CHROMIC ACID OXIDATION OF AROMATIC ALDEHYDES - SOME OBSERVATIONS CONCERNING OXIDATION BY CHROMIUM SPECIES OF INTERMEDIATE VALENCE
CHROMIC ACID OXIDATION OF AROMATIC ALDEHYDES - SOME OBSERVATIONS CONCERNING OXIDATION BY CHROMIUM SPECIES OF INTERMEDIATE VALENCE
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DOI：
10.1021/ja00873a031
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发表时间：
1962-01-01
影响因子：
15
通讯作者：
RICHARDSON, WH
中科院分区：
文献类型：
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作者：
WIBERG, KB;RICHARDSON, WH
通过竞争技术测定了中间价铬物质氧化苯甲醛的取代基效应和动力学同位素效应。已发现三苯乙醛的氧化产生三苯乙酸、三苯甲醇和一氧化碳作为主要产物。从反应的可能机制方面讨论了结果的重要性。许多铬酸氧化的第一步似乎涉及产生铬（IV）的双电子转移。 2 铬(IV) 可以与铬(VI) 反应生成两个铬-(V)，也可以与有机底物反应生成铬(III) 和一个自由基。后者可能会与铬（VI）反应生成氧化的有机物质和铬-（V），这反过来又会引起进一步的氧化。 3 在任何一种情况下，三分之二的净反应将通过铬物质的氧化进行
The effect of substituents and the kinetic isotope effect for the oxidation of benzaldehyde by the chromium species of intermediate valencehas been determined by a competition technique. The oxidation of triphenylacetaldehyde has been found to give triphenylacetic acid, triphenylcarbinol and carbon monoxide as the main products. The significance of the results is discussed in terms of the possible mechanisms for the reaction.The first step in many chromic acid oxidations appears to involve a two-electron transfer giving chromium (IV). 2 The chromium (IV) may either react with chromium (VI) to give two chromium-(V), or it mayreact with the organic substrate to give chromium (III) and a free radical. The latter would probably react with chromium (VI) to give the oxidized organic species andchromium-(V), which would in turn effect further oxidation. 3 In either case, two-thirds of the net reaction will proceed via oxidation by the chromium species