Transition metal complexes of 3-amino-1-nitroguanidine as laser ignitible primary explosives: structures and properties.

3-Amino-1-nitroguanidine (ANQ, 2) was synthesized via hydrazinolysis of nitroguanidine. By dissolving 2 in solutions containing transition metal salts, several complexes M(2+)(ANQ)2X2(H2O)y with M(2+) = Co, Ni, Cu, Zn as well as M(ANQ)2X(H2O)y with M = Ag could be isolated. In these cases, nitrate as well as perchlorate and chloride served as the respective anions X.

The chemistry of 5-(tetrazol-1-yl)-2H-tetrazole: an extensive study of structural and energetic properties.

5-(Tetrazol-1-yl)-2H-tetrazole (1), or 1,5'-bistetrazole, was synthesized by the cyclization of 5-amino-1H-tetrazole, sodium azide and triethyl orthoformate in glacial acetic acid. A derivative of 1, 2-methyl-5-(tetrazol-1-yl)tetrazole (2) can be obtained by this method starting from 5-amino-2-methyl-tetrazole. Furthermore, selected salts of 1 with nitrogen-rich and metal (alkali and transition metal) cations, including hydroxylammonium (4), triaminoguanidinium (5), copper(I) (8) and silver (9), as well as copper(II) complexes of both 1 and 2 were prepared.

5,5'-Azoxytetrazolates--a new nitrogen-rich dianion and its comparison to 5,5'-azotetrazolate.

A modification of the synthesis of sodium 5,5'-azotetrazolate pentahydrate, described by Thiele in 1898, yields the unknown and unexpected corresponding 5N-oxido derivative sodium 5,5'-azoxybistetrazolate pentahydrate (Na(2)zTO·5H(2)O, 1). Purification was achieved by recrystallization based on the better solubility of Na(2)zTO·5H(2)O in water. Different nitrogen-rich salts, such as the diammonium (3), the dihydroxylammonium (4), the bis-diaminoguanidinium (5), the bis-triaminoguanidinium (6) and the diaminouronium salt (7), have been prepared using metathesis reactions starting from barium 5,5'-azoxybistetrazolate pentahydrate (2) and ammonium, hydroxylammonium, diaminoguanidinium or diaminouronium sulfate and triaminoguanidinium chloride, respectively.

Nitrogen-rich 5,5'-bistetrazolates and their potential use in propellant systems: a comprehensive study.

A large variety of twice-deprotonated nitrogen-rich 5,5'-bistetrazolates, that is, the ammonium (1), hydrazinium (2), hydroxylammonium (3), guanidinium (4), aminoguanidinium (5), diaminoguanidinium (6), triaminoguanidinium (7), and diaminouronium (8) salts, have been synthesized. Energetic compounds 1-8 were fully characterized by single-crystal X-ray diffraction (except 8), NMR spectroscopy, IR and Raman spectroscopy, and differential scanning calorimetry (DSC) measurements. With respect to their potential use in propellant applications, the sensitivity towards impact, friction, and electrical discharge were determined.

Sensitivities of some imidazole-1-sulfonyl azide salts.

Imidazole-1-sulfonyl azide hydrochloride, an inexpensive and effective diazotransfer reagent, was recently found to be impact sensitive. To identify safer-to-handle forms of this reagent, several different salts of imidazole-1-sulfonyl azide were prepared, and their sensitivity to heat, impact, friction, and electrostatic discharge was quantitatively determined. A number of these salts exhibited improved properties and can be considered safer than the aforementioned hydrochloride.

N-rich salts of 2-methyl-5-nitraminotetrazole: secondary explosives with low sensitivities.

2-Methyl-5-nitraminotetrazole (1) was formed by nitration of 2-methyl-5-aminotetrazole. 2-Methyl-5-aminotetrazole was obtained by an improved synthesis starting from sodium 5-aminotetrazolate, which is methylated with dimethyl sulfate in dimethyl formamide giving 2-methyl-5-aminotetrazole in 29% yield. Nitrogen-rich salts such as guanidinium (2), 1-aminoguanidinium (3), 1,3-diamino-guanidinium (4), 1,3,5-triamino-guanidinium (5), azidoformamidinium (6), hydrazinium (7), diaminouronium 2-methyl-5-nitraminotetrazolate (8), as well as an urea adduct (9), were prepared by facile deprotonation or metathesis reactions.