有机化学 ›› 2020, Vol. 40 ›› Issue (1): 78-83.DOI: 10.6023/cjoc201908001 上一篇    下一篇

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a,b, 王莹淑b, 余珺b, 成佳佳c, 郑辉东b   

  1. 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 出版日期:2020-01-25 发布日期:2019-09-18
  • 通讯作者: 王莹淑 E-mail:1187562077@qq.com
  • 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.

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

Chen Jingjinga,b, Wang Yingshub, Yu Junb, Cheng Jiajiac, Zheng Huidongb   

  1. 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:2019-08-01 Revised:2019-09-02 Online:2020-01-25 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).

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 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