Computational study of FOX-7 synthesis in a solvated reaction system

摘要

Ethene and two kinds of nitrating reagents (HNO_3 and N _2O_5) in a variety of solvents were included in respective molecular systems, and each underwent a two-stage electrophilic and free radical nitro-substitution reaction to obtain the corresponding nitroethene compounds. Subsequent halogenation (using Cl_2 and Br_2) and amination (using NH_3) were then performed in solvents, also by electrophilic and radical substitution, to produce the desired 1,1-diamino-2,2-dinitroethene (FOX-7) derivatives. The reaction energy barrier in the nitration stage for obtaining each kind of mononitro ethene exhibited a stepwise decreasing trend when the reaction was carried out in H_2O-solvated and CH _3OH-solvated systems, no matter what nitrating agent was used. Related energy barrier data showed that the nitration reaction is more feasible in an H_2O-solvated than a CH_3OH-solvated system. The modeling results suggested that N_2O_5 is the better agent for nitration to proceed in water, bromine is suitable for halogenation, and the bromine derivatives are convenient for further amination in an H _2O-solvated system.