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第 36 卷第 7 期 精 细 化 工 Vol.36, No.7
201 9 年 7 月 FINE CHEMICALS J u l y 2019

有机电化学工业
2-氯-5-三氯甲基吡啶电化学脱氯合成

2-氯-5-氯甲基吡啶

*
郭利巧，韩方玉，李 斌，毛信表，徐颖华
（浙江工业大学 化学工程学院，绿色化学合成技术国家重点实验室培育基地，浙江 杭州 310032）

摘要：对 2-氯-5-三氯甲基吡啶（TCMP）采用电化学脱氯合成 2-氯-5-氯甲基吡啶（CCMP），考察了支持电解质、
阴极材料及目数、反应温度和电流密度等工艺条件对上述反应的影响和 TCMP 及其脱氯中间产物的脱氯电位。
结果表明：在乙酸锂、氯化锂、高氯酸锂、氯化铵、四丁基高氯酸铵中，乙酸锂为最佳支持电解质。各阴极材
料上 CCMP 收率从高到低次序为：铜＞铅＞石墨＞银＞锌＞镍。在优化条件下〔阴极液：含 10%（体积分数）
乙酸+5%（体积分数）水+0.2 mol/L 乙酸锂+0.1 mol/L TCMP 的甲醇溶液；阴极：80 目铜网；反应温度：30 ℃；
2
2
电流密度：前期电流密度为 333 A/m ，后期为 166 A/m 〕，0.1 mol/L TCMP 能较高效地转化为 CCMP，其收率
可达 56.9%。TCMP 脱氯成 2-氯-5-二氯甲基吡啶（DCMP）的电位明显正于 DCMP 脱氯成 CCMP 的脱氯电位，
后者与 CCMP 进一步脱氯的电位则非常接近。
关键词：2-氯-5-三氯甲基吡啶；2-氯-5-氯甲基吡啶；铜电极；电化学脱氯
中图分类号：TQ151.5 文献标识码：A 文章编号：1003-5214 (2019) 07-1408-07

Electrochemical Dechlorination of 2-Chloro-5-trichloromethylpyridine
into 2-Chloro-5-chloromethylpridine

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GUO Li-qiao, HAN Fang-yu, LI Bin, MAO Xin-biao, XU Ying-hua
（State Key Laboratory Breeding Base for Green Chemistry Synthesis Technology, College of Chemical Engineering,
Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China）

Abstract: Synthesis of 2-chloro-5-chloromethylpyridine (CCMP) by electrochemical dechlorination of
2-chloro-5-trichloromethylpyridine (TCMP) was carried out. The influences of supporting electrolyte,
cathode materials and their mesh number, reaction temperature and current density on the dechlorination
were investigated. The dechlorination potential of TCMP and its dechlorinated products were studied. The
results showed that among lithium acetate, lithium chloride, lithium perchlorate, ammonium chloride and
tetrabutyl ammonium perchlorate, lithium acetate was the best supporting electrolyte. The yield of CCMP
on each cathode material decreasedin the following order: Cu>Pb>graphite>Ag>Zn>Ni. Under optimized
process conditions [a methanol solution containing 10% (volume fraction) acetic acid+5% (volume fraction)
water+0.2 mol/L lithium acetate+0.1 mol/L TCMP as catholyte; 80 mesh coppermesh as cathode;reaction
2
2
temperature 30 ℃, current density being 333 A/m at the early stage of reaction and 166 A/m at the last
stage of reaction], 0.1 mol/L TCMP could be effectively dechlorinated into CCMP with a yield of 56.9%.
The dechlorination potential of TCMP into 2-chloro-5-dichloromethylpyridine (DCMP) was more positive
than that of DCMP into CCMP, and the later was almost close to that of further dechlorination of CCMP.
Key words: 2-chloro-5-trichloromethylpyridine; 2-chloro-5-chloromethylpyridine; copper electrode;
electrochemical dechlorination

2-氯-5-氯甲基吡啶（CCMP）是合成吡虫啉、 3-甲基吡啶或 2-氯-5-甲基吡啶为原料的选择性氯化
啶虫脒等新型绿色农药的关键中间体 [1-2] 。目前，以 是 CCMP 主要合成方法之一 [3-4] 。该法主要缺点是：

收稿日期：2018-12-25; 定用日期：2019-03-12; DOI: 10.13550/j.jxhg.20180947
基金项目：国家自然科学基金（21106133, 21576238）；浙江省自然科学基金（LY16B060012）
作者简介： 郭利巧（1993—），男，硕士生，E-mail：471054121@qq.com。联系人：徐颖华（1979—），男，副研究员，E-mail:xuyh@zjut.edu.cn。