Theoretical investigation of methoxide ion reaction on the 7-methyl-4,6-dinitrobenzofuroxan

Abstract

Reaction of the methoxide ion on the 7-methyl-4,6-dinitrobenzofuroxan (DNBF) 1 has been studied theoretically by means of DFT/B3LYP technique to interpret the kinetic–thermodynamic competition between the three possible compounds that are carbanion DNBF− 4 and the two complexed forms (2, 3) of the methoxide group in positions 5 and 7, respectively. Optimized geometry, nbo atomic charge distribution, thermodynamic/kinetic parameters (ΔrH°T, ΔrS°T, ΔrG°T, ΔH*, ΔS*, and ΔG*) and IRC path have been calculated for possible products and their transitional states using water as solvent. All obtained ΔrG°T are negative, ranging from −19.16 to −42.87 kcal mol−1 (1 cal = 4.184 J), indicating the possible observation of all products, but the experimenters only detected the anionic form DNBF−. Fukui indices, which were calculated by means of NBO atomic charge distribution, confirm the electrophilicity of the sites C5 and C7. Transition states barriers, ΔG*, are 14.97, 15.16, and 21.94 kcal mol−1 for the three possible products 2, 3, and 4, respectively, in water. As expected, the most stable compound is carbanion, but it also exhibits the highest activation barrier. If this situation formally engenders a double kinetic–thermodynamic competition, the very weak activation energy of the two complexes in C5 and C7 makes improbable the simultaneous detection of the three expected compounds.