jp9b01772_si_001.pdf (542.49 kB)
Role of Singlet Oxygen in the Degradation of Selected Insensitive Munitions Compounds: A Comprehensive, Quantum Chemical Investigation
journal contribution
posted on 2019-08-23, 12:04 authored by Liudmyla K. Sviatenko, Leonid Gorb, Danuta Leszczynska, Sergiy I. Okovytyy, Manoj K. Shukla, Jerzy LeszczynskiDNAN (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.