Syntheses and reactions of some 4,5-dihaloimidazole-2-carboxylic acid derivatives

The preparation of 5H,10H-diimidazo[1,2-a:1′,2′-d]pyrazine-5,10-dione ( 2a ) and its 2,3,7,8-tetrabromo- and 2,3,7,8-tetrachloro- analogs ( 2b and 2c , respectively) is reported. These dimers, when allowed to react with various anilines, afford imidazole-2-carboxamides ( 3a-c ).     

On the application of the Dumas technique for the determination of nitrogen in refractory nitrides

The classical Dumas apparatus has been modified. The generally recommended oxidants CuO and V(2)O(5), were found to give relatively high blank values and were therefore replaced by Cu(2)O. The preparation of the Cu(2)O is described. It is an exceptionally suitable oxidant for the Dumas analysis of the Group Va nitrides as well as manganese nitrides and molybdenum nitrides because it does not release oxygen into the gas phase. The reaction of the Group IVa nitrides as well as of CrN with CuO and Cu(2)O is, however, not completely quantitative at 1000-1150 degrees in reasonable reaction times. The results of the Dumas analysis of a Group IVa nitride should be corrected by measuring the nitrogen content of the residue (e.g., by hot extraction). The relative standard deviations do not exceed 0.38%. The nitrogen contents (% w/w) of the residues range from <0.001% for Mo(2)N + MoN to 0.54% for Cr(2)N + CrN. BN, Si(3)N(4) and AlN could not be decomposed with copper oxides under the conditions used. AlN could be analysed by adding V(2)O(5), but the rsd was 0.55% and the nitrogen content in the residue was 0.52% w/w. Neither BN nor Si(3)N(4) could be analysed by addition of V(2)O(5).     

K-shell ionization in relativistic ion-atom collisions

We present calculations ofK-shell ionization probabilities in asymmetric ion-atom collisions at relativistic velocities of the projectile. The time-dependent Dirac equation is represented as a system of coupled differential equations. The transition probabilities are determined using the coordinate space method. This necessitates an extension of the angular momentum coupling compared with nonrelativistic collision systems. Effects of the relativistic projectile motion on the coupling matrix elements and their consequences onK-shell ionization are discussed.     

(1-Adamantanethio)pyridines and tetrahydropyridines from the reaction of 1-adamantanethiol with pyridine I-oxide in acetic anhydride

The reaction of pyridine 1-oxide with 1-adamantanethiol in acetic anhydride produced a mixture of 2- and 3-(1-adamantanethio)pyridines, 1-aeetyl-2-(1-adamantanethio)-3-hydroxy-4-acetoxy-1,2,3,4-telrahydropyridine and the corresponding 3-acetoxyderivative. Pure substances were separated by means of column chromatography on alumina. The tetrahydropyridines were identified by means of their proton magnetic and mass spectra. 4-(1-Adamantanethio)pyridine was synthesized from 4-chloropyridinc and 1-adamantanethiol. The three isomeric (1-adamantanethio)-pyridines were, each, cleaved by concentrated hydrochloric acid to give 1-chloroadamantane and the corresponding pyridinethiol.     

Bestimmung von Gleichgewichtskonstanten für Ligandenaustauschreaktionen von [TcNX4]− (X = Cl,Br) mit Hilfe der EPR

Polynuclear Complexes with Fe? As, Fe? Sb, and Fe? Bi Frameworks The anionic iron clusters Fe₃(CO)₁₁^2? and Fe₄(CO)₁₃^2? were reacted with compounds EX₃ and with organic derivatives REX₂ and R₂EX of the elements arsenic, antimony, and bismuth. Commonly redox and cluster degradation reactions were observed. The new complexes [(CO)₄Fe? AsMe₂? Fe(CO)₄]^?, [HFe₃(CO)₉(mu;₃-SbBu^t)]^?, [Fe₃(CO)₁₀ (mu;₃-Sb)]^?, and [Fe₃(CO)₁₀(mu;₃-Bi)]^? were formed and isolated as their PPN salts. The Fe? As? Fe complex was identified by a structure determination, the other complexes were identified by their spectra.     

Non-destructive determination of plutonium in nuclear fuel rods and pellets

Analytical and Bioanalytical Chemistry - A non-destructive method and an experimental set-up are described by which the Pu content in UO2/PuO2 mixed oxide (MOX) pellets and in fuel rods,...     

Eigenschaften von Chalkogen-Chalkogen-Bindungen. XII. Reversible Tellurierung von Tetraisopropyldiphosphan; Stabilisierung von Tellurobis(diisopropylphosphan) als Tetracarbonylchromkomplex

Properties of Chalcogene-Chalcogene Bonds. XII. Reversible Telluration of Tetraisopropyldiphosphane, Stabilisation of Tellurobis(diisopropylphosphane) as Tetracarbonylchromium Complex Tetraisopropyldiphosphane 1 reacts with elemental tellurium by tellurium atom insertion to give tellurobis(diisopropylphosphane) 2. 2 is also available from sodium telluride with chlorodiisopropyl phosphane. ^lH, ^l3C, ^3lP and ^l25Te n.m.r. spectra confirm that in solution 2 is in an equilibrium with the educt 1 and elemental tellurium. Reaction of this equilibrium mixture with tetracarbonyl(norbornadiene)chromium(0) provides tetracarbonyl[tellurobis(diisopropylphosphane)]-chromium(0) 3. 3 was isolated in pure state as stable compound; different from 2,3 does not suffer from loss of tellurium at room temperature.     

Importance of the Debye interaction in organic solutions: Henry's law constants for polar liquids in nonpolar solvents and vice versa

Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G ₂ ⁰ of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G ₂ ⁰ decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G ₂ ⁰ against the change in pair potential energy calculated from the classical expressions suggests that G ₂ ⁰ seriously underestimates the strength of the Debye interactions in comparison with the London interactions.     

Kinetics and mechanism of the acid-catalysed decarboxylation of thecis-α- andcis-β-carbonato(3,6-dimethyl-1,8-diamino-3,6-diazaoctane)-cobalt(III) ions

Summary The acid-catalysed decarboxylation of thecis-- andcis--[CoL(CO₃)]⁺ complexes (L = 3,6-dimethyl-1,8-diamino-3,6-diazaoctane) have been studied over a range of HClO₄ concentrations and the temperatures 25, 35 and 45° at I = 1.0 mol dm^–3 (NaClO₄). The rate expression takes the form k_obs = k₀ + k₁[H⁺] where k_obs is the observed first order rate constant at constant hydrogen ion concentration. The k₀ term makes only a minor contribution to the overall reaction. Both complexes display solvent deuterium isotope effects ofca. 2.6 for the acid-catalysed decarboxylation, consistent with a rapid proton pre-equilibrium mechanism. Activation parameters have been determined and the mechanism of the reaction discussed. The magnitude of the solvent isotope effect is consistent with an A-1 type mechanism involving formation of a 5-coordinate intermediate.