Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Proc Natl Acad Sci U S A. 2022 May 24;119(21):e2122425119. doi: 10.1073/pnas.2122425119. Epub 2022 May 19.
Aryl chlorides are among the most versatile synthetic precursors, and yet inexpensive and benign chlorination techniques to produce them are underdeveloped. We propose a process to generate aryl chlorides by chloro-group transfer from chlorophenol pollutants to arenes during their mineralization, catalyzed by Cu(NO3)2/NaNO3 under aerobic conditions. A wide range of arene substrates have been chlorinated using this process. Mechanistic studies show that the Cu catalyst acts in cooperation with NOx species generated from the decomposition of NaNO3 to regulate the formation of chlorine radicals that mediate the chlorination of arenes together with the mineralization of chlorophenol. The selective formation of aryl chlorides with the concomitant degradation of toxic chlorophenol pollutants represents a new approach in environmental pollutant detoxication. A reduction in the use of traditional chlorination reagents provides another (indirect) benefit of this procedure.
芳基氯化物是用途最广泛的合成前体之一，但用于生产它们的廉价且无害的氯化技术仍欠发达。我们提出了一种通过在有氧条件下，使用 Cu(NO3)2/NaNO3 作为催化剂，从氯苯酚污染物向芳烃转移氯基团，从而生成芳基氯化物的方法。该方法已成功用于多种芳烃底物的氯化。机理研究表明，Cu 催化剂与 NaNO3 分解生成的 NOx 物种协同作用，调节氯自由基的生成，从而介导芳烃的氯化以及氯苯酚的矿化。有毒氯苯酚污染物的脱毒过程中，芳基氯化物的选择性形成是一种新的方法。与传统氯化试剂的使用减少相比，这一过程还提供了另一个（间接）好处。
