Trinitromethane

Abstract: Hydroxyl radicals have been generated pulse radiolytically in N2O- and N2O–O2-saturated solutions. In their reaction with N,N,N′,N′-ethylenediaminetetraacetic acid (EDTA) they give rise to an absorption spectrum with maxima at 275 and 480 nm. The 480 nm band decays (k = 3.3 × 104 s–1) with a concomitant increase at around 290 nm. The 480 nm intermediate does not react with O2 and has been attributed to an N-centered radical cation bridged to the second nitrogen (N˙+N–EDTA). Using strong reductants as probes, e.g.N,N,N′,N′-tetramethylphenylenediamine, G(N˙+N–EDTA) = 1.6 × 10–7 mol J–1 has been obtained. Besides generating N˙+N–EDTA, the OH radicals produce C-centered radicals by H-abstraction. They have reducing properties and react rapidly with tetranitromethane forming the strongly absorbing nitroform (trinitromethane) anion [NF–; k = 109 dm3 mol–1 s–1; G(NF–) = 4.2 × 10–7 mol J–1]. This rapid formation of NF– is followed by a slower one [G(NF–) = 1.5 × 10–7 mol J–1] showing the same kinetics as the decay of the 480 nm absorption. It is hence concluded that the N˙+N–EDTA species decays into reducing C-centered radicals by deprotonation or electron transfer from a carboxylate group. The C-centered radicals react rapidly (k = 7.6 × 108 dm3 mol–1 s–1) with O2, and subsequent fast O2˙– elimination. The Schiff-bases thus formed hydrolyze yielding the final products.In the presence of oxygen the following products (G values in units of 10–7 mol J–1 in parentheses) have been observed after γ-radiolysis: formaldehyde (1.6), CO2 (2.5), formic acid (0.7), glyoxylic acid (3.6), iminodiacetic acid (2.1), ethylenediaminetriacetic acid (detected, not quantified).

Abstract: The multicomponent reaction of 2,4,6-trichloro-1,3,5-triazine with potassium trinitromethane and trinitroethanol was exploited for the first synthesis of the hetaryl trinitroethyl ether, 2,4-bis(2,2,2-trinitroethoxy)-6-trinitrometyl-1,3,5-triazine 13. The use of compound 13 as a scaffold for the synthesis of substituted trinitroethoxytriazine by sequential nucleophilic substitution processes is described. A number of trinitroethoxytriazines bearing a range of functional groups, including 2,4,6-tris(2,2,2-trinitroethoxy)-1,3,5-triazine 16, have been prepared. There has been no previous incorporation of the trinitroethoxy moiety to a heteroaromatic ring. All trinitroethoxytriazines were fully characterized using IR and multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry (DSC), and, in some cases, 16, 20 and 21, with single crystal X-ray structuring. When compared to the aliphatic trinitroethoxy compounds, the trinitroethoxytriazines show better energetic performance as calculated. The impact sensitivities and ignition points of the novel oxygen and nitrogen-rich triazines were measured. The ability of the applied trinitroethoxytriazines in solid composite propellants as well as in gas generant compositions for airbag inflators was evaluated. The straightforward preparation of these ethers highlights them as valuable new environmentally friendly and high-performing nitrogen and oxygen-rich materials.

Abstract: 1. The heats of combustion of nitromethane and dinitromethane, 168.0±0.3 and 137.3±0.2 kcal /mole, respectively, were measured. 2. The energies (kcal/mole) of dissociation of the C-N bond in nitro derivatives of methane were estimated on the basis of the available data: 60.3 in nitromethane, 53.8 in dinitromethane, 45.7 in trinitromethane, and 39.3 in tetranitromethane. 3. The energies (kcal/mole) of formation of nitromethyl radicals\([^ \cdot CH_2 NO_2 31.6;^ \cdot CH(NO_2 )_2 37.5;\) and\(^ \cdot C(NO_2 )_3 49.8]\) were estimated, and lead to energies of dissociation of the C-H bond in nitro derivatives of methane ∼103 kcal/mole.