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.
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Dedicated the 80-th anniversary of the academician of the Russian Academy of Sciences O. M. Nefedov.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1221–1232, November, 2011.
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Klenov, M.S., Churakov, A.M., Solkan, V.N. et al. The formation of aryloxenium ion in the reaction of N-nitro-O-(4-nitrophenyl)hydroxylamine with strong acids. Russ Chem Bull 60, 2263–2274 (2011). https://doi.org/10.1007/s11172-011-0346-x
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DOI: https://doi.org/10.1007/s11172-011-0346-x