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Theoretical study on the fluorination of benzene with N-Fluoropyridinium salts in acetonitrile solution

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Abstract

The prominent roles of organofluorine compounds in various fields have aroused considerable interest in the development of new methods for carbon-fluorine bond formation. Electrophilic fluorination receives much attention. Density functional theory (DFT) was used to theoretically explore the fluorination activity of 12 N-Fluoropyridinium salts on the substrate of benzene in acetonitrile solution. Geometry optimizations and frequency calculations of the reactants, transition states, and products were performed at B3LYP/6-311G(d,p) level for the 12 fluorination reaction channels. Based on the optimized structure, all the stationary points have been corrected by the single point energy at a high-level of M06-2x/6-311++G (d,p). Four substituents were considered in this paper, they are nitro-, cyano-, chloro-, methoxy-, respectively. Three substituted sites (ortho-, meso-, para-) were also concluded. Based on the obtained potential energy surfaces information and analysis of substituent effect, the fluorination reaction channel of oNO2NFpyr is most efficient due to the lowest reaction energy barrier; therefore, oNO2NFpyr is a promising optimum fluorinating reagent among the studied 12 N-Fluoropyridinium salts.

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Acknowledgements

We thank the grid computing server provided by the Chinese Academy of Sciences.

Funding

This work is supported by the National Basic Research Program of China (2012CB723308), the National Natural Science Foundation of China (51337002 and 50977019), the Doctoral Foundation by the Ministry of Education of China (20112303110005), and the Science Foundation for Distinguished Young Scholar of Heilongjiang Province (JC201206).

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Authors and Affiliations

  1. College of Material Science and Engineering & College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin, 150080, People’s Republic of China

    Xia Du, Hui Zhang, Aihua Wang & Yang Wang

  2. MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, People’s Republic of China

    Yuan Yao

  3. College of Materials and Chemical Engineering, Heilongjiang Institute of Technology, Harbin, 150050, People’s Republic of China

    Yang Lu

  4. Key Laboratory of Cluster Science of Ministry of Education and School of Chemistry, Beijing Institute of Technology, Beijing, 100081, People’s Republic of China

    Zesheng Li

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  1. Xia Du
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  2. Hui Zhang
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  5. Aihua Wang
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Correspondence to Hui Zhang.

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ESM 1

The geometry coordinates of reactants, transition states and products of twelve fluorination reactions optimized at B3LYP/6-311G(d,p)level (DOC 98 kb)

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Du, X., Zhang, H., Yao, Y. et al. Theoretical study on the fluorination of benzene with N-Fluoropyridinium salts in acetonitrile solution. Struct Chem 29, 1601–1607 (2018). https://doi.org/10.1007/s11224-018-1135-z

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  • DOI: https://doi.org/10.1007/s11224-018-1135-z

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