Polynitroalkyltetrazoles

Abstract

5‐(Fluorodinitromethyl)‐and 5‐(trinitromethyl)tetrazoles were synthesized in the reactions of fluorodinitroacetonitrile with sodium azide, and trinitroacetonitrile with trimethylsilyl azide, respectively, and characterized as their ammonium salts.

5-(Fluorodinitromethyl)-2H-tetrazole and its tetrazolates – Preparation and Characterization of New High Energy Compounds

“…The tetrazole and the salts were identified only by IR and 19 F NMR spectra and have not been well characterized. 17,18 In this manuscript we report the synthesis and full characterization of 5-(fluorodinitromethyl)-2H-tetrazole and three salts with the energetic 5-(fluorodinitromethyl)tetrazolate anion.…”

New Energetic Polynitrotetrazoles

“…After an acidic workup and treatment with aqueous ammonia (25 %) ammonium 5‐(fluorodinitromethyl)‐2 H ‐tetrazolate ( 6 ) was isolated in acceptable yields of 32 % (two steps from compound 4 ). If trimethylsilyl azide is used instead of sodium azide as known from the literature,15 with heating the risk of the formation of undesired side products including azidodinitro acetonitrile ( 7 ) is given. In fact, 19 F NMR experiments out of this reaction mixture confirmed the generation of more than three species even without heating, and ring closing reactions were continued with sodium azide.…”

“…The syntheses of 5‐trinitromethyl‐ and 5‐fluorodinitromethyl‐2 H ‐tetrazole and some of their salts were first published in 1981 by Grakauskas et al 15. and Fokin et al.,16 respectively.…”

Synthetic routes towards tetrazolium and triazolium dinitromethylides

“…A focus of recent interest in new energetic compounds has been the synthesis of azaheterocycles polynitrated in a side chain possessing high performance and low sensitivity to friction and impact [2][3][4]. Known classes include 5-(dinitromethyl)tetrazoles [4,5], 2-aminopyridinium dinitromethylides [6,7], and 1,1-diamino-2,2dinitroethane derivatives [3].…”

“…__________________________________________________________________________________________ 1 Center for Heterocyclic Compounds, University of Florida, Department of Chemistry, Gainesville, Florida 32611-7200, USA; e-mail: Katritzky@chem.ufl.edu. 3 5-(Dinitromethyl)-1H-tetrazoles have been prepared: i) from the sodium salt of dinitroacetonitrile (6) in two steps involving nucleophilic attack of the azide ion on the carbon atom of the nitrile group (8-12%) followed by ring closure to give 5-dinitromethyl-1H-tetrazole (7) with 8% yield (Scheme 3) [9]; and also by ii) 1,3-dipolar addition of fluorodinitroacetonitrile (8) with sodium azide providing 5-[fluoro(dinitro)methyl]-1H-tetrazole (9) with 85% yield [4]. 3 5-(Dinitromethyl)-1H-tetrazoles have been prepared: i) from the sodium salt of dinitroacetonitrile (6) in two steps involving nucleophilic attack of the azide ion on the carbon atom of the nitrile group (8-12%) followed by ring closure to give 5-dinitromethyl-1H-tetrazole (7) with 8% yield (Scheme 3) [9]; and also by ii) 1,3-dipolar addition of fluorodinitroacetonitrile (8) with sodium azide providing 5-[fluoro(dinitro)methyl]-1H-tetrazole (9) with 85% yield [4].…”