The safe preparation and characterization (XRD, NMR and vibrational spectroscopy, DSC, mass spectrometry, sensitivities) of a new explosive dihydroxylammonium 5,5 0 bistetrazole 1,1 0 diolate (TKX 50) that outperforms all other commonly used explosive materials is detailed. While much publicized high performing explosives, such as octanitrocubane and CL 20, have been at the forefront of public awareness, this compound differs in that it is simple and cheap to prepare from commonly available chemicals. TKX 50 expands upon the newly exploited field of tetrazole oxide chemistry to produce a material that not only is easily prepared and exceedingly powerful, but also possesses the required thermal insensitivity, low toxicity, and safety of handling to replace the most commonly used military explosive, RDX (1,3,5 trinitro 1,3,5 triazacyclohexane). In addition, the crystal structures of the intermediates 5,5 0 bistetrazole 1,1 0 diol dihydrate, 5,5 0 bistetrazole 1,1 0 diol dimethanolate and dimethylammonium 5,5 0 bistetrazole 1,1 0 diolate were determined and presented.

Adequate primary explosives such as lead azide mostly contain toxic ingredients, which have to be replaced. A new candidate that shows high potential, potassium 1,1'-dinitramino-5,5'-bistetrazolate (K2DNABT), was synthesized by a sophisticated synthetic procedure based on dimethylcarbonate and glyoxal. It was intensively characterized for its chemical (X-ray diffraction, EA, NMR and vibrational spectroscopy) and physico-chemical properties (sensitivity towards impact, friction, and electrostatic, DSC). The obtained primary explosive combines good thermal stability with the desired mechanical stability. Owing to its high heat of formation (326 kJ mol(-1)) and density (2.11 g cm(-3)), impressive values for its detonation velocity (8330 m s(-1)) and pressure (311 kbar) were computed. Its superior calculated performance output was successfully confirmed and demonstrated by different convenient energetic test methods.

Highly energetic 1,5-di(nitramino)tetrazole and its salts were synthesized. The neutral compound is very sensitive and one of the most powerful non-nuclear explosives to date. Selected nitrogen-rich and metal salts were prepared. The potassium salt can be used as a sensitizer in place of tetracene. The obtained compounds were characterized by low-temperature X-ray diffraction, IR and Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and DSC. Calculated energetic performances using the EXPLO5 code based on calculated (CBS-4M) heats of formation and X-ray densities support the high energetic performances of the 1,5-dinitraminotetrazolates as energetic materials. The sensitivities towards impact, friction, and electrostatic discharge were also explored.

1-Hydroxy-5-aminotetrazole (1), which is a long-desired starting material for the synthesis of hundreds of new energetic materials, was synthesized for the first time by the reaction of aqueous hydroxylamine with cyanogen azide. The use of this unique precursor was demonstrated by the preparation of several energetic compounds with equal or higher performance than that of commonly used explosives, such as hexogen (RDX). The prepared compounds, including energetic salts of 1-hydroxy-5-aminotetrazole (hydroxylammonium (2, two polymorphs) and ammonium (3)), azo-coupled derivatives (potassium (5), hydroxylammonium (6), ammonium (7), and hydrazinium 5,5'-azo-bis(1-N-oxidotetrazolate (8, two polymorphs)), as well as neutral compounds 5,5'-azo-bis(1-oxidotetrazole) (4) and 5,5'-bis(1-oxidotetrazole)hydrazine (9), were intensively characterized by low-temperature X-ray diffraction, IR, Raman, and multinuclear NMR spectroscopy, elemental analysis, and DSC. The calculated energetic performance, by using the EXPLO5 code, based on the calculated (CBS-4M) heats of formation and X-ray densities confirm the high energetic performance of tetrazole-N-oxides as energetic materials. Last but not least, their sensitivity towards impact, friction, and electrostatic discharge were explored. 5,5'-Azo-bis(1-N-oxidotetrazole) deflagrates close to the DDT (deflagration-to-detonation transition) faster than all compounds that have been investigated in our research group to date.

3,3′‐Diamino‐4,4′‐bifurazane (1), 3,3′‐diaminoazo‐4,4′‐furazane (2), and 3,3′‐diaminoazoxy‐4,4′‐furazane (3) were nitrated in 100 % HNO3 to give corresponding 3,3′‐dinitramino‐4,4′‐bifurazane (4), 3,3′‐dinitramino‐4,4′‐azofurazane (5) and 3,3′‐dinitramino‐4,4′‐azoxyfurazane (6), respectively. The neutral compounds show very imposing explosive performance but possess lower thermal stability and higher sensitivity than hexogen (RDX). More than 40 nitrogen‐rich compounds and metal salts were prepared. Most compounds were characterized by low‐temperature X‐ray diffraction, all of them by infrared and Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and by differential scanning calorimetry (DSC). Calculated energetic performances using the EXPLO5 code based on calculated (CBS‐4M) heats of formation and X‐ray densities support the high energetic performances of the nitraminofurazanes as energetic materials. The sensitivities towards impact, friction, and electrostatic discharge were also explored. Additionally the general toxicity of the anions against vibrio fischeri, representative for an aquatic microorganism, was determined.