摘要
为解决1-氨基-4-溴蒽醌-2-磺酸(溴氨酸)芳胺化反应催化剂Cu+易失活、影响溴氨酸芳胺化反应效率的问题,设计并制备了一种促Cu^(2+)释放的含Mn碱式碳酸铜电催化剂,并在两电极体系中采用电化学还原方法进行溴氨酸芳胺化反应。利用循环伏安法(CV)、扫描电镜(SEM)、电化学阻抗谱(EIS)等研究了还原电压、电催化剂组成对芳胺化反应的影响,并进行了底物拓展和放大实验。结果表明,所制备的含Mn碱式碳酸铜电催化剂能有效促进Cu^(2+)释放,并在-0.4 V的还原电压下被还原为Cu+原位催化溴氨酸与2,4,6-三甲基-1,3-二氨基苯磺酸(M酸)的芳胺化,反应收率达93%,脱溴副产仅3%。对于苯胺、间乙酰氨基苯胺及对乙酰氨基苯胺这三种底物,本策略均能使其芳胺化反应收率达90%以上。此外,在20 g(溴氨酸)级的放大反应中,使溴氨酸与M酸的芳胺化反应取得90%的收率,具有优异的放大制备潜力。
In order to solve the problem of easy inactivation of Cu+in 1-amino-4-bromoanthraquinone-2-sulfonic acid(bromaminic acid)amination reaction,a basic copper carbonate electrocatalyst containing Mn to promote Cu^(2+)release was designed and prepared,and the amination of bromaminic acid was carried out by electrochemical reduction method in a two-electrode system.The effects of reduction voltage and electrocatalyst composition on the arylation reaction were studied by cyclic voltammetry(CV),scanning electron microscopy(SEM),electrochemical impedance spectroscopy(EIS),and substrate expansion and amplification experiments were carried out.The results showed that the prepared basic copper carbonate electrocatalyst containing Mn could effectively promote the release of Cu^(2+),and could be reduced to Cu+in situ to catalyze the amination of bromaminic acid with 2,4,6-trimethyl-1,3-diaminobenzenesulfonic acid(M acid)at a reduction voltage of-0.4 V,with the yield reaching 93%and the debromination byproduct only 3%.The amination yields of aniline,3-acetylaminoaniline and 4-acetylaminoaniline could reach more than 90%by this strategy.In addition,the amination reaction of bromaminic acid with M acid in 20 g(bromaminic acid)grade achieved 90%yield,which has excellent amplification potential.
作者
唐志成
王添巍
吕荣文
张淑芬
TANG Zhicheng;WANG Tianwei;LYU Rongwen;ZHANG Shufen(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116012,Liaoning,China)
出处
《化工学报》
北大核心
2025年第11期5923-5932,共10页
CIESC Journal
基金
国家自然科学基金项目(22238002)
大连理工大学研究与创新团队基金项目(DUT2022TB10)
中央高校基本科研业务费专项资金项目(DUT22LAB610)。
关键词
溴氨酸芳胺化
碱式碳酸铜
成核
一价铜离子
电化学还原
沉淀
溶解性
amination of bromaminic acid
basic copper carbonate
nucleation
monovalent copper ion
electrochemical reduction
precipitation
solubility
