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Z. Naturforsch. 2012, 67b, 573 – 588
doi:10.5560/ZNB.2012-0066
1-Amino-3-nitroguanidine (ANQ) in High-performance Ionic Energetic Materials
Niko Fischer, Thomas M. Klapötke, and Jörg Stierstorfer
Department of Chemistry, Energetic Materials Research, Ludwig-Maximilian University of Munich, Butenandtstr. 5–13 (Haus D), D-81377 Munich, Germany
Reprint requests to Prof. Dr. Thomas M. Klapötke. Fax: (+49-(0)89-2180 77492). E-mail: tmk@cup.uni-muenchen.de
Received March 5, 2012 / revised April 3, 2012 / published online July 6, 2012
Dedicated to Professor Wolfgang Beck on the occasion of his 80th birthday
1-Amino-3-nitroguanidine (ANQ, 2) was synthesized via hydrazinolysis of nitroguanidine (1). An appropriate Lewis structure of ANQ is drawn based on VB calculations. Due to its basicity, it can be protonated by strong mineral acids or acidic heterocycles. In order to synthesize new energetic materials the nitrate (3) and perchlorate (4) salts of 1-amino-3-nitroguanidine were synthesized by protonation of 2 with 40% nitric acid and 60% perchloric acid, respectively. 5-Nitrimino-1,4H-tetrazole obtained by reacting 5-amino-1H-tetrazole with 100% HNO3 was used to synthesize the nitriminotetrazolate salt 5. Furthermore, the dinitramide salt 6 of 1-amino-3-nitroguanidine was synthesized by metathesis reaction of silver dinitramide and 1-amino-3-nitroguanidinium chloride. The dinitroguanidinate salt 7 was synthesized by protonation of 2 with 1,3-dinitroguanidine, which was prepared from nitroguanidine in anhydrous nitric acid/N2O5. All compounds were fully characterized by single-crystal X-ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, and DSC measurements. The heats of formation of 27 were calculated using the atomization method based on CBS-4M enthalpies. With these values and the experimental (X-ray) densities several detonation parameters such as the detonation pressure, velocity, energy, and temperature were computed using the EXPLO5 code. In addition, the sensitivities towards impact, friction and electrical discharge were tested using the BAM drophammer, friction tester as well as a small-scale electrical discharge device. A Koenen test with 1-amino-3-nitroguanidinium nitrate (3) was carried out in order to evaluate its explosive performance and shipping classification.
Key words: Nitroguanidine, Energetic Materials, Crystal Structure, Sensitivity
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