以六甲基二硅胺烷为氮源一锅法电氧化醇制腈

doi:10.7503/cjcu20170245

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (1): 78.doi: 10.7503/cjcu20170245

以六甲基二硅胺烷为氮源一锅法电氧化醇制腈

范仲全^1,², 陈晨^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. 浙江工业大学分析测试中心, 杭州 310032

收稿日期:2017-04-19 出版日期:2018-01-10 发布日期:2017-12-21
作者简介:联系人简介: 李美超, 女, 博士, 教授, 博士生导师, 主要从事有机电合成研究. E-mail:limc@zjut.edu.cn
基金资助:
国家自然科学基金(批准号: 21376224)和浙江省自然科学基金(批准号: LY17B060007)资助

One-pot Electrochemical Oxidation Synthesis of Nitriles from Alcohols with Hexamethyldisilazane as the Nitrogen Source^†

FAN Zhongquan^1,², CHEN Chen^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:2017-04-19 Online:2018-01-10 Published:2017-12-21
Contact: LI Meichao E-mail:limc@zjut.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21376224) and the Natural Science Foundation of Zhejiang Province, China(No.LY17B060007)

摘要/Abstract

摘要：

以2,2,6,6-四甲基哌啶氮氧自由基(TEMPO)为电催化氧化媒介, 六甲基二硅胺烷(HMDS)为氮源, 在室温下实现了一锅法电氧化醇类化合物为腈类化合物. 采用循环伏安法和电化学原位红外光谱技术分别对TEMPO的电催化性能和一锅法电氧化历程进行了研究. 在优化条件下, 将该反应体系拓展到系列醇类化合物的电催化氧化中, 结果表明, 不同的醇类化合物, 特别是苄醇, 取得了较好的反应收率. 基于以上研究结果提出了可能的反应机理.

关键词: 2,2,6,6-四甲基哌啶氮氧自由基, 电氧化, 六甲基二硅胺烷, 醇, 腈

Abstract:

One-pot electrochemical oxidation synthesis of nitriles from alcohols was developed with hexamet-hyldisilazane(HMDS) as the nitrogen source, 2,2,6,6-tetramethylpiperidinyl-1-oxy(TEMPO) as the electrooxidation medium at the room temperature. The catalytic performance of TEMPO was studied by cyclic voltammetry, and the oxidation process was monitored by in situ FTIR analysis. Under the optimized conditions, the constant potential electrolysis of various alcohols, especially of benzylic alcohols, afforded the corresponding nitriles in moderate to excellent yields. Finally, the corresponding reaction mechanism of one-pot electrochemical oxidation of alcohols to nitriles was proposed.

Key words: 2,2,6,6-Tetramethylpiperidinyl-1-oxy(TEMPO), Electrooxidation, Hexamethyldisilazane(HMDS), Alcohol, Nitrile

中图分类号:

O621
O646

TrendMD:

范仲全, 陈晨, 沈振陆, 李美超. 以六甲基二硅胺烷为氮源一锅法电氧化醇制腈. 高等学校化学学报, 2018, 39(1): 78.

FAN Zhongquan, CHEN Chen, SHEN Zhenlu, LI Meichao. One-pot Electrochemical Oxidation Synthesis of Nitriles from Alcohols with Hexamethyldisilazane as the Nitrogen Source^†. Chem. J. Chinese Universities, 2018, 39(1): 78.

图/表 8

Scheme 1 One-pot electrochemical synthesis of nitriles from alcohols

Fig.1 Cyclic voltammograms recorded in 0.1 mol/L NaClO4-CH3CN solution in the presence of 1.0 mmol benzyl alcohol(a), 0.15 mmol TEMPO(b), 0.15 mmol TEMPO+1.0 mmol benzyl alcohol(c) and 0.15 mmol TEMPO+1.0 mmol benzyl alcohol+2.5 mmol HMDS+5.0 mmol AcOH(d)

Fig.2 In situ FTIR spectra collected on Pt electrode during the oxidation of 1mmol benzyl alcohol with 0.15 mmol TEMPO, 2.5 mmol HMDS and 5.0 mmol AcOH in 0.1 mol/L NaClO4-CH3CN solution

Table 1 Optimization of electrochemical synthesis of benzonitrilea

Entry	n_HMDS/mmol	x_TEMPO(molar fraction, %)	n_AcOH/mmol	Potential/V	Yield of benzonitrile^b(%)
1	2.5	15	3.0	1.5	27
2	2.5	15	4.0	1.5	88
3	2.5	15	5.0	1.5	95
4	1.0	15	5.0	1.5	62
5	3.0	15	5.0	1.5	97
6	2.5	5	5.0	1.5	58
7	2.5	10	5.0	1.5	84
8	2.5	15	0	1.5	0
9	2.5	15	5.0	1.2	12
10	2.5	15	5.0	1.8	60

