Computational investigation of thermal decomposition mechanism of 5-nitro-5-R-1,3-dioxane compounds

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 with M06-2X, MPWB1K, PBE0 and omega B97X-D functionals, and 6-311 + G(d,p) basis set 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 substituent groups 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 bond indices were obtained for the reactions studied and the results were examined in terms of bond formation and bond breaking progress as well.

Automated summary

This paper presents computational study results on the thermal decomposition reaction of 5-nitro-5-R-1,3-dioxane compounds with different substituents. The findings suggest that the reaction is more favorable when substituent groups are present and when the reaction is conducted in DMSO.