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2000 (1)
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1Author    Akinori Shuto, ToruYasushi Takahashi, Tsutomu Ohga, Hirokazu Asano, Saito, Kohei Matsuo, Hans-Dietrich LüdemannRequires cookie*
 Title    Pressure Effects on the Thermal Z/E Isomerization of 4-(Dimethylamino)-4'-nitroazobenzene in a Liquid Polymer. A Comparison of Dynamic Solvent Effects in Polymerie and Monomeric Solvents  
 Abstract    Effects of pressure on the thermal Z/E isomerization of4-(dimethylamino)-4'-nitroazobezene were stud-ied in a silicon oil at various temperatures. The results were compared with the ones previously obtained in glycerol triacetate (GTA) and 2-methylpentane-2,4-diol (MPD).Even in the polymer, pressure effects expected from the transition state theory were obtained at low pressures (P < 200 MPa).However, as in GTA and MPD, the transition state theory became invalid at higher pressures. For the polymeric liquid, the macroscopic shear viscosity obviously does not suffice for a quantitative description of the micro-scopic frictions between the reactant and the solvent molecules. 
  Reference    Z. Naturforsch. 55a, 616—622 (2000); received January 3 2000 
  Published    2000 
  Keywords    High-pressure Kinetics, Z/E Isomerization, Dynamic Solvent Effects, Liquid Polymer 
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 TEI-XML for    default:Reihe_A/55/ZNA-2000-55a-0616.pdf 
 Identifier    ZNA-2000-55a-0616 
 Volume    55 
2Author    H. Tiltscher, R. LohmüllerRequires cookie*
 Title    High Pressure Reactions, I Evidence for Two Concurrent Mechanisms in Lewis-Acid Catalyzed Alkylation of Aromatics with Olefins  
 Abstract    A kinetic study was made of the primary step of the alkylation of benzene with propy-lene and ferric chloride as catalyst under homogeneous reaction conditions at several pressures up to 2 kbar. Initial reaction rate of cumene formation shows a minimum in the medium pressure range, thus indicating that product formation occurs via two different reaction paths with opposite pressure de-pendence. 
  Reference    (Z. Naturforsch. 31b, 277—278 [1976]; received September 27 1975) 
  Published    1976 
  Keywords    Friedel-Crafts Alkylation, Aromatics, Olefins, High Pressure Kinetics, Concurrent Mechanisms 
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 TEI-XML for    default:Reihe_B/31/ZNB-1976-31b-0277_n.pdf 
 Identifier    ZNB-1976-31b-0277_n 
 Volume    31 
3Author    Yasushi Ohga, Tsutomu Asano, Norbert Karger, Thomas Gross, Hans-Dietrich LüdemannRequires cookie*
 Title    Dynamic Solvent Effects in the Degenerate Isomerization of a Hexafluoroacetone Anil Studied by High-Pressure 19 F NMR  
 Abstract    The rate of the degenerate isomerization of A^-hexafluoroisopropylidene-V,V-dimethyl-/?-phe-nylenediamine was measured by high-pressure 19 F NMR spectroscopy in a viscous hydrocar-bon, 2,4-dicyclohexyl-2-methylpentane. Pressure-induced retardations that cannot be rationalized within the framework of the transition state theory (TST) were observed, and it was concluded that the reaction was cast into the TST-invalid nonequilibrium conditions by high pressure. 
  Reference    Z. Naturforsch. 54a, 417—21 (1999); received April 19 1999 
  Published    1999 
  Keywords    High-pressure 19 F NMR, High-pressure Kinetics, Hexafluoroacetone Anil, Degenerate Isomerization, Dynamic Solvent Effect 
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 TEI-XML for    default:Reihe_A/54/ZNA-1999-54a-0417.pdf 
 Identifier    ZNA-1999-54a-0417 
 Volume    54