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2020 , Vol. 40 >Issue 1: 78 - 83

DOI: https://doi.org/10.6023/cjoc201908001

研究论文

钴(II)催化2-乙基-3-甲基吡嗪绿色氧化方法

  • 陈晶晶 ,
  • 王莹淑 ,
  • 余珺 ,
  • 成佳佳 ,
  • 郑辉东
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  • a 福州大学材料科学与工程学院 福州 350108;
    b 福州大学石油化工学院 福州 350108;
    c 福州大学化学学院 福州 350108

收稿日期: 2019-08-01

  修回日期: 2019-09-02

  网络出版日期: 2019-09-18

基金资助

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.

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A Green and Scalable Cobalt(II)-Catalyzed Oxidation of 2-Ethyl-3-methylpyrazine

  • Chen Jingjing ,
  • Wang Yingshu ,
  • Yu Jun ,
  • Cheng Jiajia ,
  • Zheng Huidong
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  • a College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108;
    b College of Chemical Engineering, Fuzhou University, Fuzhou 350108;
    c College of Chemistry, Fuzhou University, Fuzhou 350108

Received date: 2019-08-01

  Revised date: 2019-09-02

  Online published: 2019-09-18

Supported by

Project supported by the National Natural Science Foundation of China (No. 21476049), the Regional Development Project of Fujian Province (No. 2016H4023), the University-Industry Cooperation Project of Fujian Province (No. 2019H6010), the Industrial Technology Joint Innovation Special Project of Fujian Province (No. FG-2016005) and the Program for New Century Excellent Talents in University of Fujian Province (No. HG2017-17).

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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

本文引用格式

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 , 40(1) : 78 -83 . DOI: 10.6023/cjoc201908001

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.

Key words： 2-ethyl-3-methylpyrazine (EMP); 2-acetyl-3-methylpyrazine (AMP); allylic oxidation; reaction mechanism; kinetics; scale-up

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