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Understanding the Mechanism of Nitrobenzene Nitration with Nitronium Ion: A Molecular Electron Density Theory Study
Author(s) -
Cyrille Naouhou,
Idrice Adjieufack Abel,
Maraf Mbah Bake,
Charles Fon Abi,
Ibrahim Mbouombouo Ndassa,
RíosGutierrez Mar,
Domingo Luis Ramon
Publication year - 2019
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201903699
Subject(s) - nitrobenzene , nitration , chemistry , electrophile , nucleophile , density functional theory , photochemistry , electrophilic aromatic substitution , computational chemistry , reaction mechanism , ion , nitro compound , medicinal chemistry , nitro , organic chemistry , catalysis , alkyl
Abstract The nitration reaction of nitrobenzene with nitronium ion yielding ortho ‐, meta ‐ and para ‐dinitrobenzenes has been studied within the Molecular Electron Density Theory, using DFT computational methods at the B3LYP/6‐311G(d,p) level. This electrophilic aromatic substitution (EAS) reaction takes place through a two‐step mechanism involving the formation of a tetrahedric cation intermediate. The electrophilic attack of nitronium ion on nitrobenzene is the rate‐determining step of this EAS reaction, and consequently, responsible for the composition of the reaction mixture. The subsequent proton abstraction from the cation intermediate is barrierless. From the computed activation Gibbs free energies, a relationship 11.0 ( ortho ) : 87.3 ( meta ) : 1.7 ( para ) of the dinitrobenzenes is estimated, in clear agreement with the experimental outcome. The similar nucleophilic activation of the ortho and meta carbons of nitrobenzene makes it possible to question the hypothesis for the orientation in EAS reactions involving nucleophilically deactivated benzenes based on the relative stability of the tetrahedric cation intermediates.