Isomerism of nitratoalkylazoles

In the field of energetic materials, traditional materials with high toxicity or other disadvantages are mostly used. There is an urgent need for trinitrotoluene replacements (TNT), which itself is toxic and its production is problematic due to red wastewater. New materials should be safe to handle, have good performance, and be inexpensive to synthesize. Nitratoalkylazoles are known to have low melting points and good energetic properties compared to TNT. In this paper, seven energetic compounds are synthesized starting from 5-methyltetrazole, 5-hydroxymethyltetrazole and 4,5-bishydroxymethyltriazole. The nitrates are characterized in terms of their physical, chemical, and energetic properties. Of those seven compounds, five are solid, melting between 27 °C and 110 °C, and two are liquid. Methylation and hydroxyalkylation were performed and discussed extensively. The organic nitrate is introduced in the last step so that the synthesis remains safe and scalable. Correlations between the molecular geometry and the melting points are explained. Calculations indicate detonation velocities that are 6%–11% higher than those of TNT. A discussion of the effect of isomerism on the properties leads to surprising insights and should help focus and accelerate research on the replacement of TNT.