Department of General and Biological Chemistry N2, Donetsk National Medical University, 1 Velyka Perspectyvna Str., Kropyvnytskyi, 25015, Ukraine.
Department of Molecular Biophysics, Institute of Molecular Biology and Genetics, National Academy of Sciences of Ukraine, Kyiv 03143, Ukraine.
J Phys Chem A. 2019 Sep 5;123(35):7597-7608. doi: 10.1021/acs.jpca.9b01772. Epub 2019 Aug 23.
DNAN (2,4-dinitroanisole), NTO (3-nitro-1,2,4-triazol-5-one), and NQ (nitroguanidine) are important energetic materials used in military applications. They may find their way to the environment during manufacturing, transportation, storage, training, and disposal. A detailed investigation of possible mechanisms for reactions of the nitrocompounds with singlet oxygen, one of the potential methods for their degradation, was performed by computational study using the PCM(Pauling)/M06-2X/6-311++G(d,p) approach. Obtained results suggest that reactivity of the investigated munitions compounds toward singlet oxygen follows the order: DNAN > NTO(anion) > NQ ≫ NTO. DNAN is involved in [4 + 2]-addition with oxygen, and further formation of diepoxide or epoxyketone through diradical intermediates have been predicted. The NTO may undergo intramolecular rearrangement with formation of peroxide compound or nitrite radical elimination, and NQ may be transformed into urea.
DNAN（2,4-二硝基苯甲醚）、NTO（3-硝基-1,2,4-三唑-5-酮）和 NQ（硝胍）是用于军事应用的重要含能材料。它们在制造、运输、储存、培训和处置过程中可能会进入环境。通过使用 PCM（鲍林）/M06-2X/6-311++G（d，p）方法的计算研究，详细调查了这些硝基化合物与单线态氧反应的可能机制，单线态氧是它们降解的潜在方法之一。获得的结果表明，研究的弹药化合物对单线态氧的反应性遵循以下顺序：DNAN > NTO（阴离子）> NQ > NTO。DNAN 参与与氧的[4 + 2]-加成，并且通过自由基中间体进一步预测了二环氧或环氧化酮的形成。NTO 可能通过形成过氧化物化合物或亚硝酸盐自由基消除进行分子内重排，而 NQ 可能转化为尿素。
