Kinetik und stereochemischer Verlauf der thermischen Umlagerung der vier stereoisomeren Propenyl-(but-2′-enyl)-äther

The gas-phase rearrangement of (1Z, 2′E)-, (1Z, 2′Z)-, (1E, 2′E)-, and (1E, 2′Z)- propenyl but-2′-enyl ether (Z, E)-, (Z, Z)-, (E, E)-, and (E, Z)-1) into erythro- and threo-2, 3-dimethyl-pent-4-en-al (erythro- and threo-2) was investigated over a temperature range from 142,5° to 190,0° at 20–35 Torr (for kinetic data and activation parameters see table 2). All four stereoisomeric ethers 1 rearrange preferentially via a chair-like transition state C into the aldehydes 2 (ΔΔG^≠ (160°) = 2,5–2,7 kcal/mol for B – C (B = boat-like transition state). The relative rates (k_rel) for (Z, Z)-1, (Z, E)-1, (E,Z)-1, and (E,E)-1 at 160° are 1,0, 2,9, 4,3 and 9,0 respectively (see table 5). Taking into account the relative enthalpies of the ethers 1 and the steric interaction in the C transition state of the ethers 1 (see table 6), k_rel values can be estimated. They are in good agreement with those observed (see table 5).     

Impact of electron-electron interaction on the electron energy distribution function in molecular plasmas under rf field action

Calculations of the electron energy distribution and of relevant macroscopic quantities of collision-dominated, weakly ionized plasmas under rf field action have been performed with increasing degrees of ionization, and the impact of the electron-electron interaction on these quantities was determined. The investigations were performed for the gas plasmas in CO and H₂ as representatives of molecular plasmas The energy distribution and macroscopic quantities are obtained by solving the nonstationary Bolizmann equation for a given rf field and degree of ionization taking into accoung and additional Fokker-Planck term besides the collision integrals for the elastic and the main inelastic collision processes. In these molecular plasmas a remarkable impact of the electron-electron interaction connected with increasing Maxwellization is observed for degrees of ionization greater than 10.     

3,7-Dioxaazelaamides as Ionophores for Lithium Ion Selective Liquid Membrane Electrodes

Lipophilic neutral carriers were synthesized which show Li⁺/Na⁺ selectivities of up to ca. 80 in highly lipophilic liquid membranes. The sensor membranes exhibit improved response times and increased lifetimes as compared to systems described earlier. They allow reliable measurements of Li⁺ in blood serum within the clinical concentration range. A 1:1 Li⁺/ionophore complex of one representative (N,N,N′,N′-tetracyclohexyl-5,5-dimethyl-3,7-dioxaazelaamide) has been prepared, and its structure was elucidated by X-ray analysis.     

Synthese und Kristallstruktur von Blei(II)‐oxidhalogenid‐Alkoholaten mit unterschiedlichen Verknüpfungsvarianten von Pb4O4‐Heterokubaneinheiten

Synthesis and Crystal Structure Determination of Lead(II) Oxide Halide Alcoholates with Different Connectivity of Pb₄O₄ Heterocubane‐like Subunits The reaction of red lead(II) oxide (Litharge) and lead(II) halide (Cl^? and Br^?) with diethylene glycole at a temperature of 180 °C leads to the isotypic compounds [Pb₆(C₄H₈O₃)O₂Cl₆] (1) and [Pb₆(C₄H₈O₃)O₂Br₆] (2) . In a similar synthesis with PbI₂ as educt at temperature of 160 °C the two modifications β‐[Pb₆(C₄H₈O₃)O₂I₆] (3) and α‐[Pb₆(C₄H₈O₃)O₂I₆] (4) were found, whereas at a reaction temperature of 180 °C [Pb₉(C₂H₄O₂)(C₄H₈O₃)O₃I₈] (5) was surprisingly obtained as product. The X‐ray diffraction data show that at a temperature of 180 °C a splitting of the ether took place. The cited compounds show cubane like subunits built by lead and oxygen atoms. These fragments are connected by alkoholate molecules. In 5 additionally an I₆ octahedra centered by lead is observed.     

Synthese und Fluoreszenzeigenschaften von cyansubstituierten 2-Aminopyridinen

The synthesis of several 2-aminopyridines is described. The reaction of tetracyanoethylene with 3-imino-propane-carbonitrile gives 2-amino-3,4,5-tricyano-pyridines with alkyl and aryl-substituents, resp., in position 6. Nucleophilic substitution of 2-amino-6-chloro-3,5-dicyanopyridines and 2-amino-6-chloro-3,4,5-tricyano-pyridines with phenolates leads to a variety of pyridines. Spectroscopical data of absorption and fluorescence are presented and the influence of the cyano groups is discussed. The results are in good agreement with quantum chemical calculations (PPP).

Herrn Univ-Prof. Dr.A. Holasek zum 60. Geburtstag gewidmet.