 1,6-hexamethylene diamine (HDA). The feasibility of the system was explored using the thermodynamics analysis, the reaction mechanism and the experiment results. The optimal reaction was carried out to get higher HDU yield. The thermodynamic analysis showed that the methoxycarbonylation of HDA with MPC, the Gibbs free energy of which was negative, was a spontaneous process. Furthermore, the equilibrium constant of the methoxycarbonylation of HDA with MPC was much greater than that of the transesterification of dimethyl carbonate (DMC) with phenol, so the reaction coupling could be realized under mild conditions. The reaction mechanism analysis indicated that phenoxy anion was the key species for reaction coupling. Higher MPC concentration was detected when sodium phenoxide was used as transesterification reactant with DMC, since the phenoxy anion of sodium phenoxide could be dissociated more easily. Sodium phenoxide was more suitable to prepare HDU through reaction coupling. A yield of HDU as high as 98.3% could be reached under the optimal conditions of m(PhONa)/m(DMC) = 0.027 and n(DMC)/n(HDA) = 8/1 at 90 degrees C in 2 h. (C) 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.