Highly Dense Nitranilates‐Containing Nitrogen‐Rich Cations

Abstract

High density energetic salts containing nitrogen-rich cations and the nitranilic anion were readily synthesized in high yield by metathesis reactions of sodium nitranilate 2 and an appropriate halide. All of the new compounds were fully characterized by elemental, spectral (IR, (1)H, (13)C NMR), and thermal (DSC) analyses. The structure of hydrazinium nitranilate (4) was also determined by single-crystal X-ray analysis. The high symmetry and oxygen content of the anion give these salts extensive hydrogen bonding capability which further results in the high densities, low water solubilities, and high thermal stabilities (T(d)> 200 degrees C) of these compounds. Theoretical performance calculations were carried out by using Gaussian 03 and Cheetah 5.0. The calculated detonation pressures (P) for these new salts fall between 17.5 GPa (10) and 31.7 GPa (4), and the detonation velocities (nuD) range between 7022 m s(-1) (13) and 8638 m s(-1) (4).

Alkali Salts of Nitranilic and Cyanochloranilic Acids

“…The molecular geometries of the nitranilate anions (Table 2) are in a good agreement with the previously determined ones [30,31,33,34] and also dianions of other substituted 2,5-dihydroxyquinones. [2,[19][20][21] Therefore, the resonance depicted in Scheme 1a is well-justified.…”

“…Dihedral angles between the quinoid ring plane and a nitro group for the previously known structures range between 3.9 ° [34] and 56.6 °; [36] in the nitranilic acid hexahydrate it is 23 °. [31,31] Apparently, rotation about the C-N bond is easy and the orientation of the nitro group depends on the molecular environment.…”

“…Only several crystal structures comprising a nitranilate anion have been deposited in the Cambridge Structural Database (CSD). Those include the hydronium, [30] ammonium [33] and hydrazinium [34] nitranilate, its calcium and strontium salts [35] and a few salts with organic cations. [34,36] Of alkali salts, there are potassium nitranilate and monoclinic sodium nitranilate dihydrate.…”

“…Those include the hydronium, [30] ammonium [33] and hydrazinium [34] nitranilate, its calcium and strontium salts [35] and a few salts with organic cations. [34,36] Of alkali salts, there are potassium nitranilate and monoclinic sodium nitranilate dihydrate. [37] Despite its obvious potential as a ligand, only a few complexes with iron [38] and manganese [39] have been studied.…”

Unexpected formation of ammonium thiocyanate from the reaction of aqueous hydroxylamine with carbon disulfide

“…Hydroxylamine is used as reducing agents in a variety of organic and inorganic reactions [1][2][3]. Further, hydroxylamine nitrate (HAN), a derivative of hydroxylamine has been used for applications that include equipment decontamination in nuclear industry and also as aqueous or solid propellants [4][5][6].Synthetic utility of the reactions between carbon disulfide and Nnucleophiles to form wide range of organosulfur compounds are well known [7]. Carbon disulfide is known to deoxygenate tertiary amine N-oxides to tertiary amines [8] and N, N-disubstituted hydroxylamines to secondary amines [9].…”