Electrophilic Aromatic Nitration: Understanding Its Mechanism and Substituent Effects
The Journal of Organic Chemistry2006Vol. 71(16), pp. 6192–6203
Citations Over TimeTop 13% of 2006 papers
Jorge Freire de Queiroz, José Walkimar de M. Carneiro, Adão A. Sabino, Regina Sparrapan, Marcos N. Eberlin, Pierre M. Esteves
Abstract
Theoretical calculations and gas-phase mass spectrometric studies were performed for the reaction of the naked (NO2+) and monosolvated (CH3NO2.NO2+) nitronium ion with several monosubstituted aromatic compounds. From these studies, we propose a general model for regioselectivity based on the single-electron transfer (SET) mechanism and an alternative mechanistic scheme for electrophilic aromatic nitration. This scheme considers the SET and the polar (Ingold-Hughes) mechanisms as extremes in a continuum pathway, the occurrence and extents of both mechanisms being governed mainly by the ability, or lack of ability, of the aromatic compound to transfer an electron to NO2+.
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