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 80–85%. 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.

Cite: Klenov M.S. , Churakov A.M. , Solkan V.N. , Strelenko Y.A. , Tartakovsky V.A.
The formation of aryloxenium ion in the reaction of N-nitro-O-(4-nitrophenyl)hydroxylamine with strong acids
Russian Chemical Bulletin. 2011. V.60. N11. P.2263-2274. DOI: 10.1007/s11172-011-0346-x WOS Scopus OpenAlex

Identifiers:

≡ Web of science:	WOS:000307517100016
≡ Scopus:	2-s2.0-84865502183
≡ OpenAlex:	W2145166948

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