Thermal stability studies on a homologous series of nitroarenes

Jimmie C. Oxley, New Mexico Institute of Mining and Technology
James L. Smith, New Mexico Institute of Mining and Technology
Hong Ye, New Mexico Institute of Mining and Technology
Robert L. McKenney, Eglin Air Force Base
Paul R. Bolduc, Eglin Air Force Base


The thermal stabilities of a number of nitroarenes were examined in solution and in condensed phase. In general, increasing the number of nitro groups decreased thermal stability. Changing the substituent on 1-X-2,4,6-trinitrobenzene from X = H to NH2 to CH3 to OH accelerated decomposition; this effect was attributed to increased ease of intramolecular proton transfer to an ortho nitro group, thus weakening the carbon-nitrogen bond. In solution, the effect of increasing substitution from n = 1 to n = 3 on Xn(NO2)3C6H3-n, was uniformly that of decreasing the thermal stability of the species. However, in condensed phase, results suggested that crystal habit may be more important than molecular structure; for X = Br, CH3, and NH2, the more substituted species was the more stable. © 1995 American Chemical Society.