Ionic Liquids as Unique Solvents in One‐Pot Synthesis of 4‐(N,2,2,2‐Tetranitroethylamino)‐3‐R‐Furazans

Abstract

An efficient two-step one-pot protocol for the synthesis of N-nitrated trinitroethylamino furazans in an ionic liquid has been developed involving the condensation of aminofurazans with trinitroethanol and the N-nitration of an intermediate Mannich base. Trinitroethylnitramino derivatives have been synthesized and characterized by multinuclear NMR spectroscopy and X-ray crystallography. A role of the N,2,2,2-tetranitroethylamino group for stabilization of the high-density crystal-packing motif is described. The performance calculations gave detonation pressures and velocities for the furazan derivatives in a range of about 31-36 GPa and 8330-8745 ms(-1), respectively, which makes them competitive energetic materials. Furthermore, due to the positive oxygen balance, the compounds could be potential oxidizers for energetic formulations.

Synthesis of 1-(N-nitropyrazolyl)-1Н-tetrazoles – a new type of heteronuclear N-nitropyrazole derivatives

“…[48][49][50][51] We should also note that compound 5k, featuring a weaker hydrogen bond, has a denser crystal packing than compound 5a. The X-ray structural data obtained at room temperature showed that the decrease of density was 3.3% for both compounds, in agreement with the aforementioned results from our earlier multitemperature X-ray crystallography studies of nitro compounds, [52][53][54] according to which the decrease in density upon heating from 100 to 298 K is in the relatively narrow range of 3−4%.…”

Synthesis of 4-Acyl-3-Aminofurazans from 3,4-Diacylfuroxans

“…For this reason, the further analysis of electron density distribution within the framework of Quantum Theory of Atoms in Molecules [43][44] was performed for calculations in M052X/6-311G(df,pd) approximation. As it was expected from non-covalent intramolecular contacts, in molecule 2c, two intramolecular hydrogen bonds are formed (Table 3) The most frequently used visual presentation of molecular packaging in crystals, based on the consideration of shortened intermolecular contacts [47][48][49], showed that the molecules in crystal formed hydrogen bonded ribbons through N-H···O and N-H···N interactions ( Table 3, Fig. 2).…”

“…This conclusion is in agreement with the relatively high density of compound 2с (1.539 g/cm 3 ) compared to organic compounds in general. Higher density is usually associated with isotropic distribution of intermolecular interactions in crystals [47,56].…”

Nitropyrazoles 23. Synthesis of substituted N-amino-3-nitro-5-R-pyrazoles

“…Calculated (%): C,45.98;H,2.70;N,26.81. 1 H NMR,: 7.65 (m,3 H,Ph); 8.08 (d,2 H,Ph,J = 7.0 Hz); 8.28 (s, 1 H, H(4)); 9.36 (s, 1 H, HC=N). 13 C NMR, : 103.0 (C(4)); 129.3 (CH); 129.7 (CH); 130.9; 133.6 (CH); 149.5 (br.s, C(3)); 154.0 (br.s, C(5)); 160.1 (N=C).…”

“…(4)); 121.3; 131.6; 132.0 (CH); 132.5 (CH); 134.9 (C(5)); 150.5 (br.s, C(3)). IR, /cm -1 : 3445, 3330, 1533-1 : 3445, 3330, , 1474-1 : 3445, 3330, , 1395-1 : 3445, 3330, , 1374-1 : 3445, 3330, , 1319-1 : 3445, 3330, , 1009 (1:1) (d,2 H,Ph,J = 8.1 Hz). 13 C NMR, : 20.6 (Me); 103.7 (C(4)); 127.5; 130.5 (CH); 131.7 (CH); 138.0 (C(5)); 138.6 (CH); 150.5 (br.s, C(3)).…”