高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (11): 2308-2313.doi: 10.7503/cjcu20190330

• 有机化学 • 上一篇    下一篇

伯胺在电催化媒介ABNO作用下的自氧化偶联反应

蔡延超1,2,牛鹏飞1,2,沈振陆1,李美超1,2,*()   

  1. 1. 浙江工业大学化学工程学院, 杭州 310032
    2. 分析测试中心, 杭州 310032
  • 收稿日期:2019-06-11 出版日期:2019-11-10 发布日期:2019-08-20
  • 通讯作者: 李美超 E-mail:limc@zjut.edu.cn
  • 基金资助:
    国家自然科学基金资助(21773211);国家自然科学基金资助(21776260)

Electrocatalytic Oxidative Coupling of Primary Amines with the Medium ABNO

CAI Yanchao1,2,NIU Pengfei1,2,SHEN Zhenlu1,LI Meichao1,2,*()   

  1. 1. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China
    2. Research Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310032, China
  • Received:2019-06-11 Online:2019-11-10 Published:2019-08-20
  • Contact: LI Meichao E-mail:limc@zjut.edu.cn
  • Supported by:
    ? Supported by the National Natural Science Foundation of China(21773211);? Supported by the National Natural Science Foundation of China(21776260)

摘要:

以9-氮杂双环[3.3.1]壬烷-N-氧基自由基(ABNO)为电催化媒介, 在NaClO4-MeCN溶液中伯胺通过自氧化偶联反应生成对应的亚胺. 采用循环伏安法研究了ABNO对伯胺的电催化性能. 在相同条件下, 与2,2,6,6-四甲基哌啶氮氧自由基相比, ABNO在伯胺的自氧化偶联反应中表现出更好的电催化反应活性. 采用电化学原位红外光谱技术分析其中间产物为Ph—CH=NH. 在优化的反应条件下, 一系列芳香伯胺可在ABNO电催化作用下自氧化偶联生成对应的亚胺, 产率较高.

关键词: 9-氮杂双环[3.3.1]壬烷-N-氧基自由基, 循环伏安法, 原位红外光谱, 电催化, 自氧化偶联

Abstract:

In the NaClO4-MeCN solution, an electrochemical oxidative coupling of primary amines was developed with the electrocatalytic medium 9-azabicyclo[3.3.1]nonane-N-oxyl(ABNO). The electrocatalytic performance of ABNO for the primary amines was studied by cyclic voltammetry. As compared with 2,2,6,6-tetramethylpiperidine nitroxyl radical under similar conditions, ABNO showed higher electrocatalytic perfor-mance in the oxidation coupling reaction. The Ph—CH=NH was analyzed as the intermediate by electrochemical in situ FTIR. Under the optimized conditions, a series of aromatic primary amines underwent the electrochemical oxidative coupling to form corresponding imines in good to excellent yields with the ABNO as the electrocatalytic medium.

Key words: 9-Azabicyclo[3.3.1]nonane-N-oxyl, Cyclic voltammetry, in situ FTIR spectrum, Electro-catalysis, Oxidative coupling

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