ANILINE CHLORINATION
Maciej Przybyłek, Jerzy Gaca, Reaction of aniline with ammonium persulphate and concentrated hydrochloric acid: Experimental and DFT studies, 2012, Chemical Papers, 66 (7), 699–708. DOI: https://doi.org/10.2478/s11696-012-0163-1
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, 2,4,6-trichloroaniline, DFT
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AUTHORS (1)
CATEGORIES
- Chemical thermodynamics and energetics
- Computational chemistry
- Environmental biogeochemistry
- Other chemical sciences not elsewhere classified
- Organic chemical synthesis
- Organic chemistry not elsewhere classified
- Organic green chemistry
- Physical organic chemistry
- Theoretical quantum chemistry
- Reaction kinetics and dynamics
- Theoretical and computational chemistry not elsewhere classified