Scheme 2 Scheme 2 Silylation reaction

Fig.3 Reaction profiles for electrochemical synthesis of benzonitrile from benzyl alcohol in 0.1 mol/L NaClO4-CH3CN solution containing 0.15 mmol TEMPO, 2.5 mmol HMDS and 5.0 mmol AcOH

Table 2 Electrochemical conversion of various alcohols to nitrilesa

Entry	Time/h	Conversion^b(%)	Yield^b(%)
1	15	>99	99
2	12	>99	98
3	12	>99	95
4	12	>99	>99
5	12	>99	96
6	12	>99	90
7	12	>99	92
8	12	>99	94
9	12	>99	97
10^c	20	>99	68
11^c	15	18
12^c	15	>99	9

Scheme 3 Plausible electrochemical reaction mechanism

参考文献 33

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以六甲基二硅胺烷为氮源一锅法电氧化醇制腈

One-pot Electrochemical Oxidation Synthesis of Nitriles from Alcohols with Hexamethyldisilazane as the Nitrogen Source^†

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Entry	n_HMDS/mmol	x_TEMPO(molar fraction, %)	n_AcOH/mmol	Potential/V	Yield of benzonitrile^b(%)
1	2.5	15	3.0	1.5	27
2	2.5	15	4.0	1.5	88
3	2.5	15	5.0	1.5	95
4	1.0	15	5.0	1.5	62
5	3.0	15	5.0	1.5	97
6	2.5	5	5.0	1.5	58
7	2.5	10	5.0	1.5	84
8	2.5	15	0	1.5	0
9	2.5	15	5.0	1.2	12
10	2.5	15	5.0	1.8	60

Entry	n_HMDS/mmol	x_TEMPO(molar fraction, %)	n_AcOH/mmol	Potential/V	Yield of benzonitrile^b(%)
1	2.5	15	3.0	1.5	27
2	2.5	15	4.0	1.5	88
3	2.5	15	5.0	1.5	95
4	1.0	15	5.0	1.5	62
5	3.0	15	5.0	1.5	97
6	2.5	5	5.0	1.5	58
7	2.5	10	5.0	1.5	84
8	2.5	15	0	1.5	0
9	2.5	15	5.0	1.2	12
10	2.5	15	5.0	1.8	60

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Entry	n_HMDS/mmol	x_TEMPO(molar fraction, %)	n_AcOH/mmol	Potential/V	Yield of benzonitrile^b(%)
1	2.5	15	3.0	1.5	27
2	2.5	15	4.0	1.5	88
3	2.5	15	5.0	1.5	95
4	1.0	15	5.0	1.5	62
5	3.0	15	5.0	1.5	97
6	2.5	5	5.0	1.5	58
7	2.5	10	5.0	1.5	84
8	2.5	15	0	1.5	0
9	2.5	15	5.0	1.2	12
10	2.5	15	5.0	1.8	60

Entry	n_HMDS/mmol	x_TEMPO(molar fraction, %)	n_AcOH/mmol	Potential/V	Yield of benzonitrile^b(%)
1	2.5	15	3.0	1.5	27
2	2.5	15	4.0	1.5	88
3	2.5	15	5.0	1.5	95
4	1.0	15	5.0	1.5	62
5	3.0	15	5.0	1.5	97
6	2.5	5	5.0	1.5	58
7	2.5	10	5.0	1.5	84
8	2.5	15	0	1.5	0
9	2.5	15	5.0	1.2	12
10	2.5	15	5.0	1.8	60

以六甲基二硅胺烷为氮源一锅法电氧化醇制腈

One-pot Electrochemical Oxidation Synthesis of Nitriles from Alcohols with Hexamethyldisilazane as the Nitrogen Source†

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参考文献 33

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One-pot Electrochemical Oxidation Synthesis of Nitriles from Alcohols with Hexamethyldisilazane as the Nitrogen Source^†

Entry	n_HMDS/mmol	x_TEMPO(molar fraction, %)	n_AcOH/mmol	Potential/V	Yield of benzonitrile^b(%)
1	2.5	15	3.0	1.5	27
2	2.5	15	4.0	1.5	88
3	2.5	15	5.0	1.5	95
4	1.0	15	5.0	1.5	62
5	3.0	15	5.0	1.5	97
6	2.5	5	5.0	1.5	58
7	2.5	10	5.0	1.5	84
8	2.5	15	0	1.5	0
9	2.5	15	5.0	1.2	12
10	2.5	15	5.0	1.8	60

Entry	n_HMDS/mmol	x_TEMPO(molar fraction, %)	n_AcOH/mmol	Potential/V	Yield of benzonitrile^b(%)
1	2.5	15	3.0	1.5	27
2	2.5	15	4.0	1.5	88
3	2.5	15	5.0	1.5	95
4	1.0	15	5.0	1.5	62
5	3.0	15	5.0	1.5	97
6	2.5	5	5.0	1.5	58
7	2.5	10	5.0	1.5	84
8	2.5	15	0	1.5	0
9	2.5	15	5.0	1.2	12
10	2.5	15	5.0	1.8	60