ChemInform Abstract: Reactions of Aromatic Nitro Compounds. Part 73. Reaction of Anionic m‐Dinitrobenzene σ‐Complexes with Arenediazonium Salts

Abstract

2001 azo compounds azo compounds (diazo compounds, triazenes etc.) (benzene compounds) Q 0160 05 -077 Reactions of Aromatic Nitro Compounds. Part 73. Reaction of Anionic m-Dinitrobenzene σ-Complexes with Arenediazonium Salts -[replacement of one nitro group in m-dinitroarenes (I) and (IV) to furnish the corresponding nitroazoarenes (III) and (V)/(VI), respectively]. -(ATROSHCHENKO, YU. M.; BLOKHINA, N. I.; SHAKHKEL'DYAN, I. V.; GRUDTSYN, YU. D.; GITIS, S. S.; BORBULEVICH, O. YA.; BLOKHIN, I. V.; KAMINSKII, A. YA.; SHISHKIN, O. V.; ANDRIANOV, V. F.; Russ. J.

Nucleophilic Dearomatizing (DNAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

“…Electrophilic attack at the carbon atom of the aci -nitro group of 604 was observed in the reaction of these σ-adducts with aromatic diazonium salts 615 , leading to the formation of 10-arylazo-9,10-DHAs 616 (Scheme ; Table ), which were further transformed into anthraquinone arylhydrazones 617 upon treatment with a base. , The formation of 616 is a remarkable process mainly for two reasons. On the one hand, the related reactions of σ-complexes of polynitroaromatic compounds afford rearomatized products through two competing pathways: oxidation to the polynitroarene and substitution of a nitro group by the aryldiazonium ion. ,− On the other hand, the conversion of 461 into 616 represents a procedure for introducing a phenylazo moiety into an electron-deficient aromatic system, which is not feasible through conventional diazo coupling reactions. The distinct behavior of σ-complexes 604 toward aromatic diazoniun salts as compared with those derived from polynitrobenzenes and polynitronaphthalenes was attributed to the stability gained by the existence of 616 in a boat conformation, which minimizes the steric interactions between the substituents and the peri hydrogens.…”

“…On the one hand, the related reactions of σ-complexes of polynitroaromatic compounds afford rearomatized products through two competing pathways: oxidation to the polynitroarene and substitution of a nitro group by the aryldiazonium ion. 250,[322][323][324][325] On the other hand, the conversion of 461 into 616 represents a procedure for introducing a phenylazo moiety into an electron-deficient aromatic system, which is not feasible through conventional diazo coupling reactions. The distinct behavior of σ-complexes 604 toward aromatic diazoniun salts as compared with those derived from polynitrobenzenes and polynitronaphthalenes was attributed to the stability gained by the existence of 616 in a boat conformation, which minimizes the steric interactions between the substituents and the peri hydrogens.…”