4- -3,5-dinitro-l ,2,4-triazole

Treatment of the ammonium salt of 3,5-dinitro-1,2,4-triazole (113) with hydrazine hydrate leads to selective reduction of one of the nitro groups to yield 3-amino-5-nitro-1,2,4-triazole (ANTA) (114), a high performance explosive (calculated VOD 8460 m/s) possessing thermal stability (m.p. 238 °C) and an extremely low sensitivity to impact. ANTA (114) is also synthesized from the nitration of 3-acetyl-l,2,4-triazole with anhydrous nitric acid in acetic anhydride at subambient temperature followed by hydrolysis of the acetyl functionality. The ammonium salt of 3,5-dinitro-l,2,4-triazole (113) is itself a useful explosive which forms a eutectic with ammonium nitrate. ... 

Dinitro-l,2,4-triazole copper salt Cast explosive... 

MNTA Molotov cocktail l-Methyl-3,5-dinitro-l,2,4-triazole... 

Very recently there has developed an interest in the detonation behavior of eutectic mixts containing Ammonium Nitrate (AN). Stine-cipher (Ref 30) studied eutectics of AN/ADNT as well as AN/ADNT/org HE (ADNT is the ammonium salt of 3,5-Dinitro-l,2,4 Triazole). 

Ethyltriazole and derivs 6 E335—E336 4(l)-ethyl-3,5-dinitro-l, 2,4-triazole 6 E336 4-ethyl-3-nitro-l, 2,4-triazole 6 E335 4-(2-nitroethyl)-3,5-dinitro-l, 2,4-triazole 6E336... 

Katritzky et al. have described synthetic routes toward l//-tetrazole-5-dinitromethylide sodium salt 618 <2005CHE111>. Energetic salts comprised of substituted tetrazolium cations and the 3,5-dinitro-l,2,4-triazolate anion, viz. 1,4,5-trimethyltetrazolium 3,5-dinitro-l,2,4-triazolate 619 and 4,5-dimethyl-l-aminotetrazolium 3,5-dinitro-1,2,4-triazolate 620, were obtained and characterized by Shreeve and co-workers <2005JMC3459>. 

The reaction of 5-bromo-3-nitro-l,2,4-triazole and 3,5-dinitro-l,2,4-triazole with a variety of oxiranes yielded the expected 1-substituted imidazoles, and also resulted in the formation of 5,6-dihydrooxazolo[3,2-6]-s-triazoles upon treatment with base (75CHE612). The proposed pathway involves proton abstraction from the imidazole and subsequent attack of the oxirane on the N-anion followed by cyclization in a concerted fashion (equation 56). 2,4(5)-Dinitroimidazole reacts analogously with oxiranes to give isomeric nitro-imidazo[2,1 -f>]oxazoles in good overall yield (8UMC601). 

Dinitro-l,2,4-triazole has been synthesized from 3,5-diamino derivative with sodium nitrite excess [667], and the protocol was proposed for the preparation of 3,5-dinitro-l,2,4-triazole from dicyanodiamide and hydrazine without isolation of 3,5-diamino-l,2,4-triazole. 

Both absorption bands (vas) and (vs) in 3-nitro-l,2,4-triazole isomers are shifted to the lower frequency region on 25-34 cm1 in comparison with 5-nitro isomers [554], Splitting of the N02 absorption bands in the IR spectra of 3,5-dinitro-l,2, 4-triazole derivatives reported in [1060] may testify to dimensional and electronic... 

An unusual feature of triazole chemistry is the ready exchange of nitro groups of nitro-and dinitro-triazoles and nitrotriazolinones (67cb2250, 70KGS269, 70KGS1701). The reaction of l-methyl-3,5-dinitro-l,2,4-triazole with hydrazine (7OKGS997) exemplifies such reactions... 

Xue H, Twamley B, Shreeve JM (2005) Energetic salts of substituted 1,2,4-triazolium and tetrazolium 3,5-dinitro-l,2,4-triazolates. J Mat Chem 15 3459-3465... 

For 1-chlorotriazole 39 (R=H) the equilibrium involving its formation is shifted toward the final products (72JPR923). At the same time, 1-chloro-3,5-dinitro-l,2,4-triazole 43 cannot be prepared due to the high acidity of the starting dinitro compound (70KGS558) and the shift of the equilibrium is toward the starting compounds (90IZV2814) (Scheme 23). 

N 19.26% OB to CO2 0% yel, v volatile solid mp, V violent decompn on heating. Insol in w. Prepn is by dropwise addn of a 0.025M aq soln of Na 3,5-dinitro-l,2,4 triazole to 0.055M nitric acid. The pptd product is then filtered off, washed with distld w, and dried under vac at 50°. The salt has an impact sensy of 34cm (2.5-kg wt) and a 100° vac stab value of 0.12cc of gas/g/48 hrs... 

Refs 1) Beil, not found 2) H.P. Burchfield et al, Research and Development in Connection with New High Explosives..Progress Report No 3, Naugatuck Chem Div, US Rubber Co, Contract NOrd 10121 (Feb 1949), III, A-8 2) F. Taylor, Synthesis and Examination of. .. the Metal Salts of 3,5-Dinitro-l,2,4-Triazole , NAVORD 2307(1951)... 

Lithium dicyano- 1,2,3-triazolate was reported as a useful electrolyte (38) [45]. 1-Butyl-3-methylimidazoliiun 3,5-dinitro-l,2,4-triazolate (39) (Fig. 2) (m.p. 32 °C, rmaterial Some novel ionic liquids made up of azolium cations and anions were also reported. These salts are 1-ethyl-3-methyUmidazohum 1,2,4-triazolate (40) (Tg - 76 °C, T 207 °C, 7] 60.2 cP at 25 "C) and tetrazolate (41) (Tg -89°C, t] 42.5 cP at 25 °C) (Fig. 2). Both 40 and 41 were prepared by the coupUng reactions of 1-ethyl-3-methylimidazolium hydroxide with triazole or tetrazole, respectively [50]. 

The syntheses of urotropinium and N-methylurotropinium salts were extended to include several other energetic organic and inorganic anions, such as 3,5-dinitro-pyrazolate, 4,5-dinitro-imidazolate, 3,5-dinitro-l,2,4-triazolate, 5-nitro-tetrazolate, perchlorate, nitrate, and azide [94]. In methanol solution, urotropine was found to react readily with 3,5-dinitro-pyrazole, 4,5-dinitro-imidazole, 3,5-dinitro-1,2,4-triazole, and 5-nitro-tetrazole to form urotropinium 3,5-dinitro-pyrazolate (89a), 4,5-dinitro-imidazolate (89b), 3,5-dinitro-1,2,4-triazolate (89c), and 5-nitro-tetrazolate (89d). Reaction of silver salts of 3,5-dinitro-l,2,4-triazole, nitric, perchloric, and hydrofluoric acid with N-methylurotropinium iodide led to N-methylurotropinium 3,5-dinitro-1,2,-triazolate (90a), nitrate (90b), perchlorate (90c), and fluoride (90d)... 

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