A series of 1,2,4-oxadiazole-derived energetic compounds were successfully synthesized using 1,2,4-oxadiazole-3-chloroxime as a versatile starting material. These energetic compounds were fully characterized by NMR spectroscopy, IR spectroscopy, and elemental analysis. The structures of compounds 5, 6a, 6c, 8 and 8a were determined by single crystal X-ray diffraction. The physicochemical and energetic properties of all the synthesized energetic compounds, including density, thermal stability and energetic performance (e.g., detonation velocities and detonation pressures) were investigated. Among these energetic compounds, hydrazinium salts 6b and 8b and hydroxylammonium salts 6c and 8c exhibit satisfactory calculated detonation performances, which outperform the commonly used high explosive RDX. Potassium salt 5 shows good detonation performance, high density as well as high sensitivity, making it a potential primary explosive. Compound 9 is a potential candidate for melt-cast explosives due to its remarkable liquid range between melting point (Tm = 98 °C) and decomposition temperature (Td = 208 °C).

Herein, a series of esteryl-bridged energetic compounds were prepared using a simple and efficient esterification approach. All the compounds were fully characterized by IR spectroscopy, multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, thermogravimetric analysis (TG), and differential scanning calorimetry (DSC). Structures of 1 and 4 were further confirmed by single crystal X-ray diffraction. Energetic performance was evaluated by EXPLO5 based on the measured densities and calculated heats of formation (Gaussian 09). These fluorodinitroethyl esters have good thermal stabilities (190.7–208.3 °C) and high densities (1.81–1.90 g cm−3). Detonation pressures and velocities of 1–5 fall in the range of 27.4–36.6 GPa and 7870–8459 m s−1, respectively. Sensitivity data based on impact and friction tests show that these compounds are insensitive (IS = 27.6–40 J; FS > 360 N). Moreover, two of the representative compounds 1 and 4 exhibit the desired melting points (1: 85.0 °C; 4: 94.7 °C) as the ideal melt cast explosives, relatively high detonation properties (D = 8459, 8196 m s−1; P = 36.6, 29.8 GPa), as well as relatively low sensitivities (IS = 30.5, 27.6 J; FS > 360 N).

Herein, the novel, thermally stable explosive 14,16,34,36,54,56,74,76-octanitro-2,4,6,8-tetraoxa-1,3,5,7(1,3)-tetrabenzenacyclooctaphane (4a) and its derivatives are reported. These compounds can be prepared via a facile synthetic procedure and show outstanding properties (detonation velocity, detonation pressure, sensitivity towards mechanical stimuli, and temperature of decomposition). Moreover, 4a and its derivatives were isolated and characterized via mass spectrometry and multinuclear (1H, 13C) NMR spectroscopy. The structures of 4a and 4b in the crystalline state were determined via low-temperature single-crystal X-ray diffraction. From the calculated standard molar enthalpies of formation (CBS-4M) and densities, the Chapman–Jouguet detonation properties were predicted using the EXPLO5 V6.01 thermochemical computer code. The sensitivities of 4a and its derivatives towards impact, friction, and electrostatic discharge were determined.

Two energetic N-trinitroethyl-substituted aminofurazans 11 and 12, as well as nitramine 13 (the N-nitration product of 12) were synthesized. All the compounds were well characterized by NMR spectra, IR spectroscopy, elemental analysis, differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). Their structures were further confirmed by X-ray diffraction studies, which show favorable densities (1.82–1.87 g cm−3). Interestingly, they exhibit good thermal stability (Tdec = 159–230 °C), acceptable oxygen balance (−15.31%–0) and high positive heats of formation (268–1259.5 kJ mol−1). In addition, the performance calculations gave detonation pressures and velocities for the furazan derivatives in the range of 35.4–40.8 GPa and 8900–9486 m s−1, respectively. Furthermore, nitramine 13 (nitrate product of 12), having an oxygen balance of zero, exhibits outstanding detonation properties (ΔfHm, 1259.5 kJ mol−1; D, 9486 m s−1; P, 40.8 GPa), which could be used as a high detonation performance energetic material.

