Development of a New N-Amination Reagent for Direct Electrophilic Amination of Energetic Nitrogen-Rich Heterocycles.

Nitrogen-rich heterocycles bearing amino groups can enhance their stability and energetic performance. Herein, we report the application of 6-(aminooxy)dibenzo[c,e][1,2]oxaphosphinine 6-oxide as a stable and convenient electrophilic amination reagent for the direct N-amination of nitrogen-rich heterocycles. Compared with currently known reagents, this reagent demonstrates superior performance in the N-amination of various energetic nitrogen-rich heterocycles (e.g., LLM-116, DNT, NTO, TNBP, TNBI, PTO, and DFP), which possess diverse electronic properties and structures. In addition, it exhibits distinctive regiochemical control in the reaction with 1-aminotetrazole, thereby creating opportunities for developing new energetic materials.