Computational Investigation of Thermal Decomposition Mechanism of 5-Nitro-5-R-1,3-Dioxane Compounds

Abstract This paper features the results of the computational study of thermal decomposition reaction of 5-nitro-5-R-1,3-dioxane compounds, with R=H, Br and CH3. Computational calculations were performed on M06-2X/6-311+G(d,p) in gas phase and also in solution with DMSO, at different temperatures. The kinetic and thermodynamic data obtained indicate a favoring of the reaction when the molecule presents a CH3 substituent group in position 5 and when carried out in DMSO, the stability of the molecules in their energetic components was discussed, too. For R=H two different reaction mechanisms were proposed and studied. Wiberg bonds indices were obtained for the reactions studied and the results were examined in terms of bond formation and bond breaking progress as well.