Acidity and basicity of primary N‐phenylnitramines: catalytic effect of protons on the nitramine rearrangement

Abstract

AbstractPara‐substituted N‐phenylnitramines were prepared either by oxidation of diazonium salts or by nitration under alkaline or acidic conditions. Isotopic [15N‐NO2] labelling indicated that the bands characteristic of the N‐nitro group appear in the 1318–1323 and 1585–1607 cm−1 regions. In the nitrogen NMR spectra, the nitramino group gives two resonances at −193 ± 3 (NH) and −32 ± 3 ppm (NO2). The chemical shifts in proton and carbon NMR spectra are predictable, based on increments and the additivity rule. The spectral data indicate the lack of conjugation between the nitramino group and another substituent bound to the ring. It seems to contradict the well‐known fact that substituents strongly (ρ = 4) influence the rate of nitramine rearrangement. The acidities of primary N‐phenylnitramines (3.77 < pKA < 5.62) are similar to those of benzoic acids and weakly dependent (ρ = 1) on the electronic character of a substituent. Based on the analogy with benzoic acids, it has been calculated that basicities of nitramines (pKB ≈ 21) are extremely low. Consequently, addition of protons to an intact nitramine molecule, as the preliminary step of the rearrangement, seems to be improbable. Migration of the N‐nitro group precedes protonation; the latter process facilitates transformation of intermediates into stable final products. Copyright © 2001 John Wiley & Sons, Ltd.