Abstract
The two-step synthesis of diphenyl carbonate (DPC) from dimethyl carbonate (DMC) and phenol has been compared in liquid phase and gas phase, both over heterogeneous catalysts. In the first step, equilibrium yields of methyl phenyl carbonate (MPC) in the transesterification of DMC and phenol were very low at low temperatures in the liquid phase although reaction rates were fast. This endothermic reaction was more favorable at high temperatures in the gas-phase reaction. Titanium oxide catalysts supported on SiO2 or activated carbon were found to be effective in a continuous gas flow reactor. In case of the second step, the disproportionation of MPC, selective formation of DPC was not feasible in the gas-phase reaction due to extensive side reactions. However, there was no by-product in the liquid-phase reaction over the TiO2/SiO2 catalyst. Therefore, our proposed two-step synthesis process consists of the gas-phase transesterification of DMC and phenol followed by the liquid-phase disproportionation of MPC to DPC, both over the TiO2/SiO2 catalyst.
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References
Chemistry in Britain 30 (1994) 970.
U. Curtius, L. Bottoenbruch and H. Schnell, US Patent 3 442 854 (1969).
H. Yamana, T. Kuni, T. Furusawa, H. Nakai and Y. Hiro, US Patent 3 888 826 (1975).
D. Brunelle, US Patent 4 321 356 (1982).
J.B. Starr and A. Ko, US Patent 4 383 092 (1983).
K. Komiya, S. Fukuoka, M. Aminaka, K. Hasegawa, H. Hachiya, H. Okamoto, T. Watanabe, H. Yoneda, I. Fukawa and T. Dozono, in: Green Chemistry: Designing Chemistry for the Environment, eds. P.T. Anastas and T.C. Williamson (Am. Chem. Soc., Washington, 1996) p. 20.
S. Fukuoka, M. Tojo and M. Kawamura, US Patent 5 210 268 (1993).
G.E. Harrison, A.J. Dennis and M. Sharif, US Patent 5 426 207 (1995).
K. Murata, K. Kawahashi and M. Watabiki, US Patent 5 380 908 (1995).
Z.-h. Fu and Y. Ono, J. Mol. Catal. A 118 (1997) 293.
S. Li and J.S. Lee, J. Catal. 162 (1996) 76.
J.S. Lee, L. Volpe, F.H. Ribeiro and M. Boudart, J. Catal. 112 (1988) 44.
G. Barcelo, D. Grenouillat, J.-P. Senet and G. Sennyey, Tetrahedron 46 (1990) 1848.
P. Tundo, F. Trotta, G. Moraglio and F. Ligorati, Ind. Eng. Chem. Res. 27 (1988) 1565.
W.B. Kim, Synthesis of diphenylcarbonate over heterogeneous catalysts, MS thesis, Pohang University of Science and Technology (1998).
W.B. Kim and J.S. Lee, J. Catal., submitted.
W.B. Kim, J.S. Lee and Y.G. Kim, Appl. Catal. A, in preparation.
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Kim, W.B., Lee, J.S. A new process for the synthesis of diphenyl carbonate from dimethyl carbonate and phenol over heterogeneous catalysts. Catalysis Letters 59, 83–88 (1999). https://doi.org/10.1023/A:1019087530460
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DOI: https://doi.org/10.1023/A:1019087530460