伯胺在电催化媒介ABNO作用下的自氧化偶联反应

doi:10.7503/cjcu20190330

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

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. 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 Yanchao^1,²,NIU Pengfei^1,²,SHEN Zhenlu¹,LI Meichao^1,^2,^*()

^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/Abstract

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

中图分类号:

O621

TrendMD:

蔡延超,牛鹏飞,沈振陆,李美超. 伯胺在电催化媒介ABNO作用下的自氧化偶联反应. 高等学校化学学报, 2019, 40(11): 2308.

CAI Yanchao,NIU Pengfei,SHEN Zhenlu,LI Meichao. Electrocatalytic Oxidative Coupling of Primary Amines with the Medium ABNO ^†. Chem. J. Chinese Universities, 2019, 40(11): 2308.

图/表 9

Scheme 1 Electrocatalytic oxidative coupling of benzylamine with the medium ABNO

Fig.1 Cyclic voltammograms of Pt electrode in 0.1 mol/L NaClO4-MeCN solution with 1.0 mmol benzylamine(a), 0.1 mmol ABNO(b) and 0.1 mmol ABNO+1.0 mmol benzylamine(c) at the scan rate of 50 mV/s

Scheme 2 Mutual transformation of ABNO and ABNO+

Fig.2 Cyclic voltammograms of Pt electrode in 0.1 mol/L NaClO4-MeCN solution with 0.1 mmol TEMPO(a) and 0.1 mmol TEMPO+1.0 mmol benzylamine(b) at the scan rate of 50 mV/s

Fig.3 In situ FTIR spectra collected on Pt electrode in 0.1 mol/L NaClO4-MeCN solution with 0.1 mmol ABNO and 1.0 mmol benzylamine at different potential

Fig.4 In situ FTIR spectra collected on Pt electrode in 0.1 mol/L NaClO4-MeCN solution with 0.1 mmol ABNO and 1.0 mmol benzylamine at 200 mV

Scheme 3 Proposed reaction mechanism for benzylamine to N-benzyl-1-phenylmethanimine

Table 1 Comparison of different methods for the detection of AFB1

Entry	Catalyst	E/mV	Yield(%)^b	Entry	Catalyst	E/mV	Yield(%)^b
1	ABNO	600	76	6	ABNO^c	800	60
2	ABNO	700	89	7	—	800	Trace
3	ABNO	800	98	8	—	1500	4
4	ABNO	900	94	9	TEMPO	800	80
5	ABNO	1000	94

Table 2 Electrochemical oxidation of amines to imines catalyzed by ABNOa

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伯胺在电催化媒介ABNO作用下的自氧化偶联反应

Electrocatalytic Oxidative Coupling of Primary Amines with the Medium ABNO ^†

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伯胺在电催化媒介ABNO作用下的自氧化偶联反应

Electrocatalytic Oxidative Coupling of Primary Amines with the Medium ABNO †

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Electrocatalytic Oxidative Coupling of Primary Amines with the Medium ABNO ^†