Open AccessTransetherification of 2,4-dimethoxynitrobenzene by aromatic nucleophilic substitution
Author(s) -
Jang Ho Song,
Hae Ju Kang,
Jung Wuk Lee,
Michelle A. Wenas,
Seung Hwarn Jeong,
TaeHo Lee,
Kyungsoo Oh,
Kyung Hoon Min
Publication year - 2017
Publication title -
plos one
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.99
H-Index - 332
ISSN - 1932-6203
DOI - 10.1371/journal.pone.0183575
Subject(s) - nucleophilic substitution , nucleophilic aromatic substitution , chemistry , aniline , yield (engineering) , medicinal chemistry , nucleophile , toluene , dimethoxyethane , substitution reaction , alkoxy group , selectivity , acid hydrolysis , leaving group , organic chemistry , hydrolysis , catalysis , materials science , alkyl , electrode , electrolyte , metallurgy
In view of the few reports concerning aromatic nucleophilic substitution reactions featuring an alkoxy group as a leaving group, the aromatic nucleophilic substitution of 2,4-dimethoxynitrobenzene was investigated with a bulky t -butoxide nucleophile under microwave irradiation. The transetherification of 2,4-dimethoxynitrobenezene with sodium t -butoxide under specific conditions, namely for 20 min at 110°C in 10% dimethoxyethane in toluene, afforded the desired product in 87% yield with exclusive ortho -selectivity. A variety of reaction conditions were screened to obtain the maximum yield. The aromatic nucleophilic substitution of 2,4-dimethoxynitrobenzene with t -butoxide should be carried out under controlled conditions in order to avoid the formation of byproducts, unlike that of dihalogenated activated benzenes. Among the formed byproducts, a major compound was elucidated as 2,4-dimethoxy- N -(5-methoxy-2-nitrophenyl)aniline by X-ray crystallography.