Kinetic studies on the liquid‐phase catalytic oxidation of 4‐methyl guaiacol to vanillin

愈创木酚 化学 催化作用 反应机理 香兰素 吡啶 动力学 动力学分辨率 乙醚 传质 光化学 有机化学 色谱法 对映选择合成 物理 量子力学
作者
Qiyi Ma,Kejing Liu,Jianyong Mao,Kexian Chen,Liang Cheng,Jia Yao,Zhirong Chen,Haoran Li
出处
期刊:Canadian Journal of Chemical Engineering [Wiley]
卷期号:95 (8): 1544-1553 被引量:13
标识
DOI:10.1002/cjce.22798
摘要

Kinetic studies on the catalytic oxidation of 4‐methyl guaiacol using an ether intermediate towards vanillin in an agitator bubbling reactor were presented. The reaction was catalyzed by N,N′ ‐ethylenebis(acetylacetoniminato)‐cobalt(II) hexafluorophosphoric pyridinium (Co‐[Salen‐Py][PF 6 ] 2 ) under strong alkaline conditions with molecular oxygen as the terminal oxidant. The reaction scheme was demonstrated by a detailed analysis of the products distribution and control experiments. The intrinsic kinetics were explored based on our proposed p ‐benzoquinone methide mechanism, which revealed that the oxidation rate was determined by the oxidation of phenoxyl anion to phenoxyl radical catalyzed by LCo 3+ (O 2 ·) (L = [Salen‐Py][PF 6 ] 2 ). The kinetic experiments were performed under a mass transfer‐reaction condition due to the inevitable mass transfer resistance involved. Pseudo‐first order fast reactions were observed for both steps of the consecutive reactions based on the calculated physical and mass transfer parameters. The intrinsic kinetic equations for the first and second steps can be written as and , respectively, which are well in accordance with the mechanism. These conclusions are expected to give a clue for the mechanistic study, kinetic investigation, reaction optimization, and catalyst design for the oxidation of various p ‐cresols.
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