A proposed interpretation of the destabilizing effect of hydroxyl groups on nitroaromatic molecules Academic Article uri icon

abstract

  • Whereas an amino group stabilizes nitroaromatic molecules toward shock and impact, presumably through a resonance interaction that strengthens the CNO2 bonds, hydroxyl substituents have a sensitizing effect despite having resonance capabilities. This may reflect the formation, by hydroxyaromatics, of the unstable nitronic acid tautomer. A computational analysis (SCF, 3-21G) of the o-nitrophenol system, used as a model, shows that transfer of the phenolic proton to the nitro group produces an equilibrium nitronic acid structure, with a calculated energy 15.4 kcal/mol above o-nitrophenol. Such proton transfer might result from vibrational excitation of the OH bond produced by shock or impact. No analogous equilibrium structure is found for a possible nitronic acid tautomer of o-nitroaniline. © 1989.

author list (cited authors)

  • Politzer, P., Seminario, J. M., & Bolduc, P. R.

citation count

  • 44

complete list of authors

  • Politzer, Peter||Seminario, Jorge M||Bolduc, Paul R

publication date

  • June 1989