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.

The reaction of boron oxide with various nitro-substituted ethanols (2-nitroethanol, 2-fluoro-2,2-dinitroethanol, 2,2,2-trinitroethanol) furnished the corresponding nitroethyl borates B(OCH2CH2NO2)3 (1), B(OCH2CF(NO2)2)3 (2), and B(OCH2C(NO2)3)3 (3). Fluorination of the anion [(NO2)2CCH2OH](-) (4) resulted in 2-fluoro-2,2-dinitroethanol (5), a precursor for 2, and was thoroughly characterized. An interesting condensation was observed with the anion 4 to form the unusual dianion [(NO2)2CCH2C(NO2)2](2-) (6). All compounds were fully characterized by multinuclear NMR spectroscopy, vibrational spectroscopy (IR, Raman), mass spectrometry and elemental analysis. The chemical, physical and energetic properties of 1-3 and 5 are reported, as well as quantum chemical calculations at the CBS-4M level of theory to predict the enthalpies and energies of formation. X-ray diffraction studies were performed, and the crystal structures for compounds 1-6 were determined and discussed thoroughly. The boron esters 1-3 are of interest as possible candidates for smoke-free, green colorants in pyrotechnic applications, and in case of 2 and 3 also as promising high energy oxidizers.

The reaction of organomercury(II) halogenides (RHgHal, Hal = Cl, I) with silver azide furnished the corresponding covalent organomercury(II) azides RHgN 3 (R = Me (1), tBu (2), Ph (3)). In addition to the characterization by multinuclear NMR spectroscopy, IR and Raman spectroscopy as well as mass spectrometry, the mercury 507 content was determined. A dependance on the solventpolarity for the 14 N NMR resonances was observed. Furthermore, X-ray diffraction studies were performed and the crystal structures for mercury(II) azides 1-3 are reported. A comparison of the bond lengths and angles with data from theoretical calculations is given. at all. In this contribution, a detailed study of the synthesis and characterization of the three organomercury(II) azides with methyl-(1), tert-butyl-(2) and phenyl-(3) substituents is presented. Results and DiscussionThe synthesis route for the preparation of the organomercury(II) azides 1-3 was the reaction of organomercury(II) halogenides (RHgHal, Hal = Cl, I) with silver azide to obtain the corresponding covalent organomercury (II) azides RHgN 3 (R = Me (1), tBu (2), Ph (3)) (Scheme 1). Scheme 1. Synthesis of the organomercury(II) azides 1-3.The route described here is more convenient than the syntheses reported in literature, because the used organomercury(II) halogenides are less toxic than the diorganomercury compounds and also because of the more straightforward reactions [1][2][3]9]. For a high conversion rate silver azide was used in excess with a ratio of 2:1 with respect to the organomercury(II) halogenides. The reaction of RHgHal with sodium azide was reported to be effective, but no details given [9,10]. However, we could not confirm a positive reaction with NaN 3 .The non-hygroscopic compounds 1-3 are soluble in polar organic solvents like acetone, acetonitrile, benzene, chloroform and methanol, whereas the alkyl compounds 1 and 2 are more soluble than the aryl compound 3. In water and non-polar solvents like hexane all compounds are insoluble. Compounds 1-3 were found not sensitive to shock and friction. In a Bunsen burner the compounds deflagrate quite fast, with the alkyl de-