Abstract.A new simple synthesis route for 2,2,2-trinitroethyl chloroformate (1), from easily available starting materials 2,2,2-trinitroethanol and phosgene is presented. 2,2,2-Trinitroethyl carbamate (2) was obtained by the reaction of 1 with aqueous ammonia. The nitration of 2 with anhydrous nitric acid and sulfuric acid yields 2,2,2-trinitroethyl nitrocarbamate (3), which has potential as a perchlorate free high

Tetrakis(2,2,2‐trinitroethyl) orthocarbonate (1) and 2,2,2‐trinitroethyl formate (2) were synthesized by the reaction of carbon tetrachloride, respectively chloroform, with the corresponding equivalents of 2,2,2‐trinitroethanol and catalytic amounts of anhydrous iron(III)chloride. 2,2,2‐Trinitroethyl formal (3) was prepared by the condensation of paraformaldehyde with 2,2,2‐trinitroethanol. The compounds were fully characterized by single‐crystal X‐ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, and multi‐temperature DSC measurements. Due to the positive oxygen balance, the suitability of all three compounds mentioned as potential oxidizers in energetic formulations was investigated and discussed. In addition, the heats of formation of the products were determined experimentally using bomb calorimetric methods. With this value and the experimental (X‐ray) density, several detonation parameters such as the detonation pressure, velocity, energy, and temperature were computed using the EXPLO5 code. Furthermore, the sensitivity towards impact, friction and electrical discharge was tested using the BAM drop hammer, a friction tester as well as a small‐scale electrical discharge device.

The halogenotrinitromethanes FC(NO2 )3 (1), BrC(NO2 )3 (2), and IC(NO2)3 (3) were synthesized and fully characterized. The molecular structures of 1-3 were determined in the crystalline state by X-ray diffraction, and gas-phase structures of 1 and 2 were determined by electron diffraction. The Hal-C bond lengths in F-, Cl-, and Br-C(NO2 )3 in the crystalline state are similar to those in the gas phase. The obtained experimental data are interpreted in terms of Natural Bond Orbitals (NBO), Atoms in Molecules (AIM), and Interacting Quantum Atoms (IQA) theories. All halogenotrinitromethanes show various intra- and intermolecular non-bonded interactions. Intramolecular N⋅⋅⋅O and Hal⋅⋅⋅O (Hal=F (1), Br (2), I (3)) interactions, both competitors in terms of the orientation of the nitro groups by rotation about the C-N bonds, lead to a propeller-type twisting of these groups favoring the mentioned interactions. The origin of the unusually short Hal-C bonds is discussed in detail. The results of this study are compared to the molecular structure of ClC(NO2 )3 and the respective interactions therein.

A modified synthesis for carbonyl diisocyanate, CO(NCO)2, starting from trichloroisocyanuric acid and diphosgene is described. In addition to the previously reported (13)C NMR resonances, the (15)N NMR shift is determined for the first time. The structure in the solid state was determined by X-ray diffraction (XRD) on in situ grown crystals, that in the gas phase was experimentally determined by electron diffraction (GED) and for single molecules theoretically by quantum-chemical calculations. The structures are compared and discussed with related systems. Quantum-chemical calculations as well as GED and XRD prove syn-syn to be the conformation of lowest energy. In quantum-chemical calculations and GED the presence of a syn-anti conformer was confirmed and the structure of this conformer was determined.

The fluorine-containing polynitro energetic molecule (2fluoro-2,2-dinitroethyl)-2,2,2-trinitroethylnitramine and the corresponding precursors were synthesized and investigated as potential high-energy dense oxidizers. The compounds have been characterized by using various analytical methods, single-crystal X-ray diffraction, vibrational spectroscopy (IR and Raman), multinuclear NMR spectroscopy, elemental analysis, mass spectrometry, and differential scanning calorimetry (DSC) measurements. The suitability of the compounds as potential oxidizers in energetic formulations has[a]