Oxetane Monomers Based On the Powerful Explosive LLM-116: Improved Performance, Insensitivity, and Thermostability.

3-Bromomethyl-3-hydroxymethyloxetane represents an inexpensive and versatile precursor for the synthesis of 3,3-disubstituted oxetane derivatives. In the present work, its synthesis was improved and energetic oxetanes based on the explosive LLM-116 (4-amino-3,5-dinitro-1H-pyrazole) prepared. Reaching detonation velocities and pressures of up to 7335 ms-1 and 20.9 GPa in combination with a high thermostability and insensitivity, these surpass the prior art by far. Next to a symmetric LLM-116 derivative, three asymmetric compounds were prepared using azido-, nitrato- and tetrazolyl-moieties. All compounds were intensively characterized by vibrational-, mass- and multinuclear (1 H, 13 C, 14 N) NMR spectroscopy, differential scanning calorimetry and elemental analysis. The molecular structures were elucidated by single crystal X-ray diffraction. Hirshfeld analysis allowed to estimate their sensitivity next to a practical evaluation using BAM standard procedures. Their performance was calculated using the EXPLO5 V6.04 code and a small-scale shock reactivity test and initiation test demonstrated their insensitivity and performance.

Synthesis and Characterization of Binary, Highly Endothermic, and Extremely Sensitive 2,2'-Azobis(5-azidotetrazole).

2,2'-Azobis(5-azidotetrazole) (C2N16, 3), a highly energetic nitrogen-rich binary CN compound was obtained in a three-step synthesis through the formation of 5-azidotetrazole (1), subsequent amination using O-tosylhydroxylamine to give 2-amino-5-azidotetrazole (2), and oxidative azo coupling of 2 using tBuOCl as an oxidant in MeCN. A nitrogen:carbon ratio of 8:1, eight nitrogen atoms in a row, and a nitrogen content of over 90% was unknown for a binary heterocyclic compound until now. The successful isolation was confirmed through X-ray diffraction as well as by vibrational and 13C NMR spectroscopy. C2N16 can explode instantly and shows mechanical sensitivities far higher than quantitatively measurable. Nevertheless, it features interesting energetic performances, which were calculated using different quantum-chemical methods.

Synthesis, Characterization and Energetic Performance of Oxalyl Diazide, Carbamoyl Azide, and N,N'-Bis(azidocarbonyl)hydrazine.

As pure compounds, small carbonyl azides enjoy a bad reputation, due to the high explosive sensitivity and instability they demonstrate. Consequently, most reported examples have only been poorly characterized. The compounds oxalyl diazide (1), carbamoyl azide (2), as well as N,N'-bis(azidocarbonyl)hydrazine (3) were obtained by performing a diazotation reaction on the corresponding hydrazo precursor. Carbamoyl azide (2) could also be obtained from oxalyl diazide via Curtius rearrangement to the reactive isocyanate, followed by reaction with water. Further, different trapping reactions of the isocyanate with hydroxyl (methanol, oxetan-3-ol) and amino (2-amino-5H-tetrazole) functions are described. All products were extensively analyzed using IR, EA, DTA and multinuclear NMR spectroscopy, and the crystal structures elucidated using single crystal X-ray diffraction. In addition, the sensitivities toward friction and impact were determined and the energetic performances of the carbonyl azides were calculated using the EXPLO5 code.

3,3-Dinitratooxetane - an important leap towards energetic oxygen-rich monomers and polymers.

3-Substituted oxetanes are valuable monomers for modern ring-opening polymerizations. A new solid-state oxidizer, 3,3-dinitratooxetane (C3H4N2O7), which has an oxygen content of 62.2% was synthesized by the addition of N2O5 to oxetan-3-one. Monoclinic single crystals suitable for X-ray diffraction (ρ 1.80 g cm-3) were obtained by recrystallization from dichloromethane. In addition, 3-nitratooxetane was prepared by an improved method and 3-nitrato-3-methyloxetane was synthesized for the first time. Theoretical calculations were computed by the EXPLO5 software and additionally sensitivities towards impact and friction were determined.