18102-29-9Relevant articles and documents
Studies on photochemical reaction of air pollutants. X. Identification of nitrophenols in suspended particulates
Nojima,Kawaguchi,Ohya,et al.
, p. 1047 - 1051 (1983)
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Eco-Friendly Methodology for the Formation of Aromatic Carbon–Heteroatom Bonds by Using Green Ionic Liquids
Richards, Kenza,Petit, Eddy,Legrand, Yves-Marie,Grison, Claude
supporting information, p. 809 - 814 (2020/11/30)
A new sustainable method is reported for the formation of aromatic carbon–heteroatom bonds under solvent-free and mild conditions (no co-oxidant, no strong acid and no toxic reagents) by using a new type of green ionic liquid. The bromination of methoxy arenes was chosen as a model reaction. The reaction methodology is based on only using natural sodium bromine, which is transformed into an electrophilic brominating reagent within an ionic liquid, easily prepared from the melted salt FeCl3 hexahydrate. Bromination reactions with this in-situ-generated reagent gave good yields and excellent regioselectivity under simple and environmentally friendly conditions. To understand the unusual bromine polarity reversal of sodium bromine without any strong oxidant, the molecular structure of the reaction medium was characterised by Raman and direct infusion electrospray ionisation mass spectroscopy (ESI-MS). An extensive computational investigation using density functional theory methods was performed to describe a mechanism that suggests indirect oxidation of Br? through new iron adducts. The versatility of the methodology was successively applied to nitration and thiocyanation of methoxy arenes using KNO3 and KSCN in melted hexahydrated FeCl3.
I. Photochemical nitration of methoxybenzenes from charge-transfer complexes with tetranitromethane
Sankararaman, S.,Kochi, J. K.
, p. 278 - 285 (2007/10/02)
The direct irradiation of the charge-transfer (CT) absorption band of the 1/1 electron donor-acceptor complexes of dimethoxybenzenes with tetranitromethane leads to aromatic nitration with a high quantum yield.The analogous methoxytoluenes under the same photochemical conditions are converted in equally high yields to products of aromatic trinitromethylation.This dichotomy with different methoxybenzenes (ArH) is discussed within the context of the common reactive intermediates derived from the CT excitation of the complex.The subsequent interactions of the geminate fragments, i.e., +., C(NO2)3-, .NO2>, by radical-pair and ion-pair annihilation represent a unifying mechanism for the CT photochemistry leading to aromatic nitration and trinitromethylation.
