3.5- Dinitro-1,2,4-triazole, reaction with

Amino derivatives of 1,2,3- and 1,2,4-triazoles are useful precursors to the corresponding nitro-substituted triazoles. 3-Amino-1,2,4-triazole (98) undergoes diazotization on reaction with nitrous acid the resulting diazonium salt (110) can react with a range of nucleophiles, including an aqueous solution of sodium nitrite which yields 3-nitro-1,2,4-triazole (111). Diazotization of 3,5-diamino-l,2,4-triazole (112), followed by heating with an aqueous solution of sodium nitrite, yields 3,5-dinitro-1,2,4-triazole (113). ... 

In the reaction of 3-nitro-5-R-l,2,4-triazolate-anion with 3,5-dinitro-l-(2-oxo-propyl)-l,2,4-triazole both the products of nucleophilic substitution in position 5 and condensed compounds [5-methyl-5-(3-nitro-5-R-l,2,4-triazol-l-yl)-5,6-dihydroxazolo[3,2-b]-l,2,4-triazoles] are formed. Their structures were established by H NMR and IR spectroscopy [585],... 

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... 

PTs can be prepared by involving the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)-1,2,4-triazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents, such as sulfolane or diphenyl sulfone, using alkaU metal bases, such as potassium carbonate, at elevated temperatures under nitrogen. 

PTs can be prepared by involving the aromatic nucleophilic displacement reaction of di(hydro-xyphenyl)-1,2,4-triazole monomers with activated aromatic dihalides or activated aromatic dinitro... 

Amino-5-nitro-1,2,3-triazole (ANTZ) (130), an explosive showing high thermal stability, has been synthesized via this route the reaction of sodium azide, acetaldehyde and 2,2-dinitroethyl acetate forming 4-methyl-5-nitro-1,2,3-triazole, which on conversion of the methyl group to an amino group yields ANTZ (130). Treatment of ANTZ (130) with hydrogen peroxide in sulfuric acid yields 4,5-dinitro-1,2,3-triazole (DNTZ) (131). 

Wang and co-workers [57,58] reported several Michael-type enantioselective additions with nitro-olefins. Under neat conditions, 1,3-dinitro compounds were generated in the 74 addition of nitroalkanes 75 to various P-substituted nitro-olefins (Scheme 15). Other Michael-type involving nitro-olefins reactions were illustrated using triazole donors 77 to offer good yields and high enantioselectivities (Scheme 16). 

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). 

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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