This project's goal is to develop electrochemical decarboxylative nitration as an alternative methods to synthesize currently used energetic compounds and doubly decarboxylative cross-coupling (dDCC) as a new methodology to synthesize novel energetic compounds. 

Electrochemical decarboxylative nitration will be studied via both a reductive approach, using a Ni-catalyst and a redox active NO₂ donor, and an oxidative approach in which carboxylate and nitrite species are simultaneously oxidized resulting in an alkyl radical and nitro radical that can combine to generate the desired nitrated species. Transitioning to aromatic species, the project team will explore electrochemical reactions with silver catalysts and elevated temperatures to afford the desired nitroaromatic compounds. This work will start with simple model compounds and then transition to the synthesis of trinitrotoluene (TNT), triaminotrinitrobenzene (TATB), and trinitrobenzene. The atom-efficient synthesis of energetic materials containing strained ring systems will be accomplished by utilizing the recently developed electrochemical process dDCC. The work here will focus on compounds with strained ring systems and easily nitratable groups to produce novel energetic compounds. This approach enables the synthesis of a wide variety of energetic materials from cheap substrates containing carboxylic acid groups. Throughout the project the project team will utilize high-throughput robotic screening hardware to optimize electrochemical reaction conditions including catalysts, solvents, concentrations, and temperatures.

Electrochemical decarboxylative nitration is expected to be a game-changing technology that dramatically improves efficiency of producing targeted energetics. As such, the process will reduce the amount of mixed acid reagent needed for nitration, should reduce red water formation if applied to TNT production, and should reduce production costs. The synthesis of energetic materials via dDCC could enable the production of energetic materials from inexpensive and widely available substrates containing carboxylic acids. This approach allows for excellent atom economy and is expected to reduce life cycle costs. Further, it will provide a platform technology for the generation of low vapor pressure energetic materials with custom tailored densities and melting points. (Anticipated Project Completion - 2027)