Selective Oxidation of Heterocyclic Amines

ABSTRACT: This proposal sets out a plan to continue the method development for selective chemical oxidization of one amine of a polyamino, multi-heterocyclic class of energetic materials. The approach is based on screening one substrate (DAAzF) with many different oxidants under a variety of conditions including microwave heating to find those conditions where one amine group has been oxidized to a nitro group to give ANAzF. The reaction mixtures are analyzed by liquid chromatography/mass spec (LC/MS) instrument with a refined method that separates, quantifies, and identifies more than 20 compounds within 15 min. Promising methods showing feasibility in Phase I will be optimized to give a scalable, robust method that delivers ANAzF in good yield with high purity. The method will be shown to effect selective oxidation of at least three other substrates of the same class. These are also known to be insensitive energetic materials but with higher explosive power than TNT. The developed method will be useful to provide the large quantities of new, promising energetic materials for further performance testing, formulation, and field tests to enable more rapid deployment of faster, longer range delivery systems and more powerful weapons. BENEFIT: The new synthetic method will facilitate the development of new energetic materials of interest to the Air Force and DoD. Such materials are key mission enablers that provide new and needed capabilities for propulsion systems, munitions, warheads, and military pyrotechnics. They can provide the increases in perfomance for increased pulse, range, ligher weight as well as safety and survivability of personal and munitions. The methods developed here will allow the production of new energetic materials at a scale where all development testing can be performed.