Computational study of FOX-7 synthesis in a solvated reaction system
Abstract
Ethene and two kinds of nitrating reagents (HNO3 and N2O5) 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 Cl2 and Br2) and amination (using NH3) 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 H2O-solvated and CH3OH-solvated systems, no matter what nitrating agent was used. Related energy barrier data showed that the nitration reaction is more feasible in an H2O-solvated than a CH3OH-solvated system. The modeling results suggested that N2O5 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 H2O-solvated system. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011
