Electrochemical Efficient Synthesis of Two Azo Energetic Compounds

Abstract

Azo compounds with a high density, high enthalpy, and excellent detonation performance have received increasing research attention. The conventional method of chemical dehydrogenation that is used to form azo compounds involves the use of strong oxidants, resulting in environmental pollution. Electrochemical organic synthesis is considered an old method and a new technology. In this work, azofurazan tetrazole {H₂AzFT; 5,5′-[diazene-1,2-diylbis(1,2,5-oxadiazole-4,3-diyl)]bis-1H-tetrazole} and azofurazan hydroxytetrazole (H₂AzFTO) were synthesized by a green and efficient electrochemical dehydrogenation coupling of 5-(4-aminofurazan-3-yl)-1H-tetrazole and 5-(4-aminofurazan-3-yl)-1-hydroxytetrazole, respectively. The structures of H₂AzFT and (NH₄)₂AzFTO were fully characterized by infrared spectroscopy, nuclear magnetic resonance, and elemental analysis, and their thermal stabilities were determined by differential thermal analysis.

Key words

azo compounds - energetic materials - electrochemistry - green chemistry - dehydrogenation - coupling reaction

Publication History

Received: 05 January 2024

Accepted after revision: 07 March 2024

Accepted Manuscript online:
08 March 2024

Article published online:
27 March 2024

• References and Notes

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• 20 Azofurazan Tetrazole (H₂AzFT): Typical Procedure A cell equipped with a commercial C rod (6 × 90 mm) anode and Pt plate (10 × 10 × 0.3 mm) cathode was charged with HAFT (1.0 mmol), (NH₄)₂CO₃ (0.75 mmol), Et₄NCl (2.0 mmol), and H₂O (30 mL). The mixture was then electrolyzed at a constant potential of 1.8 V at r.t. for 3–4 h. The resultant mixture was acidified with 2 M HCl and extracted with EtOAc. The organic solvent was removed to give yellow crystals; yield: 0.284 g (94%); T _onset (DTA, 10 ℃/min): 241 ℃. IR (KBr): 3448,2915, 1636, 1469, 1418, 1321, 1223, 1170, 1092, 1059, 997, 897, 767, 704, 611, 481 cm^–1. ¹³C NMR (150 MHz, DMSO-d ₆): δ = 162.32, 155.81, 136.56. Anal. Calcd for C₆H₂N₁₄O₂ (302.18): C, 23.85; H, 0.67; N, 64.89. Found: C, 23.66; H, 0.91; N, 65.24.