Zhao Ziwei, Zhang Zhanrong, Xu Qingling, Jia Shunhan, Wang Ying, Yuan Wenli, Liu Mingyang, Liu Huizhen, Meng Qinglei, Zhang Pei, Chen Bingfeng, Yang Haijun, Han Buxing
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China.
J Am Chem Soc. 2025 Jan 8;147(1):1155-1161. doi: 10.1021/jacs.4c14875. Epub 2024 Dec 19.
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 O as the terminal oxidant under mild reaction conditions (80 °C, 5 atm O). 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.
己二腈（ADN）有广泛的应用，尤其是在聚合物工业中。随着全球对ADN的需求大幅且不断增加，使用安全且丰富的起始原料有效生产ADN是非常必要的，但极具挑战性。在此，我们发现，在温和的反应条件（80℃，5个大气压的氧气）下，溴化铜与1,10 - 菲咯啉（phen）结合，能有效地促进环己酮氨氧化反应生成ADN，以氨水作为氮源，氧气作为终端氧化剂，产率>99%。此外，具有不同碳原子数和取代基的环状酮也能高产率地转化为相应的二腈产物。详细的机理研究表明该反应通过自由基介导的途径进行，并讨论了对ADN具有高选择性的原因。本研究提供了一种生产ADN和其他二腈产物的新的、简单且具有成本效益的路线。
