5-(1H-Tetrazolyl)-2-Hydroxy-Tetrazole: A Selective 2N-Monoxidation of Bis(1H-Tetrazole)

Sodium 5‐cyanotetrazolate sesquihydrate (1) is prepared from sodium azide and two equivalents of sodium cyanide under acidic conditions. 1 is then N‐oxidized with Oxone to sodium 5‐cyanotetrazolate monohydrate (2). Compound 2 is treated with sodium azide and a Lewis acid to form 5‐(1H‐tetrazolyl)‐2‐...

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Bibliographic Details
Published in:ChemPlusChem (Weinheim, Germany) Germany), 2015-01, Vol.80 (1), p.97-106
Main Authors: Klapötke, Thomas M., Kurz, Matthias Q., Scharf, Regina, Schmid, Philipp C., Stierstorfer, Jörg, Sućeska, Muhamed
Format: Article
Language:English
Subjects:
energetic materials
heterocycles
N-oxides
tetrazoles
X-ray diffraction
Online Access:Get full text
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Summary:Sodium 5‐cyanotetrazolate sesquihydrate (1) is prepared from sodium azide and two equivalents of sodium cyanide under acidic conditions. 1 is then N‐oxidized with Oxone to sodium 5‐cyanotetrazolate monohydrate (2). Compound 2 is treated with sodium azide and a Lewis acid to form 5‐(1H‐tetrazolyl)‐2‐hydroxytetrazole monohydrate (3). Compound 3 can be deprotonated twice by various bases to give ionic derivatives such as the bis(hydroxylammonium) (4), bis(hydrazinium) (6), bis(guanidinium) (7), bis(aminoguanidinium) (8), bis(ammonium) (9), and diaminouronium (11) salt. In addition, compound 3 can only be deprotonated once, as demonstrated by the hydroxylammonium (4) and triaminoguanidinium (10) salts. Compounds 2–5 and 10–11 are structurally characterized by single‐crystal X‐ray diffraction. Additionally, compounds 2–11 are characterized by using NMR and vibrational (IR, Raman) spectroscopy as well as mass spectrometry and elemental analysis. Their thermal behaviors are studied from differential thermal analysis measurements, and the sensitivities of the compounds toward shock, friction, and electrostatic discharge are determined. In addition, the heats of formation are calculated (atomization method, CBS‐4M enthalpies), and several detonation/propulsion parameters are computed with the EXPLO5 code. Energetic materials: Following the recent trend in the synthesis of new energetic materials with high densities and stabilities, the first bistetrazole 2N‐monoxide was prepared (see figure). 5‐(1H‐Tetrazolyl)‐2‐hydroxy‐tetrazole and several energetic salts were synthesized, characterized, and compared with RDX and other energetic tetrazole‐N‐oxides.
ISSN:2192-6506
2192-6506
DOI:10.1002/cplu.201402124