On the Viability of Nitronic Acids in the Decomposition of Nitroaromatics: A Theoretical Study of Nitronic Acids
Abstract
The nitro <-> aci-nitro, keto <-> enol, and imine <-> enamine tautomeric processes in nitromethane, acetaldehyde, and acetaldimine were investigated at the G1 level of theory, in nitroacetaldehyde, 2- nitroacetaldimine, and 3-nitropropene at MP4/6-31G*, in 2-nitroaniline, 2- nitrophenol, and 2-nitrotoluene at MP2/6-31 G*, and in 2,6-dinitroaniline, 2,6- dinitrophenol, 2,6-dinitrotoluene, 2,4,6-trinitroaniline (picramide), 2,4,6- trinitrophenol(picric acid, PA), and 2,4,6-trinitrotoluene (NT) at HF/6-31 G*. These studies demonstrate that the ease of tautomerization is in the order PA (easiest), TNT then picramide, which parallels their sensitivity to impact. The nitronic acid tautomer of TNT is calculated at HF-/6-31G* to lie 39 kcal/mol above TNT with a 65 kcal/mol barrier (with an extrapolated value of 48 kcal/mol under MP2), while the nitronic acid tautomer of picaramide lies 48 kcal/mol above picramide beyond a 51 kcal/mol barrier. Cyclization and dehydration of the latter two nitronic acids should be overall exothermic processes. Nitronic acid, TNT, Picric acid, Picramide, Nitromethane, Cyclization, Nitroaromatics.
Document Details
- Document Type
- Technical Report
- Publication Date
- Aug 01, 1993
- Accession Number
- ADA273594
Entities
People
- Koop Lammertsma
Organizations
- University of Alabama at Birmingham