A Proposed Interpretation of the Destabilizing Effect of Hydroxyl Groups on Nitroaromatic Molecules
Abstract
One of the important objectives of current research in the area of high-energy molecules is to learn more about the factors that determine their sensitivities toward shock and impact. A better understanding of these factors could lead to the design and synthesis of chemical systems that combine high performance with improved stability. Whereas an amino group stabilizes nitroaromatic molecules toward shock and impact, presumably through a resonance interaction that strengthens the C-NO2 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, 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 O-H bond produced by shock or impact. No analogous equilibrium structure is found for a possible nitronic acid tautomer of o-nitroaniline. Keywords: Explosive; Sensitivity; Reprints.
Document Details
- Document Type
- Technical Report
- Publication Date
- Aug 01, 1989
- Accession Number
- ADA211516
Entities
People
- Jorge M. Seminario
- Paul R. Bolduc
- Peter Politzer
Organizations
- University of New Orleans