PHOTOOXIDATION OF PHENOL CRESOLS AND DIHYDROXYBENZENES
PHOTOOXIDATION OF PHENOL CRESOLS AND DIHYDROXYBENZENES
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DOI：
10.1021/ja00966a019
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发表时间：
1966-01-01
影响因子：
15
通讯作者：
MILLER, SI
中科院分区：
文献类型：
--
作者：
JOSCHEK, HI;MILLER, SI
苯酚水溶液在2537 A的条件下，在氧、二氮氧化物和醋酸铜的存在下，或在氮的作用下，稳定辐照，可得到相当相似的产物。鉴定出五种碳-碳或碳-氧二聚体和两种二羟基苯，但没有三羟基苯。羟基化产物部分由碳-氧二聚体产生，部分由直接羟基化产生，但不是由碳-碳二聚体产生。这些光氧化结果与苯酚化学或电化学氧化的结果有很大不同；我们发现2,2 '-二羟基联苯是苯酚与高锰酸盐或铁氰化物氧化时唯一可分离的产物。溶剂的辐照是相似的，即发生类似的二聚化和羟基化反应。二羟基苯只产生二聚化产物。对醌产生对对苯二酚以及羟基化产物。下面的途径似乎适用于简单的酚类。
Thesteady irradiation at 2537 A of aqueous solutions of phenol in the presence of oxygen, dinitrogen oxide, and cupric acetate or under nitrogen yields rather similar products. Five carbon-carbon or carbon-oxygen dimers and two dihydroxybenzenes, but no trihydroxybenzenes, were identified. The hydroxylation products arise in part from the carbon-oxygen dimers and in part by direct hydroxylation but not from the carbon-carbon dimers. These photooxidation results differ substantially from those reported for chemical or electrochemical oxidationsof phenol; we find 2, 2'-dihydroxybiphenyl as the only isolable product in the oxidation of phenol with permanganate or ferricyanide. The irradiation of thecresols is similar, that is, analogous dimerization and hydroxylation occurs. The dihydroxybenzenes give only dimerization products. p-Quinone yields p-hydroquinone as well as hydroxylated products. The following routes to products appears to hold for the simple phenols.