The Electrochemical Synthesis of High Nitrogen and Energetic Materials

Developing high-nitrogen materials is highly important to industries, such as pharmaceuticals and energetic materials development. The production of such materials is often wrought with hazardous conditions that raise manufacturing costs and produce toxic waste streams. This is often observed using heavy-metal redox reagents such as potassium permanganate, lead acetate, zinc, and silver metal. Elucidating novel synthesis techniques to alleviate these issues is highly important for reducing environmental toxicity and lowering reaction costs. One green technique that has gained popularity in the past few decades is synthetic organic electrochemistry. Electrochemistry is a technique that utilizes the direct flow of electrons to drive chemical reactions. This is advantageous as the direct use of electrons supplied from an electrode is an inherently cheap and environmentally friendly redox reagent. Additionally, electrochemistry allows for unique reaction pathways that would be difficult, if not impossible, to obtain via traditional chemical methodologies.

Herein, I discuss our work on advancing electrochemical synthesis for synthesizing high-nitrogen and energetic materials, which includes: An overview of potential reaction pathways toward developing promising high-nitrogen heterocyclic small molecules and polymers. Studies of the reaction efficiency of the decagram scale electrochemical production of useful energetic feedstocks, such as potassium dinitroethane. Novel azo bridged energetic materials produced via electrochemical amine oxidation reactions that were further utilized to prepare a series of energetic N-nitramines. Finally, a novel sequential electrochemical-photochemical methodology has been developed that has produced annulated heterocycles with promising pharmaceutical and energetic applications.