Improved Synthesis and X‐Ray Structure of 5‐Aminotetrazolium Nitrate

Denffer, Moritz von; Klapötke, Thomas M.; Kramer, Gernot; Spieß, Gunnar; Welch, Jan M.; Heeb, Gerhard

doi:10.1002/prep.200500004

Cited by 85 publications

(48 citation statements)

References 15 publications

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“…Heterocyclic compounds like tetrazoles are of particular interest because nitrogen content of such compounds can be increased to over 70% by substitution with suitable functional groups [8][9][10][11]. Different tetrazole derivatives such as salts of 5,5 0 -azotetrazole [12], bistetrazoles [13], the perchlorate and nitrate of 1,5-diaminotetrazole [14], salts of 1-methyl-5-nitriminotetrazolate [15], alkali metal 5,5 0 -hydrazinebistetrazolate salts [16], 5-nitroaminotetrazole salts [17], and organic salts of nitrotetrazole [18] have been tested as potential materials for modifying the combustion rates of rocket propellants, as gas generators and explosive materials.…”

Section: Introductionmentioning

confidence: 99%

Computational studies on tetrazole derivatives as potential high energy materials

2011

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The tetrazole is an important functionality of the most of energetic materials due to 80% nitrogen content, stability, and high enthalpy of formation. The present structure-property relationship study focuses on the optimized geometries of tetrazole derivatives obtained from density functional theory (DFT) calculations at B3LYP/6-31G* levels. The heat of formation (HOF) of tetrazole derivatives have been calculated by designing the appropriate isodesmic reactions. The increase in nitro groups on azole rings shows the remarkable increase in HOF. Density has been predicted by using CVFF force field. Increase in the nitro group increases the density. Detonation properties of the designed compounds were evaluated by using the Kamlet-Jacobs equation based on predicted densities and HOFs. Designed tetrazole derivatives show detonation velocity (D) over 8 km/s and detonation pressure (P) of about 32 GPa. Thermal stability was evaluated via bond dissociation energies (BDE) of the weakest C-NO 2 bond at B3LYP/6-31G* level. Charge on the nitro group has been used to assess the sensitivity correlation. Overall, the study implies that designed compounds of this series are found to be stable and expected to be the novel candidates of high energy materials (HEMs).

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Section: Introductionmentioning

confidence: 99%

Computational studies on tetrazole derivatives as potential high energy materials

2011

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“…These are the first CO-balanced EILs. Although an oxygenbalanced tetrazolium salt, 5-aminotetrazolium nitrate, was recently reported, [10] its melting point of 173 8C does not classify it as an ionic liquid.…”

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confidence: 99%

Oxygen‐Balanced Energetic Ionic Liquid

et al. 2006

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Energetic ionic liquids (EILs) are of great interest. [1][2][3] They offer enhanced stability, higher densities, no vapor pressure, and, hence, no vapor toxicity. As a general principle, the stability of energetic ionic compounds can be greatly enhanced by making the cation the fuel and the anion the oxidizer. The formal positive charge increases the ionization potential of the fuel cation, and the formal negative charge decreases the electron affinity of the anion. In this manner, the fuel cation becomes more oxidizer-resistant, and the oxidizer anion is protected against premature reduction by the cation. For environmental reasons, it is also desirable to avoid halogen-containing ingredients, such as perchlorates.The previously known EILs consist of small oxidizing anions, such as ClO 4 À , NO 3 À , or N(NO 2 ) 2 À , and large fuel cations containing quaternary nitrogen heterocycles with long, asymmetric, poorly packing side chains. The most serious drawback of these EILs is that they are underoxidized. The small anions do not carry sufficient oxygen for complete oxidation of the large fuel cations to carbon monoxide, resulting in poor performance. In rocket propulsion, a low molecular weight of the exhaust products is very important. [4,5] Furthermore, at high flame temperatures CO 2 is dissociated almost completely to CO and O 2 (Boudouard equilibrium).[6] Therefore, it is often sufficient to oxidize the carbon content only to CO and not to CO 2 to achieve nearmaximum performance.[5] The aim of this study was the preparation of halogen-free, CO-balanced, EILs.In 1998, the concept of oxidizer-balanced EILs was proposed, and in 2002, its practicability was shown by the preparation of 1-ethyl-3-methylimidazolium tetranitratoborate, [7] a compound that turned out to be indeed an ionic liquid with a freezing point of À25 8C. However, its energy content and thermal stability were marginal. Herein, we report on a significantly improved compound using the tetranitratoaluminate anion as a thermally more stable highoxygen carrier and the 1-ethyl-4,5-dimethyltetrazolium cation as a more energetic counterion (imidazole, DH o f = + 49.8 kJ mol À1 ; [8] tetrazole, DH o f = + 237.1 kJ mol À1 [9] ). These are the first CO-balanced EILs. Although an oxygenbalanced tetrazolium salt, 5-aminotetrazolium nitrate, was recently reported, [10] its melting point of 173 8C does not classify it as an ionic liquid.Polynitratoaluminates were first studied in the 1960s in the USA [11] and, subsequently, during the 1970s in the USSR. [12][13][14][15][16][17][18][19][20][21][22][23] Several examples of alkali metal, [12][13][14][15][16][17][18][19][20][21] NO 2 + , [22,23] and ethylammonium salts [24] of tetra-, penta-, and hexanitratoaluminate anions are known. The tetranitratoaluminate anion contains 12 oxygen atoms; of these, 10.5 are available to oxidize a fuel cation.Alkylated tetrazolium cations were used in this work because of their large positive heats of formation and their potential to form ionic liquids. Ionic salts of the t...

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“…5-aminotetrazolium nitrate. [27] In the structure of 3 layers are formed, which are formed by a strong hydrogen-bond network. All of the oxygen atoms of the nitrate anions participate in strong hydrogen bonds listed in Table 2.…”

Section: Tablementioning

confidence: 99%

Synthesis and Characterization of 3,5‐Diamino‐1,2,4‐triazolium Dinitramide

Klapötke¹,

Martin²,

Mayr³

et al. 2010

Zeitschrift anorg allge chemie

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.3,5-Diamino-1,2,4-triazole (1, guanozol) was protonated with diluted hydrochloric acid, nitric acid, as well as perchloric acid forming 3,5-diamino-1,2,4-triazolium chloride hemihydrate (2), 3,5-diamino-1,2,4-triazolium nitrate (3) and 3,5-diamino-1,2,4-triazolium perchlorate (4), respectively. In a second step 4 was reacted with potassium dinitramide forming 3,5-diamino-1,2,4-triazolium dinitramide (5) and low soluble potassium perchlorate. 2-5 were characterized by low temperature single X-ray diffraction, IR and Raman as well as multinuclear NMR spectroscopy, mass spectrometry and differential scanning calorimetry.The heat of formation of 1-5 were calculated by the CBS-4M method to be 81.1 (1), 124.7 (2), -76.1 (3), -25.2 (4) and 138.7 (5) kJ mol -1 . With these values as well as the X-ray densities several detonation parameters were calculated using both computer codes EXPLO5.03 and EXPLO5.04. In addition, the sensitivities of 1-5 were determined by the BAM drophammer and friction tester as well as a small scale electrical discharge device.

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Improved Synthesis and X‐Ray Structure of 5‐Aminotetrazolium Nitrate

Cited by 85 publications

References 15 publications

Computational studies on tetrazole derivatives as potential high energy materials

Computational studies on tetrazole derivatives as potential high energy materials

Oxygen‐Balanced Energetic Ionic Liquid

Synthesis and Characterization of 3,5‐Diamino‐1,2,4‐triazolium Dinitramide

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