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

Abstract

5-(Fluorodinitromethyl)-2H-tetrazole (HFDNTz) has been prepared by the cycloaddition reaction of HN3 with F(NO2)2CCN, which in turn was prepared by aqueous fluorination of sodium dinitrocyanomethanide. HFDNTz was converted into the ammonium, silver and tetraphenylphosphonium 5-(fluorodinitromethyl)tetrazolates. While the reaction of trinitroacetonitrile with HBr, followed by the treatment with NaOH, resulted in the formation of sodium dinitrocyanomethanide, the reaction of trinitroacetonitrile with aqueous ammonia produced ammonium dinitrocyanomethanide. Hydrazinium dinitromethanide was obtained from trinitroacetonitrile and hydrazine hydrate. All compounds were fully characterized by multinuclear NMR spectroscopy, IR spectroscopy and X-ray crystal structure determinations. Initial safety testing (impact and friction sensitivity) and thermal stability measurements (DTA) were also carried out.

Synthesis and Characterization of Nitro‐, Trinitromethyl‐, and Fluorodinitromethyl‐Substituted Triazolyl‐ and Tetrazolyl‐trihydridoborate Anions

“…The coordination of BH 3 to [FDNMeNTrz] − and [FDNMeTz] − has also only a modest effect on the 19 F chemical shift of the anions. The 19 F NMR resonances for the fluorodinitromethyl group in 4 , 5 , 8 , 9 , 11 were found in the range between −93.0 and −97.3 ppm, as expected for fluorodinitromethyl compounds . These resonances were typically observed as poorly resolved broad multiplets due to the 2 J coupling to the N ‐atoms of the two neighboring nitro groups.…”

“…The DTA trace of a 1: 0.15 mixture of 8 a / 9 a, which contained significant amounts of residual water (as observed by 1 H NMR) showed an endotherm with an onset of 85 °C and a decomposition onset of 112 °C. This decomposition onset is significantly lower than that observed for the parent compound [PPh 4 ][FDNMeTz] at 175 °C …”

“…3,5‐Dinitro‐1 H ‐1,2,4‐triazole (HDNT) and its salts were prepared following literature methods . 5‐(trinitromethyl)tetrazole, 5‐(fluorodinitromethyl)tetrazole, (trinitromethyl)nitro‐1,2,4‐triazole and (fluorodinitromethyl)nitro‐1,2,4‐triazole and their salts were prepared in our laboratory.…”

Synthesis and Characterization of N5‐(2‐Fluoro‐2,2‐dinitroethyl)‐N1‐methyl‐1H‐tetrazole‐5‐amine and its Nitramide Based on Functionalized Amino Group in 5‐Amino‐1H‐tetrazole

“…Compound 4 crystallizes in the monoclinic space group P 2 1 /n with four molecules per unit cell and a density of 1.681 g cm −3 at 173 K. The molecular structure is depicted in Figure a. The bond length C2=N1 (1.324(4) Å) of tetrazole is basically the same as that in HFDNTz (1.325(2) Å), which lies between the length of C–N single bond (1.47 Å) and C=N double bonds (1.22 Å), indicating the structural delocalization and aromaticity. The N2=N3 (1.292(5) Å) double bond of tetrazole framework is clearly shorter than N1–N2 (1.359(4) Å) and N3–N4 (1.351(4) Å) single bonds.…”

“…As a useful and versatile molecular structure, tetrazole has been widely used in construction of energetic primary explosives, energetic ionic salts, energetic coordination polymers, energetic co‐crystals, etc for decades, because of its relatively nitrogen‐rich heterocyclic framework. R. Haiges and K. O. Christe firstly reported 5‐fluoronitromethyl‐2H‐tetrazole (HFNDTz), but it showed unstable thermal property ( T d : 110 o C) and sensitive physical performance ( IS : 3.5 J, FS : 40 N) . Then T. M. Klapotke and co‐workers reported its ammonium salt ( IS : 1 J, FS : 16 N) and another derivative 2‐(2‐nitro‐2‐azapropyl)‐5‐(fluorodinitromethyl)‐tetrazole ( IS : 2 J, FS : 36 N).…”