Elaborating NH-Bridged Nitrogen-Rich Energetic Materials via Base-Mediated Dimroth Rearrangement: Synthesis, Characterization, and Performance Study

• Published in: Journal of organic chemistry 2024-05, Vol.89 (11), p.8192-8200
• Main Authors: Jujam, Manojkumar, Ghule, Vikas D., Dharavath, Srinivas
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.4c01063

The pursuit of heat-resistant energetic materials featuring high thermostability and energy has gained keen interest in recent years owing to their use in coal mining and aerospace domains. In this study, we synthesized 4-((4,6-diamino-1,3,5-triazin-2-yl) amino)-1H-1,2,3-triazole-5-carbonitrile (6) and its perchlorate and nitrate energetic salts (6a and 6b) by incorporating amino bridging (−NH−) using the Dimroth rearrangement (DR) from inexpensive starting materials as a heat-resistant energetic materials. All of the compounds were thoroughly characterized by infrared (IR), NMR, elemental analysis (EA), high-resolution mass spectrometry (HRMS), and thermogravimetric analysis-differential scanning calorimetry (TGA-DSC) studies. Compounds 6a and 6b showed good densities (1.81 and 1.80 g cm–3), detonation performance (VOD = 7505 and 8257 m s–1, DP = 23.47 and 24.41 GPa), insensitivity to mechanical stimuli (IS = 40 J and FS = >360 N), and excellent thermal stability (T d = 307 and 334 °C), surpassing presently used heat-resistant explosive HNS (318 °C). The molecular electrostatic potentials and noncovalent interactions were pursued to understand possible interaction sites and structure-directing interactions in these salts. Their facile synthetic approach, good energetic performance, and outstanding thermal stability indicate that they are the ideal combination for replacing current benchmark heat-resistant explosive HNS. Additionally, this study highlights the use of classical DR for making new energetic materials with fine-tuned properties.