基于芳香胺化合物的光催化脱卤加氢

引用本文: 孟涤, 朱倩, 魏燕, 甄胜利, 段苒, 陈春城, 宋文静, 赵进才. 基于芳香胺化合物的光催化脱卤加氢[J]. 催化学报, 2020, 41(10): 1474-1479. doi: 10.1016/S1872-2067(20)63582-3 shu

Citation: Di Meng, Qian Zhu, Yan Wei, Shengli Zhen, Ran Duan, Chuncheng Chen, Wenjing Song, Jincai Zhao. Light-driven activation of carbon-halogen bonds by readily available amines for photocatalytic hydrodehalogenation[J]. Chinese Journal of Catalysis, 2020, 41(10): 1474-1479. doi: 10.1016/S1872-2067(20)63582-3 shu

基于芳香胺化合物的光催化脱卤加氢

a 中国科学院化学研究所光化学重点实验室, 中国科学院分子科学科教融合卓越中心, 北京 100190;
b 中国科学院大学, 北京 100049;
c 北京高能时代环境技术股份有限公司, 北京 100095
基金项目:
国家重点研发计划（2018YFA0209302）；国家自然科学基金（21590811，21677148，21827809，21922609）；中国科学院前沿科学重点研究计划（QYZDY-SSW-SLH028）.

摘要: 近年来，光催化活化碳卤键已经成为构筑新化学键的有力方法.其基本原理在于利用光激发产生的高活性激发态或中间物种，经由电子转移过程实现碳卤键的断裂产生碳自由基和卤离子（C-X+e^- → C·+X^-）.碳自由基通过加氢或者或亲电进攻等途径完成反应，实现碳卤键到碳氢、碳碳等化学键的转化.目前已报道的用于活化碳卤键的光催化剂包括过渡金属（如钌、铱）配合物，过渡金属盐（Ce^IIICl₆^3-）、有机小分子光（二氢苯二嗪、苯基吩噻嗪、苝酰亚胺以及芘类衍生物分子）等.
本工作中我们开发了基于小分子芳香胺，包括N，N，N'，N'-四甲基对苯二胺（TMPD）与N，N，N'，N'-四甲基联苯胺（TMB）等作为光催化剂实现高惰性芳香卤代化合物脱卤加氢的催化体系.荧光强度/寿命测试表明芳香胺的强还原性单重激发态可通过扩散控制的电子转移实现惰性卤代底物（氯苯，六氟苯等）中碳卤键的解离；并且原位顺磁共振直接观察到了这一步骤产生的芳基自由基以及TMPD正离子自由基；自由基捕获实验也为解离电子转移活化碳卤键提供了进一步的支持.
芳香胺分子在计量反应条件下可同时作为光敏剂和电子/氢给体可在紫外光照下（λ> 360nm）实现芳香卤代化合物的脱卤加氢，并表现出较高的转化率和选择性：溴苯乙酮（86%，90%）、六氟苯（91%，五氟苯26%/1，2，4，5-四氟苯17%）、氯苯（63%，80%）.引入N，N-二异丙基乙二胺（DIPEA）作为电子给体，能够还原芳香胺正离子自由基完成催化剂循环，DIPEA同时作为氢给体参与芳基自由基加氢.我们在催化反应条件下（5 mol%芳香胺）调研了脱卤加氢的卤代底物范畴.以TMPD为例，对溴苯乙酮光照4小时后可得到90%脱溴产物；相对难还原的溴苯经过6小时光反应脱卤达到37%.六氟苯经过24小时反应后可以脱去1-2个氟，生成五氟苯（25%）和1，2，4，5-四氟苯（50%）.对氯苯甲酸甲酯在7.5小时反应后得到了72%的加氢产物；而对于更难还原的氯苯两小时光照可生成约40%的脱氯产物（增加TMPD用量可进一步提高脱氯效率至63%）.TMPD催化杂环卤代化合物脱卤的效果也较好，如3-溴噻吩（18h，41%）和3-溴-4甲基吡啶（25h，60%）.另外TMB和4，4'，4"-（1，3，5-三嗪-2，4，6-三基）三苯胺作为光催化剂也可实现脱卤加氢.
我们进一步研究了典型持久性有机污染物2，2'，4，4'-四溴联苯醚（BDE47）的光催化脱溴反应，30小时光照后脱溴效率可达83%，并且产生了40%的全脱溴产物联苯醚.脱溴中间产物分布表明邻位溴脱除速率高于对位溴.这一结果与解离电子转移活化碳卤键的机理一致.
总而言之，我们的工作表明小分子芳香胺光敏剂的激发态能够通过扩散控制的电子转移活化碳卤键.它们作为光催化剂可实现多种有机卤化物的脱卤加氢.

关键词:

English

Light-driven activation of carbon-halogen bonds by readily available amines for photocatalytic hydrodehalogenation

a Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China;
b University of Chinese Academy of Sciences, Beijing, 100049, China;
c Beijing GeoEnviron Engineering&Technology, lnc., Beijing, 100095, China
Received Date: 20 January 2020
Revised Date: 05 March 2020
Fund Project:
This work was supported by the National Key R&D Program of China (2018YFA0209302), National Natural Science Foundation of China (21590811, 21677148, 21827809, 21922609), the Key Research Program of Frontier Sciences (QYZDY-SSW-SLH028) of the Chinese Academy of Sciences.

Abstract: A straightforward protocol using readily available aromatic amines, N,N,N',N'-tetramethyl-p-phenylenediamine or N,N,N',N'-tetramethylbenzidine, as photocatalysts was developed for the efficient hydrodehalogenation of organic halides, such as 4'-bromoacetophenone, polyfluoroarenes, cholorobenzene, and 2,2',4,4'-tetrabromodiphenyl ether(a resistant and persistent organic pollutant). The strongly reducing singlet excited states of the amines enabled diffusion-controlled dissociative electron transfer to effectively cleave carbon-halogen bonds, followed by radical hydrogenation. Diisopropylethylamine served as the terminal electron/proton donor and regenerated the amine sensitizers.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

基于芳香胺化合物的光催化脱卤加氢

English

Light-driven activation of carbon-halogen bonds by readily available amines for photocatalytic hydrodehalogenation

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

基于芳香胺化合物的光催化脱卤加氢

English

Light-driven activation of carbon-halogen bonds by readily available amines for photocatalytic hydrodehalogenation

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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