Fluorination of benzene with disubstituted N-fluoropyridinium salts in acetonitrile solution: a DFT study

  • Xia Du
  • Hui ZhangEmail author
  • Yuan Yao
  • Yang Lu
  • Aihua Wang
  • Yang Wang
  • Zesheng Li
Regular Article


In this work, fluorination activities of disubstituted N-fluoropyridinium salts on the substrate of benzene in acetonitrile solution have been investigated by density functional theory. At SMD-B3LYP/6-311G(d,p) level, geometry optimizations and frequency calculations of the reactants, transition states and products were carried out in 16 fluorination reaction channels. A high level of SMD-M06-2x/6-311++G(d,p) was used to correct the single-point energy of the stationary points based on the optimized structure. On the basis of 2-nitro-substituted N-fluoropyridinium salt, nitro, cyano, chloro, methoxy groups were substituted, respectively, at 3-,4-,5-,6-position on pyridine ring to further clarify the influence of substituents and substitution sites on fluorination activity. According to the obtained potential energy surface information and substituent effect analysis, the fluorination channel of 2,6-dinitro-substituted N-fluoropyridinium salt is the most effective because of the lowest reaction energy barrier; as a result among the 16 studied N-fluoropyridinium salts, 2,6-dinitro-substituted N-fluoropyridinium salt is the most promising fluorinating reagent.


Fluorination Disubstituted N-fluoropyridinium salts Transition state Acetonitrile 



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

Compliance with ethical standards

Conflict of interest

The author declares that they have no conflict interest.

Supplementary material

214_2019_2417_MOESM1_ESM.docx (61 kb)
S1 The geometry coordinates of reactants, transition states and products of 16 fluorination reactions optimized at SMD-B3LYP/6-311G (d,p) level (DOCX 61 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Xia Du
    • 1
  • Hui Zhang
    • 1
    Email author
  • Yuan Yao
    • 2
  • Yang Lu
    • 3
  • Aihua Wang
    • 1
  • Yang Wang
    • 1
  • Zesheng Li
    • 4
  1. 1.College of Material Science and Engineering, College of Chemical and Environmental EngineeringHarbin University of Science and TechnologyHarbinPeople’s Republic of China
  2. 2.MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical EngineeringHarbin Institute of TechnologyHarbinPeople’s Republic of China
  3. 3.College of Materials and Chemical EngineeringHeilongjiang Institute of TechnologyHarbinPeople’s Republic of China
  4. 4.Key Laboratory of Cluster Science of Ministry of Education and School of ChemistryBeijing Institute of TechnologyBeijingPeople’s Republic of China

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