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Oxidative Nucleophilic Substitution of Hydrogen in Nitroarenes
Author(s) -
Makosza Mieczyslaw,
Staliński Krzysztof
Publication year - 1997
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19970031217
Subject(s) - carbanion , chemistry , adduct , nitrobenzene , medicinal chemistry , nitro , nucleophile , nucleophilic substitution , yield (engineering) , iodide , hydrogen , organic chemistry , photochemistry , catalysis , alkyl , materials science , metallurgy
Abstract Carbanions of 2‐phenylpropionitrile were found to add to nitroarenes in liquid ammonia to form σ H adducts, which were oxidized with KMnO 4 to yield products of oxidative nucleophilic substitution of hydrogen (ONSH) in the position para to the nitro group. Treatment of the carbanion‐nitroarene system with methyl iodide at ‐70°C indicated that the addition proceeds almost to completion. Thus, for the first time, the persistence of σ H adducts, formed between free anions and mononitroarenes, has been demonstrated. It was also shown that KMnO 4 oxidizes σ H adducts to nitrobenzene faster than it does carbanions. This selective ONSH in the para positions of nitroarenes is a general process. However, some substituents hinder or inhibit the oxidation step.