Electrochemically driving C-C coupling of the pyrimidine ring via C-H activation for constructing the energetic skeleton

In recent years, due to the advantages of green and safe electrochemical synthesis, researchers have gradually introduced it into the field of energetic material. However, electrochemistry is mainly used to achieve the generation of azo bond through amino coupling in the field of energetic materials, and the application of the reaction is relatively limited. In this work, we achieved direct C-C coupling through electrochemical C-H bond activation, constructed a bicyclic pyrimidine-based energetic skeleton, and further enabled its self-assembly with perchloric acid to generate the energetic molecule HABPTP (2,2',4,4',6,6'-hexaamino-[5,5'-bipyrimidine]-1,1',3,3'-tetraium perchlorate). This method can be completed using commercial electrodes at room temperature without the need for transition metal catalysis, and the reaction conditions are relatively simple. The calculation results show that HABPTP has high detonation performance ( D v = 9001 m·s −1 , p = 40.65 GPa), and its comprehensive performance is basically better than that of traditional explosive RDX. This work is the first to achieve the construction of C-C coupling energetic skeleton through electrochemistry, expanding the application scope of electrochemistry in the field of explosive synthesis. Electrochemical synthesis offers a green and safe strategy for energetic material construction, yet its applications have remained limited in reaction diversity. In this work, an electrochemical approach is developed to directly construct a C-C coupled energetic framework through C-H bond activation, enabling the formation of a bicyclic pyrimidine-based skeleton. Subsequent self-assembly with perchloric acid affords a novel ionic energetic compound. The process operates under mild conditions using commercially available electrodes and avoids transition-metal catalysis. This study presents a novel electrochemical approach to constructing an energetic framework, broadening the synthetic pathways of energetic materials. (1) Electrochemical C-H bond activation was introduced into the synthesis of energetic materials, achieving direct C-C coupling without transition metal catalysis. (2) A novel bicyclic pyrimidine energetic scaffold was constructed, and HABPTP was successfully prepared through self-assembly with perchloric acid. The reaction conditions were mild, the operation was simple, and it could be completed at room temperature. (3) Theoretical calculations indicate that HABPTP exhibits excellent detonation performance ( D v = 9001 m·s -1 , p = 40.65 GPa).