title: Theoretical predictions of chemical degradation reaction mechanisms of RDX and other cyclic nitramines derived from their molecular structures.
abstract: Analysis of environmental degradation pathways of contaminants is aided by predictions of likely reaction mechanisms and intermediate products derived from computational models of molecular structure. Quantum mechanical methods and force-field molecular mechanics were used to characterize cyclic nitramines. Likely degradation mechanisms for hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) include hydroxylation utilizing addition of hydroxide ions to initiate proton abstraction via 2nd order rate elimination (E2) or via nucleophilic substitution of nitro groups, reductive chemical and biochemical degradation, and free radical oxidation. Due to structural similarities, it is predicted that, under homologous circumstances, certain RDX environmental degradation pathways should also be effective for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and similar cyclic nitramines. Computational models provided a theoretical framework whereby likely transformation mechanisms and transformation products of cyclic nitramines were predicted and used to elucidate in situ degradation pathways.
authors.affiliation: US Army ERDC 3909 Halls Ferry Rd, Vicksburg, Mississippi, MS 39180, USA. Mohammad.M.Qasim@erdc.usace.army.mil
authors.forename: M
authors.initials: M
authors.lastname: Qasim
authors.forename: H
authors.initials: H
authors.lastname: Fredrickson
authors.forename: C
authors.initials: C
authors.lastname: McGrath
authors.forename: J
authors.initials: J
authors.lastname: Furey
authors.forename: R
authors.initials: R
authors.lastname: Bajpai
mesh_terms: D001392:Azocines / Q000737:chemistry; D003198:Computer Simulation; D006573:Heterocyclic Compounds, 1-Ring / Q000737:chemistry; D017665:Hydroxyl Radical / Q000737:chemistry; D006900:Hydroxylation; D008956:Models, Chemical; D010084:Oxidation-Reduction; D014227:Triazines / Q000737:chemistry*
chemical_list: D001392:Azocines; D006573:Heterocyclic Compounds, 1-Ring; D014227:Triazines; D017665:Hydroxyl Radical; C007950:octogen; C009160:cyclonite