中国科学院化学所韩布兴团队报道了铜基催化剂环酮好氧氨氧化制二腈的研究。相关研究成果发表在2024年12月19日出版的《美国化学会杂志》。

己二腈（ADN）应用广泛，特别是在聚合物工业中。随着全球对ADN的大量需求和不断增长的需求，使用安全和丰富的起始材料有效生产ADN是非常可取的，但也是非常具有挑战性的。

该文中，研究发现，在温和的反应条件下（80°C，5 atm O₂），使用氨水作为氮源，O₂作为末端氧化剂，CuBr与1,10-邻菲咯啉（phen）结合可以有效地促进环己酮氨氧化反应生成ADN，产率>99%。此外，具有不同碳数和取代基的环酮也可以高产率转化为相应的二腈产物。详细的机理研究表明，反应是通过自由基介导的途径进行的，并讨论了ADN高选择性的原因。

该项研究为生产ADN和其他二腈产品提供了，一种新的、简单的、成本效益高的方法。

附：英文原文

Title: Aerobic Ammoxidation of Cyclic Ketones to Dinitrile Products with Copper-Based Catalysts

Author: Ziwei Zhao, Zhanrong Zhang, Qingling Xu, Shunhan Jia, Ying Wang, Wenli Yuan, Mingyang Liu, Huizhen Liu, Qinglei Meng, Pei Zhang, Bingfeng Chen, Haijun Yang, Buxing Han

Issue&Volume: December 19, 2024

Abstract: Adiponitrile (ADN) has wide applications, especially in the polymer industry. With the substantial and increasing global demand for ADN, effective production of ADN using safe and abundant starting materials is highly desirable but very challenging. Herein, we discovered that CuBr, combined with 1,10-phenanthroline (phen), could effectively promote the ammoxidation reaction of cyclohexanone to ADN with a yield of >99% using aqueous ammonia as the nitrogen source and O2 as the terminal oxidant under mild reaction conditions (80 °C, 5 atm O2). Moreover, cyclic ketones with various carbon numbers and substituent groups could also be converted into the corresponding dinitrile products with high yields. A detailed mechanistic study revealed that the reaction proceeded through a radical-mediated pathway, and the reason for the high selectivity to ADN was discussed. This study offers a new, simple, and cost-effective route to produce ADN and other dinitrile products.

DOI: 10.1021/jacs.4c14875

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c14875