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首页> 外文期刊>Physical chemistry chemical physics: PCCP >The role of onium salts in the oxidation of hydrocarbons by O-2 catalysed by cationic phase-transfer reagents
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The role of onium salts in the oxidation of hydrocarbons by O-2 catalysed by cationic phase-transfer reagents

机译：阳离子相转移剂在O-2催化下鎓盐在烃类氧化中的作用

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Experimental and theoretical evidence is presented that cationic phase-transfer catalysts promote the homolytic decomposition of hydroperoxide initiators into radicals, this being a fundamental step in the catalysis of the oxidation of hydrocarbons by O-2. Such decomposition of the model substance tert-butyl hydroperoxide (t-BHP) results in O-2, tert-butanol (90-95%) di-tert-butyl peroxide (5-10%) and traces of CO2. The stoichiometric ratio Delta[t-BHP]/Delta O-2 was found to have a value of 2, independently of the nature of the counteranion present. It is assumed that the interaction between hydroperoxide and onium cation is mainly electrostatic in nature and that its effectivity depends on the positive charge density on the onium cation, which is controlled by the nature and dimensions of the counteranion. The role of water in the decomposition of t-BHP is also elucidated. [References: 17]
机译：实验和理论证据表明，阳离子相转移催化剂促进氢过氧化物引发剂均解分解为自由基，这是O-2催化烃氧化的基本步骤。模型物质叔丁基过氧化氢（t-BHP）的这种分解会产生O-2，叔丁醇（90-95％）二叔丁基过氧化物（5-10％）和痕量的CO2。发现化学计量比Delta [t-BHP] / Delta O-2的值为2，与存在的抗衡阴离子的性质无关。假定氢过氧化物和鎓阳离子之间的相互作用本质上主要是静电的，并且其有效性取决于鎓阳离子上的正电荷密度，该密度由抗衡阴离子的性质和尺寸控制。还阐明了水在t-BHP分解中的作用。 [参考：17]

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