Synthesis of Diphenyl Carbonate from Phenol and Carbon Dioxide in the Presence of Carbon Tetrachloride and Zinc Chloride

Abstract

Diphenyl carbonate (DPC) was synthesized from phenol and dense phase CO 2 in the presence of CCl 4 and K 2 CO 3 using different catalysts of ZnCl 2 , ZnBr 2 , Lewis acid ionic liquids including 1-butyl-3-methylimidazolium chloride (BMIMCl) and bromide (BMIMBr). It was found that K 2 CO 3 was not required, ZnCl 2 and ZnBr 2 were similar in the catalytic performance, and the use of BMIMCl and BMIMBr was not effective for the production of DPC. For the reactions with ZnCl 2 in CCl 4 , the effects of such reaction variables as temperature, CO 2 pressure, the amount of ZnCl 2 , and the volume of CCl 4 were studied in detail. It was shown that the pressure was less influential while a larger amount of ZnCl 2 , a smaller volume of CCl 4 , and a low temperature of around 100°C were beneficial for the synthesis of DPC. On the basis of the results obtained, possible reaction mechanisms were discussed.

ZnBr2 supported on silica-coated magnetic nanoparticles of Fe3O4 for conversion of CO2 to diphenyl carbonate

“…31 We previously reported the study on production of DPC from CO 2 , phenol and tetrachloride carbon (CCl 4 ) catalyzed by ZnCl 2 alone and ZnCl 2 / triuoromethanesulfonic acid (CF 3 SO 3 H). [32][33][34] However, the process still showed the problems including requiring a large amount of catalyst and difficulty of recovering catalyst. Therefore, there is a need to explore an efficient and effective catalyst for direct synthesis of DPC from CO 2 .…”

Incorporation of CO2 into carbonates through carboxylation/hydration reaction

“…It was surprising that K 2 CO 3 was not indispensable in the former work. When ZnCl 2 was applied alone, the yield of DPC was 25% . In this reaction, HCl was also formed together with the production of DPC (Scheme ).…”

“…An important precursor of polycarbonate, diphenyl carbonate (DPC), can be synthesized by the reaction of phosgene and phenol, the transesterification of DMC and phenol, and the oxidative carbonylation of CO, O 2 and phenol. 97,98 However, there are many barriers, such as hazardous raw materials, thermodynamic limitations, and the need to use noble metal catalysts, making the routes unfavorable. In this case, the direct synthesis of DPC from carbon dioxide and phenol stands out from the crowd (see Scheme 19).…”

“…When ZnCl 2 was applied alone, the yield of DPC was 25%. 98 In this reaction, HCl was also formed together with the production of DPC (Scheme 20). As an efficient acid-accepter, triethylamine (Et 3 N) was added into the system and significantly improved the conversion of phenol by the interaction between Et 3 N and HCl.…”

Organic Carbonates

“…19 Since phenol is a poorer nucleophile than aliphatic alcohols such as methanol, it might be expected that the direct formation of diphenyl carbonate from its constituent parts would be a more difficult endeavour than that of, for example, the synthesis of DMC. 19 Since phenol is a poorer nucleophile than aliphatic alcohols such as methanol, it might be expected that the direct formation of diphenyl carbonate from its constituent parts would be a more difficult endeavour than that of, for example, the synthesis of DMC.…”