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钴(Ⅱ)催化2-乙基-3-甲基吡嗪绿色氧化方法
引用本文:陈晶晶,王莹淑,余珺,成佳佳,郑辉东.钴(Ⅱ)催化2-乙基-3-甲基吡嗪绿色氧化方法[J].有机化学,2020(1):78-83.
作者姓名:陈晶晶  王莹淑  余珺  成佳佳  郑辉东
作者单位:福州大学材料科学与工程学院;福州大学石油化工学院;福州大学化学学院
基金项目:国家自然科学基金(No.21476049);福建省科技厅区域发展项目(No.2016H4023);福建省科技厅高校产学合作项目(No.2019H6010);福建省发改委产业技术联合创新专项(No.FG-2016005);福建省高等学校新世纪优秀人才支持计划(No.HG2017-17)资助项目。
摘    要:以过氧化叔丁醇为氧化剂,以钴(Ⅱ)与含N配体为催化体系催化氧化2-乙基-3-甲基吡嗪(EMP),提出一种具有放大应用前景的2-乙酰基-3-甲基吡嗪绿色制备方法.考察了过渡金属催化剂的种类、配体种类、溶剂、温度等反应条件对催化氧化过程的影响,在最优反应条件下EMP转化率可达58.8%, 2-乙酰基-3-甲基吡嗪(AMP)选择性92.2%.研究了该反应体系催化氧化EMP的反应机理,建立了该反应的拟均相反应动力学模型.在以上实验基础上,对该反应体系进行了放大实验研究,结果表明该新方法具有较好的工业放大前景,但反应温度的控制是放大过程的关键因素.

关 键 词:2-乙基-3-甲基吡嗪(EMP)  2-乙酰基-3-甲基吡嗪(AMP)  烯丙基氧化  反应机理  动力学  工艺放大

A Green and Scalable Cobalt(Ⅱ)-Catalyzed Oxidation of 2-Ethyl-3-methylpyrazine
Chen Jingjing,Wang Yingshu,Yu Jun,Cheng Jiajia,Zheng Huidong.A Green and Scalable Cobalt(Ⅱ)-Catalyzed Oxidation of 2-Ethyl-3-methylpyrazine[J].Chinese Journal of Organic Chemistry,2020(1):78-83.
Authors:Chen Jingjing  Wang Yingshu  Yu Jun  Cheng Jiajia  Zheng Huidong
Institution:(College of Materials Science and Engineering,Fuzhou University,Fuzhou 350108;College of Chemical Engineering,Fiuzhou Universit,Fuzhou 350108;College of Chemistry,Fruzhou Universiy,Fuzhou 350108)
Abstract:A green and scalable oxidation of 2-ethyl-3-methylpyrazine(EMP) by tert-butylhydroperoxide was investigated with a catalytic system of cobalt(Ⅱ) and N-containing ligand. The effects of catalyst, ligand, solvent and temperature were compared, and the catalysis system of cobalt(Ⅱ) acetylacetonate and 2,2-bipyridine gave the highest selectivity. Mechanistic study of this catalysis system suggested that the oxidation of EMP followed a free radical oxidation pathway, and a homogeneous reaction kinetics model was established to calculate the reaction rate constant and activation energy. The scale-up of the oxidation system was performed to check the scalability of the oxidation reaction, and the temperature control of the system was the key part of the process.
Keywords:2-ethyl-3-methylpyrazine(EMP)  2-acetyl-3-methylpyrazine(AMP)  allylic oxidation  reaction mechanism  kinetics  scale-up
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