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Reaction of aniline with ammonium persulphate and concentrated hydrochloric acid: Experimental and DFT studies
Chemical Papers (2012)
  • Maciej Przybyłek, Nicolaus Copernicus University of Torun
  • Jerzy Gaca, University of Technology and Life Sciences in Bydgoszcz
Abstract
In this paper, the reaction of aniline with ammonium persulphate and concentrated HCl was studied. As a result of our experimental studies, 2,4,6-trichlorophenylamine was identified as the main product. This shows that a high concentration of HCl does not favour oxidative polymerisation of phenylamine, even though the ammonium persulphate/HCl system is widely used in polyaniline synthesis. On the basis of the experimental data and density functional theory for reaction path modelling, we proposed a mechanism for oxidative chlorination of aniline. We assumed that this reaction proceeded in three cyclically repeated steps; protonation of aniline, formation of singlet ground state phenylnitrenium cation, and nucleophilic substitution. In order to confirm this mechanism, kinetic, thermochemical, and natural bond orbital population analyses were performed.
Keywords
  • oxidative chlorination,
  • trichloroaniline,
  • DFT,
  • Reaction mechanisms,
  • Oxidation,
  • Chlorination,
  • Aniline,
  • Polyaniline synthesis,
  • ammonium persulphate,
  • hydrochloric acid
Publication Date
2012
DOI
10.2478/s11696-012-0163-1
Citation Information
Maciej Przybyłek and Jerzy Gaca. "Reaction of aniline with ammonium persulphate and concentrated hydrochloric acid: Experimental and DFT studies" Chemical Papers Vol. 66 Iss. 7 (2012) p. 699 - 708
Available at: http://works.bepress.com/maciej-przybyek/20/