Publication Date:
2011-05-06
Description:
The synthesis of 5,5′-diamino-3,3′-azo-1 H -1,2,4-triazole ( 3 ) by reaction of 5-acetylamino-3-amino-1 H -1,2,4-triazole ( 2 ) with potassium permanganate is described. The application of the very straightforward and efficient acetyl protection of 3,5-diamino-1 H -1,2,4-triazole allows selective reactions of the remaining free amino group to form the azo-functionality. Compound 3 is used as starting material for the synthesis of 5,5′-dinitrimino-3,3′-azo-1 H -1,2,4-triazole ( 4 ), which subsequently reacted with organic bases (ammonia, hydrazine, guanidine, aminoguanidine, triaminoguanidine) to form the corresponding nitrogen-rich triazolate salts ( 5 – 9 ). All substances were fully characterized by IR and Raman as well as multinuclear NMR spectroscopy, mass spectrometry, and differential scanning calorimetry. Selected compounds were additionally characterized by low temperature single-crystal X-ray diffraction measurements. The heats of formation of 4 – 9 were calculated by the CBS-4M method to be 647.7 ( 4 ), 401.2 ( 5 ), 700.4 ( 6 ), 398.4 ( 7 ), 676.5 ( 8 ), and 1089.2 ( 9 ) kJ · mol –1 . With these values as well as the experimentally determined densities several detonation parameters were calculated using both computer codes EXPLO5.03 and EXPLO5.04. In addition, the sensitivities of 5 – 9 were determined by the BAM drophammer and friction tester as well as a small scale electrical discharge device.
Print ISSN:
0044-2313
Electronic ISSN:
1521-3749
Topics:
Chemistry and Pharmacology
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