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N-Bound Primary Nitramines Based on 1,5-Diaminotetrazole

Authors

  • Prof. Dr. Thomas M. Klapötke,

    Corresponding author
    1. Department of Chemistry, Ludwig-Maximilian-University of Munich, Butenandtstrasse 5–13, Haus D, 81377 Munich (Germany), Fax: (+49) 89-2180-77492
    • Department of Chemistry, Ludwig-Maximilian-University of Munich, Butenandtstrasse 5–13, Haus D, 81377 Munich (Germany), Fax: (+49) 89-2180-77492
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  • Dr. Franz A. Martin,

    1. Department of Chemistry, Ludwig-Maximilian-University of Munich, Butenandtstrasse 5–13, Haus D, 81377 Munich (Germany), Fax: (+49) 89-2180-77492
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  • Dr. Jörg Stierstorfer

    1. Department of Chemistry, Ludwig-Maximilian-University of Munich, Butenandtstrasse 5–13, Haus D, 81377 Munich (Germany), Fax: (+49) 89-2180-77492
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Abstract

1,5-Diaminotetrazole can be nitrated under very mild conditions by using nitronium tetrafluoroborate to result in 5-amino-1-nitriminotetrazole (1) in good yields. The same reaction can be performed with 1-amino-5-amino-4-methyltetrazole to yield 5-amino-4-methyl-1-nitriminotetrazole (2). Both compounds have been isolated and completely characterized by using vibrational spectroscopy, mass spectrometry, and differential scanning calorimetry. Additionally, X-ray diffraction measurements of the neutral compounds could be obtained; they indicated the structure of both compounds to be zwitterionic. Compounds 1 and 2 exhibit extremely high sensitivities to impact and friction and high positive heats of formation of 496 (1) and 453 kJ mol−1 (2), respectively. Additionally, high-nitrogen-containing salts of 1 have been synthesized by metathesis reactions of silver 5-amino-1-nitriminotetrazolate with the corresponding halides so as to investigate the changes in sensitivity and thermal stability. All ionic compounds have been synthesized in good yields and characterized by means of vibrational and multinuclear NMR spectroscopy as well as X-ray diffraction measurements. Thermal stabilities have been evaluated by differential scanning calorimetry, whereas sensitivity measurements have been performed according to standardized Bundesanstalt für Materialforschung und -prüfung (BAM) tests. Theoretical calculations have been performed to investigate the heats of formation as well as the performance characteristics of the compounds.

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