Central European Journal of Energetic Materials Volume 10, Number 2, 2013

Highly Energetic Salts of 3,6-Bishydrazino-1,2,4,5- tetrazine Thomas 


Department of Chemistry, Energetic Materials Research, Ludwig-Maximilian University of Munich, Butenandtstr. 5-13, D-81377 Munich, Germany 

Abstract: 3,6-Bishydrazino-1,2,4,5-tetrazine was synthesized as described by hydrazinolysis of 3,6-bis-(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine. Doubly protonated 1:1 and 1:2 salts of the highly energetic anions were synthesized. These are bishydrazinium-tetrazine dichloride dihydrate (1:2) (BHT-2HCl·2H2O) (2), bishydrazinium-tetrazine (5,5´-azotetrazolate) dihydrate (1:1) (BHT-ATz·2H2O) (3), bishydrazinium-tetrazine bis (3,5-dinitrotriazolate) dihydrate (1:2) (BHT- (DNT)2·2H2O) (4), bishydrazinium-tetrazine bis (5-nitrotetrazolate) (1:2) (BHT- (NT)2) (5), bishydrazinium-tetrazine (5,5´-bistetrazolate) dihydrate (1:1) (BHTBT ·2H2O) (6), bishydrazinium-tetrazine bistetrazolylamine (1:1) (BHT-BTA) (7), bishydrazinium-tetrazine bis (3-amino-5-nitrotriazolate) (1:2) (BHT-(ANTA)2) (8) and bishydrazinium-tetrazine 4,4´,5,5´-tetranitro-2,2´-bisimidazolate (1:1) (9). Compounds 2-6 could be characterized by low temperature X-ray diffraction. All of the compounds were sufficiently analyzed by 1H and {1H}13C and 14N NMR spectroscopy, elemental analysis (CHN), mass spectroscopy (FAB)) and vibrational spectroscopy (IR and Raman). The detonation parameters of the most promising candidates 5 and 9 in terms of energetic applications were calculated using the EXPLO5 V5.05 computer code. The energies of formation were calculated using CBS-4M electronic enthalpies and the atomization method. Furthermore, since all of the compounds are energetic materials, sensitivity tests towards impact (IS), friction (FS) and electrostatical discharge (ESD) were carried out. In addition their thermal stabilities were determined using a differential scanning calorimeter with a heating rate of 5 °C min-1. 

Keywords: 1,2,4,5-tetrazine, energetic materials, explosives, sensitivities, crystal structures

Institute of Industrial Organic Chemistry

Warsaw, Poland