Manfred Kaiser

Synthesis and Characterization of Hydrazinium Azide Hydrazinate

Hydrazinium azide hydrazinate, [N2H5]+[N3]−ċN2H4 was synthesized from equimolar amounts of hydrazinium azide and hydrazine and characterized by single crystal X-ray diffraction: monoclinic, P 21/c, a=6.3704(2), b=12.1111(4), c=6.9940(2) A, β=91.8666(2) °, V=539.32(3) A3, Z=4, ρ=1.320 g cm−1. The compound is less hygroscopic and less volatile than hydrazinium azide. Explosion of [N2H5]+[N3]−ċN2H4 yielded dinitrogen (N2), ammonia (NH3) and dihydrogen (H2). Compared to hydrazinium azide, the hydrazine adduct produces larger amounts of ammonia in the explosion.

Triazidotrinitro Benzene: 1,3,5-(N3)3-2,4,6-(NO2)3C6

Triazidotrinitro benzene, 1,3,5-(N3)3-2,4,6-(NO2)3C6 (1) was synthesized by nitration of triazidodinitro benzene, 1,3,5-(N3)3-2,4-(NO2)2C6H with either a mixture of fuming nitric and concentrated sulfuric acid (HNO3/H2SO4) or with N2O5. Crystals were obtained by the slow evaporation of an acetone/acetic acid mixture at room temperature over a period of 2 weeks and characterized by single crystal X-ray diffraction: monoclinic, P 21/c (no. 14), a=0.54256(4), b=1.8552(1), c=1.2129(1) nm, β=94.91(1)°, V=1.2163(2) nm3, Z=4, ϱ=1.836 g⋅cm−3, Rall =0.069. Triazidotrinitro benzene has a remarkably high density (1.84 g⋅cm−3). The standard heat of formation of compound 1 was computed at B3LYP/6-31G(d, p) level of theory to be ΔH°f=765.8 kJ⋅mol−1 which translates to 2278.0 kJ⋅kg−1. The expected detonation properties of compound 1 were calculated using the semi-empirical equations suggested by Kamlet and Jacobs: detonation pressure, P=18.4 GPa and detonation velocity, D=8100 m⋅s−1.

Methylated Derivatives of Hydrazinium Azide

The synthesis and characterization of polymethylated hydrazinium azide species is reported. The crystal structure of methylhydrazinium azide and N,N′-dimethylhydrazinium azide was determined. The thermal, shock and friction sensitivity as well as the explosion products of some of the compounds were investigated.

N,N′-Diorganylsubstituted Hydrazinium Azides

1,2-Diorganylsubstituted derivatives of hydrazinium azide were examined in order to investigate their higher volatility and higher sensitivity to initiation compared to 1,1-diorganylsubstituted hydrazinium azide derivatives. The compounds were synthesized from the respective hydrazines by reaction with HN3 and characterized by elemental analysis, vibrational (IR, Raman) and multinuclear NMR spectroscopy (1H, 13C, 14N). Their sensitivity to friction, shock, electrostatic impact and heat was examined and the explosion products were investigated. The crystal structure of pyrazolidinium azide was determined. 1,2-Diorganylsubstituierte Hydraziniumazide 1,2-Diorganylsubstituierte Hydraziniumazide wurden untersucht, um ihre hohere Fluchtigkeit und ihre grosere Zundfahigkeit im Vergleich zu 1,1-diorganylsubstituierten Hydraziniumaziden zu verstehen. Es wurden 1,2-diorganylsubstituierte Hydraziniumazide verwendet, in denen das Hydrazinmolekul Teil eines Ringsystems ist, um feste Verbindungen zu erhalten. Die Verbindungen wurden aus den jeweiligen Hydrazinen durch Reaktion mit HN3 hergestellt und durch Elementaranalyse, IR-, Raman- und NMR-Spektroskopie charakterisiert. Ihre Empfindlichkeit auf Schlag, Reibung, Funken und Hitze wurde getestet und die Produkte ihrer Explosion untersucht. Die Kristallstruktur von Pyrazolidiniumazid wurde bestimmt.

New Hydrazinium Azide Compounds

The synthesis and characterization of several azide salts of organic hydrazinium derivatives is reported. The crystal structures of N-amino-1-azoniacycloheptane azide, morpholinium azide, N,N-dibenzylhydrazine and phenylhydrazinium azide phenylhydrazinate were determined. The thermal, shock and friction sensitivity of these compounds was investigated. For several compounds the products formed in the explosive decomposition were determined. Neue Hydrazinium Azide Einige Organylhydraziniumazide wurden hergestellt und die Kristallstrukturen von N-Amino-1-azoniacycloheptanazid, Morpholiniumazid, N,N-Dibenzylhydrazin and Phenylhydraziniumazid-phenylhydrazinat bestimmt. Die Verbindungen wurden auf ihre Empfindlichkeit gegenuber thermischer Belastung, Schlag und Reibung gepruft. Fur einige Verbindungen wurden die bei ihrer Explosion entstehenden Produkte bestimmt.

Methylated Ammonium and Hydrazinium Salts of 5,5′-Azotetrazolate

Abstract Salts of the 5,5′-azotetrazolate dianion with methylated ammonium and hydrazinium cations were prepared. The compounds were characterized by elemental analysis, vibrational (IR, Raman) and multinuclear NMR spectroscopy (1H, 13C, 14N). The crystal structures of the di[ammonium], the bis[dimethylammonium] and the bis[trimethylhydrazinium] 5,5′-azo tetrazolate salts were determined. The thermal, shock and friction sensitivities of these com pounds were investigated and their explosion products were analysed.

New Hydrazinium Salts of 5,5'-Azotetrazolate

Abstract Salts of the 5,5′-azotetrazolate dianion with several different hydrazinium cations were pre pared. The compounds were characterized by elemental analysis, vibrational spectroscopy (IR, Raman) and multinuclear NMR spectroscopy (1H, 13C, 14 N). The crystal structures of the di-tert-butylhydrazinium, the ethylenedihydrazinium, the diguanidinium and the bis-triamino-guanidinium azotetrazolate were determined. The thermal, shock and friction sensitivities of all compounds were investigated and their explosion products were analysed. For the 5,5′-azotetr-azolate dianion the structure was calculated with density functional theory (B3-LYP). An NBO analysis was performed for the 5,5′-azotetrazolate dianion in order to understand the charge distribution of the dianion.