SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2022, Vol. 44 ›› Issue (4): 124-130.DOI: 10.1016/j.cjche.2021.06.017

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Experimental and theoretical study on N-hydroxyphthalimide and its derivatives catalyzed aerobic oxidation of cyclohexylbenzene

Yufei Yang1, Jieyi Ma1, Junyan Wu1, Weixia Zhu1, Yadong Zhang1,2   

  1. 1 School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China;
    2 Jiyuan Research Institute, Zhengzhou University, Jiyuan 459000, China
  • Received:2020-09-17 Revised:2021-05-12 Online:2022-06-18 Published:2022-04-28
  • Contact: Yadong Zhang,E-mail:zhangyadong2016@163.com
  • Supported by:
    This work was financially supported by the National Natural Science Foundation of China (21706240). We would like to acknowledge all the reviewers for their valuable suggestions and Prof. Fuqiang Zhang of School of Chemistry and Material Science in Shanxi Normal University for DFT calculations.

Experimental and theoretical study on N-hydroxyphthalimide and its derivatives catalyzed aerobic oxidation of cyclohexylbenzene

Yufei Yang1, Jieyi Ma1, Junyan Wu1, Weixia Zhu1, Yadong Zhang1,2   

  1. 1 School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China;
    2 Jiyuan Research Institute, Zhengzhou University, Jiyuan 459000, China
  • 通讯作者: Yadong Zhang,E-mail:zhangyadong2016@163.com
  • 基金资助:
    This work was financially supported by the National Natural Science Foundation of China (21706240). We would like to acknowledge all the reviewers for their valuable suggestions and Prof. Fuqiang Zhang of School of Chemistry and Material Science in Shanxi Normal University for DFT calculations.

Abstract: The liquid phase oxidation of cyclohexylbenzene (CHB) is a new green synthetic approach to cyclohexylbenzene-1-hydroperoxide (CHBHP), a key intermediate for preparing phenol and cyclohexanone. In this work, aryl-substituted (Cl and Br) derivatives of N-hydroxyphthalimide (NHPI) were synthesized and their catalytic performances for CHB oxidation were studied. In addition, geometric optimization and transition state search were performed using DFT calculations. Both experimental and theoretical studies have proven that chloro-substitution on NHPI can significantly improve its catalytic effects on the oxidation of CHB by oxygen. Compared with NHPI, CHB conversion and selectivity of CHBHP over Cl4NHPI were increased by 10.47% and 13.24%. The strategy of aryl -substituting NHPI with halogen atoms proposed in this study would provide a potential way to the development of new NHPI-based catalysts for aerobic oxidation reactions.

Key words: N-hydroxyphthalimide, Aryl-substituted derivative, Cyclohexylbenzene, Oxidation, Radical

摘要: The liquid phase oxidation of cyclohexylbenzene (CHB) is a new green synthetic approach to cyclohexylbenzene-1-hydroperoxide (CHBHP), a key intermediate for preparing phenol and cyclohexanone. In this work, aryl-substituted (Cl and Br) derivatives of N-hydroxyphthalimide (NHPI) were synthesized and their catalytic performances for CHB oxidation were studied. In addition, geometric optimization and transition state search were performed using DFT calculations. Both experimental and theoretical studies have proven that chloro-substitution on NHPI can significantly improve its catalytic effects on the oxidation of CHB by oxygen. Compared with NHPI, CHB conversion and selectivity of CHBHP over Cl4NHPI were increased by 10.47% and 13.24%. The strategy of aryl -substituting NHPI with halogen atoms proposed in this study would provide a potential way to the development of new NHPI-based catalysts for aerobic oxidation reactions.

关键词: N-hydroxyphthalimide, Aryl-substituted derivative, Cyclohexylbenzene, Oxidation, Radical