Synthesis and Characterization of the Energetic Compounds Aminoguanidinium-, Triaminoguanidinium- and Azidoformamidinium Perchlorate

Aminoguanidinium perchlorate (2, AGClO4) was formed by the reaction of aminoguanidinium bicarbonate (1) with aqueous perchloric acid solution. Triaminoguanidinium perchlorate (3, TAGClO4) was synthesized by nucleophilic attack of aqueous hydrazine solution on aminoguanidinium perchlorate under release of ammonia. The new and highly explosive azidoformamidinium perchlorate (4, AFClO4) was formed by the reaction of aminoguanidinium perchlorate with potassium nitrite under acidic conditions. The structures of the perchlorate salts in the crystalline state were determined using low temperature single crystal X-ray diffraction yielding monoclinic as well as orthorhombic structures. The compounds were characterized comprehensively using vibrational spectroscopy (IR and Raman), multinuclear (1H, 13C and 15N) NMR spectroscopy, elemental analysis and mass spectrometry. The thermal behavior as well as the decompositions were investigated using DSC (differential scanning calorimetry) and the heats of formation were calculated using heats of combustion determined by bomb calorimetric measurements. In addition, the sensitivities were evaluated using BAM methods (drophammer and friction tester), whereby the perchlorate salts are all sensitive towards impact as well as friction.