The formation of aryloxenium ion in the reaction of N-nitro-O-(4-nitrophenyl)hydroxylamine with strong acids |
| |
Authors: | M S Klenov A M Churakov V N Solkan Yu A Strelenko V A Tartakovsky |
| |
Institution: | 1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation
|
| |
Abstract: | The reaction of N-nitro-O-(4-nitrophenyl)hydroxylamine (1) with conc. H2SO4 affords 4-nitropyrocatechol and that with conc. sulfonic acids (RSO3H where R = Me, CF3) affords 2-hydroxy-5-nitrophenyl-R-sulfonates in yields of 80?C85%. These reactions are assumed to proceed through an intermediate (phenoxy)oxodiazonium ion NO2C6H4O-N=N=O]+, which eliminates the N2O molecule to form the aryloxenium ion NO2C6H4O]+. The latter reacts with acid anions at the ortho-carbon atom of the phenyl ring. The thermodynamical parameters of the elementary reactions resulting in the formation of the (phenoxy)oxodiazonium ion NO2C6H4O-N=N=O]+ and aryloxenium ion NO2C6H4O]+ were calculated in the B3LYP/6?311+G(d) study of the combined molecular system (nitrohydroxylamine 1 + H3SO4]+). The reaction of nitrohydroxylamine 1 with aqueous solutions of strong acids (??70% H2SO4, CF3SO3H) affords mainly 4-nitrophenol. It appears that the mechanism of this reaction does not involve the formation of the aryloxenium ion. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|