Fe(III)EDTA作为氧化羰化苯酚合成碳酸二苯酯一种有效的氧化还原催化助剂

研究了氧化羰化苯酚合成碳酸二苯酯反应。发现了Fe(III)EDTA 在PdCl2/Fe(III)EDTA/1,4 苯醌/ 四丁基溴化铵催化体系中具有很好的助催化效果。讨论了上述催化体系中的每一组分的作用，并提出了一个催化反应机理。氧化羰化苯酚合成碳酸二苯酯反应的最佳温度为100℃～120℃。当反应在100℃、PCO=2.0MPa、PO2=0.5MPa、苯酚 0.5mol、 PdCl2 0.28mmol、n(PdCl2)∶n(Fe(III)EDTA)∶n(苯醌)∶n(四丁基溴化铵)=1∶1∶10∶40、 4A 分子筛 5.0g、 4h进行时，碳酸二苯酯的产率和选择性分别为8.35%和97.5%。压力越高对生成碳酸二苯酯越有利。

Fe(Ⅲ)EDTA as an efficient redox cocatalyst for oxidative carbonylation of phenol to diphenyl carbonate

The synthesis of diphenyl carbonate (DPC) by oxidative carbonylation of phenol was studied. Fe(Ⅲ)EDTA was found to be efficient in PdCl2/Fe(Ⅲ)EDTA/1,4-benzoquinone (BQ)/ tetrabutylammonium bromide (TBAB) catalyst system. The role of each component in the catalyst system was discussed. A catalytic mechanism was proposed. The optimum reaction temperature for oxidative carbonylation of phenol to DPC was 100℃～120℃. When the reaction was catalyzed over PdCl2/Fe(Ⅲ)EDTA/BQ/Bu4NBr, at 100℃,pCO=2.0MPa,pO2=0.5MPa,phenol 0.5 mol, PdCl2 0.28mmol, n(PdCl2)∶n(redox cocat.)∶n(BQ)∶n(Bu4NBr)=1∶1∶10∶40, 4 A molecular sieve 5.0 g, 4 h, the yield and selectivity of DPC were 8.35% and 97.5% respectively. High pressure was favorable for the production of DPC.