Synthesis and Promising Properties of a New Family of High-Nitrogen Compounds: Polyazido- and Polyamino-Substituted N,N′-Azo-1,2,4-triazoles

A new family of high‐nitrogen compounds, that is, polyazido‐ and polyamino‐substituted N,N′‐azo‐1,2,4‐triazoles, were synthesized in a safe and convenient manner and fully characterized. The structures of 3,3′,5,5′‐tetra(azido)‐4,4′‐azo‐1,2,4‐triazole (15) and 3,3′,5,5′‐tetra(amino)‐4,4′‐azo‐1,2,4‐triazole (23) were also confirmed by X‐ray diffraction. Differential scanning calorimetry (DSC) was performed to determine their thermal stability. Their heats of formation and density, which were calculated by using Gaussian 03, were used to determine the detonation performances of the related compounds (EXPLO 5.05). The heats of formation of the polyazido compounds were also derived by using an additive method. Compound 15 has the highest heat of formation (6933 kJ kg−1) reported so far for energetic compounds and a detonation performance that is comparable to that of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX), while compound 23 has a decomposition temperature of up to 290 °C. Showing some backbone: The N,N′‐azo heteroaromatic backbone could be used to develop new high‐nitrogen compounds with promising properties. Polyazido and polyamino compounds 1 and 2, respectively, were efficiently synthesized in a safe and convenient manner (see figure).