Theoretical screening of bistriazole-derived energetic salts with high energetic properties and low sensitivity

We designed four series of energetic anions by replacing nitro group (NO2) with trinitromethyl group (C(NO2)3) or by inserting N-bridging groups (–NH–, –NH–NH–, –NN–, –NN(O)–) into the bistriazole frameworks.

SYNTHESIS OF ADAMANTILOXYTRINITROMETHYL-1,3,5-TRIAZINES

The interaction of silver salt of 2-hydroxy-4,6-bistrinitromethyl-1,3,5-triazine with 1- and 2-bromadamantans was studied. The relative 2-adamantyloxy-4,6-bistrinitromethyl-1,3,5-triazines was synthesized for the first time. It was shown that one of trinitromethyl group in 2-adamantyloxy-4,6-bis(trinitromethyl)-1,3,5-triazines could be substituted selectively under the action of various nucleophiles.

Comparative theoretical studies of dinitromethyl- or trinitromethyl-modified derivatives of CL-20

The heats of formation (HOFs), energetic properties, strain energies, thermal stability, and impact sensitivity for a series of trinitromethyl- or dinitromethyl-modified CL-20 derivatives were studied by using density functional theory. It is found that the trinitromethyl group is an effective structural unit for improving the gas-phase HOFs and energetic properties of the derivatives. However, incorporating the dinitromethyl group into the parent compound is not favorable for increasing its HOFs and detonation properties. The effects of the dinitromethyl or trinitromethyl groups on the stability of the parent compound are discussed. The studies on strain energies show that the introduction of the trinitromethyl group intensifies the strain of the cage skeleton for the title compounds, whereas for the dinitromethyl groups, the case is quite the contrary. An analysis of the bond dissociation energies for several relatively weak bonds suggests that the substitution of the dinitromethyl or trinitromethyl group decreases the thermal stability of the derivatives. The C−NO2 bond in the dinitromethyl or trinitromethyl group is the weakest one and the homolysis of the C−NO2 bond may be the initial step in thermal decomposition. In addition, according to the calculated free space per molecule, the introduction of the dinitromethyl or trinitromethyl group increases the impact sensitivities of the derivatives. Considering the detonation performance, thermal stability, and impact sensitivity, six compounds can be regarded as the target high-energetic compounds.

Photochemical Nitration by Tetranitromethane .XVI. The Regiochemistry of Adduct Formation in the Photochemical Reaction of 1,8-Dimethylnaphthalene and Tetranitromethane; Thermal 1,3-Dipolar Nitro Addition Reactions

Photolysis of the 1,8-dimethylnaphthalene/tetranitromethane charge-transfer complex yields the triad of 1,8-dimethylnaphthalene radical cation, nitrogen dioxide, and trinitromethanide ion. In dichloromethane at +20° recombination of this triad gives predominantly the adducts (8), (9), (11), and (14), each of which is formed by attack of the trinitromethanide ion at C4 of the 1,8-dimethylnaphthalene radical cation; a minor adduct (10) is formed by similar attack but at C3 of the aromatic radical cation. The cycloadducts (12) and (13) arise by cycloaddition of the trinitromethyl group to the alkene function in adducts (9) and (14). The cycloaddition (9)→(12) has been shown to be a thermal, not photochemical, reaction. X-Ray crystal structures are reported for adducts (8) and (12).