title: Alkaline hydrolysis of hexahydro-1,3,5-trinitro-1,3,5-triazine: M06-2X investigation.
abstract: Alkaline hydrolysis mechanism of possible environmental contaminant RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) was investigated computationally at the PCM(Pauling)/M06-2X/6-311++G(d,p) level of theory. Results obtained show that the initial deprotonation of RDX by hydroxide leads to nitrite elimination and formation of a denitrated cyclohexene intermediate. Further nucleophilic attack by hydroxide onto cyclic CN double bond results in ring opening. It was shown that the presence of hydroxide is crucial for this stage of the reaction. The dominant decomposition pathway leading to a ring-opened intermediate was found to be formation of 4-nitro-2,4-diazabutanal. Hydrolytic transformation of its byproduct (methylene nitramine) leads to end products such as formaldehyde and nitrous oxide. Computational results are in a good agreement with experimental data on hydrolysis of RDX, suggesting that 4-nitro-2,4-diazabutanal, nitrite, formaldehyde, and nitrous oxide are main products for early stages of RDX decomposition under alkaline conditions.
authors.affiliation: Interdisciplinary Center for Nanotoxicity, Department of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39217, USA; Department of Organic Chemistry, Oles Honchar Dnipropetrovsk National University, Dnipropetrovsk 49000, Ukraine.
authors.forename: Liudmyla K
authors.initials: LK
authors.lastname: Sviatenko
authors.affiliation: HX5, LLC, Vicksburg, MS 39180, USA.
authors.forename: Leonid
authors.initials: L
authors.lastname: Gorb
authors.affiliation: US Army ERDC, Vicksburg, MS 39180, USA.
authors.forename: Frances C
authors.initials: FC
authors.lastname: Hill
authors.affiliation: Interdisciplinary Nanotoxicity Center, Department of Civil and Environmental Engineering, Jackson State University, Jackson, MS 39217, USA.
authors.forename: Danuta
authors.initials: D
authors.lastname: Leszczynska
authors.affiliation: Department of Organic Chemistry, Oles Honchar Dnipropetrovsk National University, Dnipropetrovsk 49000, Ukraine.
authors.forename: Sergiy I
authors.initials: SI
authors.lastname: Okovytyy
authors.affiliation: Interdisciplinary Center for Nanotoxicity, Department of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39217, USA. Electronic address: jerzy@icnanotox.org.
authors.forename: Jerzy
authors.initials: J
authors.lastname: Leszczynski
mesh_terms: D000447:Aldehydes / Q000032:analysis; D000465:Algorithms; D000814:Aniline Compounds / Q000737:chemistry; D001372:Aza Compounds / Q000032:analysis; D002244:Carbon / Q000737:chemistry; D003198:Computer Simulation; D052918:Environmental Restoration and Remediation; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007700:Kinetics; D009573:Nitrites / Q000032:analysis*; D009578:Nitrobenzenes / Q000737:chemistry; D009584:Nitrogen / Q000737:chemistry; D009609:Nitrous Oxide / Q000032:analysis*; D013056:Spectrophotometry, Ultraviolet; D013816:Thermodynamics; D014227:Triazines / Q000032:analysis*; D014874:Water Pollutants, Chemical / Q000032:analysis
chemical_list: C485205:4-nitro-2,4-diazabutanal; D000447:Aldehydes; D000814:Aniline Compounds; D001372:Aza Compounds; D009573:Nitrites; D009578:Nitrobenzenes; D014227:Triazines; D014874:Water Pollutants, Chemical; D002244:Carbon; C015384:nitramine; D009609:Nitrous Oxide; D009584:Nitrogen; C009160:cyclonite
keywords: 4-Nitro-2,4-diazabutanal; Hexahydro-1,3,5-trinitro-1,3,5-triazine; Mechanism; UV–VIS spectra