Computational study on the comparative synthesis of energetic FOX‐7 derivatives

Ethene and two kinds of nitrating reagents (HNO₃ and N₂O₅) were included in respective molecular systems, which progressed through a two‐stage electrophilic and free radical nitrosubstitution, resulting in the corresponding nitroethene compounds. Subsequent halogenation (using Cl₂ and Br₂) and amination (using ammonia) were then performed, also by electrophilic and radical substitution, to produce the target 1,1‐diamino‐2,2‐dinitroethene (FOX‐7) derivatives. All transition state species were identified using a two‐ or three‐structure Synchronous Transit‐Guided Quasi‐Newton between the Cartesian coordinates of the related molecular systems at specific reaction stages. The modeling results suggest that N₂O₅ is the better agent for nitration and bromine is suitable for use in halogenation. The comparable activation energies throughout the reaction stages were considered to imply the most feasible pathways of FOX‐7 synthesis. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010