Are DTTO and iso‐DTTO Worthwhile Targets for Synthesis?

Abstract

Theoretical calculations were carried out for the isomeric di‐1,2,3,4‐tetrazine tetraoxides (DTTO and iso‐DTTO). The most important explosion performance parameters, the detonation pressure and detonation velocity, are dominated by the densities and not by the heats of formation of these compounds. Since DTTO and iso‐DTTO are unknown, reliable predictions of their crystal densities are crucial for an evaluation of the potential of these materials as explosives. In this study, the crystal densities were predicted using both Ammon’s Atom/Functional Group and Atom Code Volume Additivity Parameters and Quantum Mechanical molecular Volume methods, resulting in similar densities and explosion parameters. Although the likely uncertainties in our predicted density values are difficult to assess due to a lack of experimental data for closely related known compounds, our results demonstrate that Shechter’s originally proposed densities and performance parameters were grossly overestimated. Furthermore, it is shown that, based on our predicted density value ranges, DTTO and iso‐DTTO could match or substantially outperform the best state of the art explosives, such as CL‐20. Therefore, the synthesis of DTTO and iso‐DTTO should be further pursued.

Synthesis of Tetrazino‐tetrazine 1,3,6,8‐Tetraoxide (TTTO)

“…Since then, a number of theoretical studies on TTTO 1 have been published . By theoretical data, the TTTO 1 heat of formation is about 206 kcal mol −1 , density 1.98 g cm −3 , estimated detonation velocity 9.71 km s −1 , and detonation pressure 432 kbar, which puts it on a par with the most powerful explosives known. Similar estimated data were obtained for [1,2,3,4]tetrazino[5,6‐ e ][1,2,3,4]tetrazine 1,3,5,7‐tetraoxide (iso‐TTTO) …”

Fused heterocycle-based energetic materials (2012–2019)

“…Compound 37 has excellent theoretical detonation properties (D ¼ 10 900 m s À1 and P ¼ 60.0 GPa). As a result, their syntheses were desirable targets for chemists and have attracted considerable interest (Scheme 14) 35.…”

Properties and Promise of Catenated Nitrogen Systems As High-Energy-Density Materials

“…420−423 Nevertheless, calculations with improved theoretical methods suggested that, even over a wide range of hypothetical densities, DTTO is predicted to have promising explosive properties and was a worthy synthetic target. 424 Just a few years ago, in 2016, the synthesis was finally achieved by the group of Churakov via a complex 8-step synthesis with 1% yield overall. 419 However, the controversy on the density of the pure phase is unresolved as the material was isolated as a benzene solvate with a lower density of 1.68 g/cm 3 (Figure 35).…”