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Reactions of Nitrosoarenes with Nitrogen Monoxide (Nitric Oxide) and Nitrogen Dioxide: Formation of Diarylnitroxides
Author(s) -
Astolfi Paola,
Carloni Patricia,
Damiani Elisabetta,
Greci Lucedio,
Marini Milvia,
Rizzoli Corrado,
Stipa Pierluigi
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200800213
Subject(s) - chemistry , nitrosobenzene , nitrogen dioxide , nitrogen , nitric oxide , adduct , inorganic chemistry , nitro , nitroso compounds , oxidizing agent , nitrone , photochemistry , organic chemistry , catalysis , cycloaddition , alkyl
Nitrosoarenes react with nitrogen monoxide (nitric oxide) at room temperature and in aprotic media to afford the corresponding diarylnitroxides by the intermediate formation of N ‐nitrosoarylnitroxides. However, these latter spin adducts, in contrast with literature reports, have never been detected by us. N ‐nitrosophenylnitroxide is obtained only in the oxidation of the ammonium salt of N ‐nitrosophenylhydroxylamine (cupferron) with trace amounts of lead tetraacetate. However, it evolves with time to diphenylnitroxide, as demonstrated by following the reaction course in the ESR cavity. On a macroscale level, the reaction between nitrosobenzene and nitric oxide leads to the formation of N ‐nitrosodiphenylamine, 4‐nitro‐ N ‐nitrosodiphenylamine, 4‐nitrodiphenylamine and 4,4′‐dinitrodiphenylamine, in addition to diphenylnitroxide. Diarylnitroxides are also obtained when nitrosoarenes react with small amounts of nitrogen dioxide; the mechanism of this reaction is proposed and discussed. The structure of 4‐nitro‐ N ‐nitrosodiphenylamine was determined by X‐ray analysis.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)