Direct synthesis of diphenyl carbonate by mediated electrocarbonylation of phenol at Pd2+-supported activated carbon anode
Direct synthesis of diphenyl carbonate by mediated electrocarbonylation of phenol at Pd2+-supported activated carbon anode
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DOI：
10.1016/j.electacta.2010.12.087
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发表时间：
2011-02-28
影响因子：
6.6
通讯作者：
Yamanaka, Ichiro
中科院分区：
文献类型：
--
作者：
Murayama, Toru;Hayashi, Tomohiko;Yamanaka, Ichiro
研究了298 K、1 atm CO中负载Pd Cl 2的活性炭阳极催化苯酚电羰基化合成碳酸二苯酯（DPC）的反应。干燥的CH 2Cl 2或CH 3CN溶剂和1 mA的恒电流电解对于DPC的形成是必要的，同时添加碱和支持电解质也是必要的。三乙胺（Et 3 N）和高氯酸四丁基铵（Bu 4 NClO 4）的组合适合于各种组合。加入2当量。在电解质（C6 H5 OH/Bu 4 NClO 4/CH 2Cl 2）中每隔1小时加入Et 3 N比一次初始加入等量Et 3 N更有效地形成DPC。DPC的产率为130%（以Pd计），电流效率（CE）为42%，反应6 h。CO2形成的CE仅为3%。苯酚钠（PhONa）显示出作为碱和支持电解质的双重功能。当在C6 H5 OH/PhONa/CH 3CN电解液中进行介导的电羰基化反应时，DPC以172%的产率和40%的CE反应6 h。CO2形成的CE为10%。DPC在单次初始添加4当量后连续形成。的Phona。苯酚锂或苯酚钾也可作为介导的苯酚电羰基化为DPC的促进剂。(C)2011爱思唯尔有限公司版权所有。
Mediated electrocarbonylation of phenol to diphenyl carbonate (DPC) at a PdCl2-supported activated carbon anode in 1 atm CO at 298 K was studied. A dry CH2Cl2 or CH3CN solvent and a galvanostatic electrolysis of 1 mA were necessary for formation of DPC, while the addition of a base and a supporting electrolyte was also essential. A combination of triethylamine (Et3N) and tetrabutylammonium perchlorate (Bu4NClO4) was suitable in various combinations. The addition of 2 equiv. of Et3N to the electrolyte (C6H5OH/Bu4NClO4/CH2Cl2) at 1-h intervals was more efficient in the formation of DPC than a single initial addition of the same amount of Et3N. The yield of DPC was 130% based on Pd and its current efficiency (CE) was 42% for 6 h. The CE of the CO2 formation was only 3%. Sodium phenoxide (PhONa) showed dual functionality as a base and supporting electrolyte. When the mediated electrocarbonylation was conducted in a C6H5OH/PhONa/CH3CN electrolyte, DPC was produced in 172% yield and 40% CE for 6 h. The CE of the CO2 formation was 10%. DPC formed continuously after a single initial addition of 4 equiv. of PhONa. Li or K phenoxide also worked as promoters for the mediated electrocarbonylation of phenol to DPC. (C) 2011 Elsevier Ltd. All rights reserved.