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

Abstract

Abstract Ethene and two kinds of nitrating reagents (HNO 3 and N 2 O 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 2 O‐solvated and CH 3 OH‐solvated systems, no matter what nitrating agent was used. Related energy barrier data showed that the nitration reaction is more feasible in an H 2 O‐solvated than a CH 3 OH‐solvated system. The modeling results suggested that N 2 O 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 2 O‐solvated system. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011