Electrophilic aromatic nitration: understanding its mechanism and substituent effects.
Electrophilic aromatic nitration: understanding its mechanism and substituent effects.
复制标题
DOI：
10.1021/jo0609475
复制
发表时间：
2006-06
期刊：
影响因子：
--
通讯作者：
Jorge Freire de Queiroz;J. Carneiro;A. Sabino;R. Sparrapan;M. Eberlin;P. Esteves
中科院分区：
文献类型：
--
作者：
Jorge Freire de Queiroz;J. Carneiro;A. Sabino;R. Sparrapan;M. Eberlin;P. Esteves
对裸态（NO2+）和单溶剂化（CH3NO2.NO2+）硝鎓离子与几种单取代芳香族化合物的反应进行了理论计算和气相质谱研究。根据这些研究，我们提出了基于单电子转移（SET）机制的区域选择性通用模型和亲电芳香硝化的替代机制方案。该方案将 SET 和极性（Ingold-Hughes）机制视为连续通路中的极端，这两种机制的发生和程度主要取决于芳香族化合物将电子转移到 NO2+ 的能力或缺乏能力。
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+.