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Simultaneous Epoxidation of Olefin and Hydroxylation of Aromatics during Water Electrolysis

水电解过程中同时进行烯烃环氧化和芳烃羟基化

基本信息

批准号：
07455320
负责人：
OTSUKA Kiyoshi
金额：
$ 4.16万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

Epoxidation of olefins is extremely important both in the current industrial process and organic synthesis because epoxide is one of the most useful synthetic intermediates. Most of all commercial epoxidation reactions are indirect, multi-step co-oxidations. Moreover, these processes require a labile, explosive and expensive oxidant such as hydrogen peroxide or tert-butyl hydroperoxide. While, phenol that is also one of the most important chemical in industry, is manufactured by the Cumene process, multi process. Therefore, one-step syntheses of epoxide and phenol are most desirable process in industry.The purpose in this work is to success simultaneous epoxidation of olefin at anode and hydroxylation of aromatics at cathode during the water electrolysis. First, many anodes were tested for the epoxidation of 1-hexene during the water electrolysis by using the cell, [1-hexene, CH_2Cl_2, anode|H_3PO_4/silica wool|cathode, H_2O/He]. We found that Pt-black anode is the most active for the epoxidation of 1-hexene at room temperature. This Pt-black anode is active for the epoxidation of propylene to propylene oxide at room temperature. During this epoxidation, much H_2 is produced at cathode. We have already reported that the hydroxylation of benzene to phenol during H_2-O_2 fuel cell reactions at cathode. The most active cathode for the formation of phenol is Pd-black+Fe_2O_3/Carbon Whisker. Then, we applied this cathode to the electrolysis cell for epoxidation. We found that simultaneou formation of 1,2-epoxyhexane at anode and formation of phenol at cathode during water electrolysis using the electrolysis cell, [1-hexene, CH_2Cl_2, Pt-black anode|H_3PO_4 aq./silica wool|Pd-balck+Fe_2O_3/CW cathode, benzne, O_2].

环氧化物是重要的合成中间体之一，烯烃环氧化反应在现代工业生产和有机合成中具有重要意义。大多数商业环氧化反应是间接的、多步共氧化。此外，这些方法需要不稳定的、爆炸性的和昂贵的氧化剂，例如过氧化氢或叔丁基过氧化氢。苯酚是重要的化工原料之一，目前主要采用异丙苯法生产。因此，一步法合成环氧化合物和苯酚是工业上最理想的工艺，本工作的目的是在水电解过程中实现阳极烯烃的同时环氧化和阴极芳烃的同时羟基化。首先，利用电解槽[1-己烯，CH_2Cl_2，阳极]对电解水过程中的1-己烯环氧化反应进行了实验研究|磷酸/硅棉|阴极H_2O/He]。我们发现，在室温下，铂黑阳极对1-己烯的环氧化反应活性最高。该铂黑阳极在室温下对丙烯环氧化为环氧丙烷具有活性。在此过程中，在阴极产生大量的H_2。我们已经报道了在H_2-O_2燃料电池阴极反应中苯羟基化为苯酚的反应。Pd黑+Fe_2O_3/碳晶须阴极对苯酚的生成活性最高。然后，我们将这种阴极应用于环氧化电解槽中。用[1-己烯，CH_2Cl_2，Pt-黑]阳极电解水时，发现在阳极有1，2-环氧己烷生成，在阴极有苯酚生成|磷酸水溶液石英棉|Pd-炭黑+Fe_2O_3/CW阴极，苯，O_2]。