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在含有杂多化合物的催化体系中,过氧化氢与氧-氢对芳香族化合物的氧化作用。

Hydrogen peroxide and oxygen-hydrogen oxidation of aromatic compounds in catalytic systems containing heteropoly compounds.

作者信息

Kuznetsova N I, Kirillova N V, Kuznetsova L I, Smirnova M Yu, Likholobov V A

机构信息

Boreskov Institute of Catalysis, Lavrentieva, 5, 630090 Novosibirsk, Russian Federation.

出版信息

J Hazard Mater. 2007 Jul 31;146(3):569-76. doi: 10.1016/j.jhazmat.2007.04.058. Epub 2007 Apr 20.

Abstract

Hydrogen peroxide and Pt activated mixture of gaseous O(2) and H(2) have been applied to oxidation of aromatic compounds in the presence of redox active heteropoly compounds in the form of acid H(4)PMo(11)VO(40) and tetrabuthylammonium (TBA) salts TBA(4)PMo(11)VO(40) and TBA(4)HPW(11)Fe(OH)O(39). Benzene, toluene and phenol were subjected to hydroxylation of the ring, which was accompanied by secondary oxidation in the reaction with hydrogen peroxide. Oxygenation of toluene was equally directed to the ring and to methyl group. The total reactivity of substrates was increased in the order of benzene<toluene<phenol in oxidation by both O(2)/H(2) and H(2)O(2). Analysis of products yield and composition indicated the identical nature of active intermediates for both oxidants. It was suggested that HPC bonded radical species are responsible for the oxidation of hydrocarbons.

摘要

在氧化还原活性杂多化合物(以酸H(4)PMo(11)VO(40)以及四丁基铵(TBA)盐TBA(4)PMo(11)VO(40)和TBA(4)HPW(11)Fe(OH)O(39)的形式存在)存在的情况下,过氧化氢以及Pt活化的气态O(2)与H(2)的混合物已被用于芳香族化合物的氧化反应。苯、甲苯和苯酚发生了环羟基化反应,在与过氧化氢的反应中还伴随着二次氧化。甲苯的氧化反应对环和甲基的作用程度相同。在O(2)/H(2)和H(2)O(2)氧化反应中,底物的总反应活性按照苯<甲苯<苯酚的顺序增加。产物产率和组成的分析表明两种氧化剂的活性中间体性质相同。有人提出,HPC键合自由基物种是烃类氧化反应的原因。

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