Azoxyfurazan derivatives based on the trinitroethyl functionality were synthesized. These energetic N-trinitroethyl-substituted azoxyfurazans were fully characterized by using 1H and 13C NMR spectroscopy, IR, elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TG) as well as single crystal X-ray diffraction, and, in the case of N-trinitroethylamino azoxyfurazan 4, with 15N NMR spectroscopy. Furthermore, compound 4 and nitramine 5 have been tested for their responses to impact, friction, and electrostatic discharge. The detonation pressures and velocities of the azoxyfurazan derivatives were calculated, ranging from 35.8 GPa to 41.2 GPa and 8861 m s−1 to 9458 m s−1, respectively. Additionally, compound 5 having an oxygen balance of near zero (+2.5%), exhibits a favorable measured density (1.92 g cm−3) and excellent detonation property (ΔfHm, 962.1 kJ mol−1; P, 41.2 GPa; D, 9458 m s−1). Thus, these compounds could be potential high detonation performance energetic materials.

The reaction of 1,5-diaminotetrazole with picryl chloride (PiCl) forms 5-picrylamino-1,2,3,4-tetrazole (PAT) rather than the expected 1-picrylamino-5-amino-1,2,3,4-tetrazole or 5-picrylamino-1-amino-1,2,3,4-tetrazole. The structure of PAT was confirmed by single-crystal X-ray diffraction. Some of the energetic properties of the synthesized compound were also studied.

A high-nitrogen compound (N10 structure), 1,1′-azobis(5-methyltetrazole) which is relatively stable, was obtained by azo coupling reactions with three different oxidants such as trichloroisocyanuric acid (TCICA), sodium dichloroisocyanurate (SDIC) and tert-butyl hypochlorite (t-BuOCl). In particular, TCICA has been used for the first time to oxidize N–NH2 to the N–NN–N linkage. The structural elucidation of the title compound was made by spectral and X-ray crystallographic analyses. The new N10 linkage containing compound exhibits both relative thermal stability and physical stability.

Novel Keggin heteropolyacid anion based Brønsted acidic ionic salts [SO3H(CH2)4Mim]nH3–nPMo12O40 (n = 1, 2, 3) were synthesized and used as catalysts in the nitration of aromatic compound in HNO3 (67%). The catalytic activity was in the order of [(CH2)4SO3HMim]3PMo12O40 > [(CH2)4SO3HMim]2HPMo12O40 > [(CH2)4SO3HMim]H2PMo12O40. The effect of catalyst loading, quantity of nitro acid and temperature on nitration of toluene was discussed, and 87.7% yield and good para selectivity with 1.19 ratio of ortho to para can be obtained with optimized catalyst [(CH2)4SO3HMim]3PMo12O40. The catalyst can be easily separated from the products and recycled for three times without significant loss of activity.

Two energetic N-trinitroethyl-substituted aminofurazans 11 and 12, as well as nitramine 13 (the N-nitration product of 12) were synthesized. All the compounds were well characterized by NMR spectra, IR spectroscopy, elemental analysis, differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). Their structures were further confirmed by X-ray diffraction studies, which show favorable densities (1.82–1.87 g cm−3). Interestingly, they exhibit good thermal stability (Tdec = 159–230 °C), acceptable oxygen balance (−15.31%–0) and high positive heats of formation (268–1259.5 kJ mol−1). In addition, the performance calculations gave detonation pressures and velocities for the furazan derivatives in the range of 35.4–40.8 GPa and 8900–9486 m s−1, respectively. Furthermore, nitramine 13 (nitrate product of 12), having an oxygen balance of zero, exhibits outstanding detonation properties (ΔfHm, 1259.5 kJ mol−1; D, 9486 m s−1; P, 40.8 GPa), which could be used as a high detonation performance energetic material.

The reaction of 1,5-diaminotetrazole with picryl chloride (PiCl) forms 5-picrylamino-1,2,3,4-tetrazole (PAT) rather than the expected 1-picrylamino-5-amino-1,2,3,4-tetrazole or 5-picrylamino-1-amino-1,2,3,4-tetrazole. The structure of PAT was confirmed by single-crystal X-ray diffraction. Some of the energetic properties of the synthesized compound were also studied.