Alkaline hydrolysis of hexahydro-1,3,5-trinitro-1,3,5-triazine: M06-2X investigation

作者：Sviatenko Liudmyla K; Gorb Leonid; Hill Frances C; Leszczynska Danuta; Okovytyy Sergiy I; Leszczynski Jerzy^*

来源：Chemosphere, 2015, 134: 31-38.

DOI：10.1016/j.chemosphere.2015.03.064

• Hexahydro-1,3,5-trinitro-1,3,5-triazine
• 4-Nitro-2,4-diazabutanal
• Mechanism
• UV-VIS spectra

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 C=N 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.

• 出版日期2015-9