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  • 1
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 295-298 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rates of gas-phase elimination reactions of methyl benzoylformate (1) and 3-hydroxy-3-methyl-2-butanone (2) were obtained at T = 600 K. The two substrates undergo unimolecular first-order elimination for which the Arrhenius equations are, respectively, log k = 13.2 - 53270/(4.574 × 600) for (1) and log k = 12.4 - 53060/(4.574 × 600) for (2). The products of pyrolysis of (1) are benzaldehyde, formaldehyde and CO, while those of (2) are acetaldehyde and acetone. The kinetics of the elimination reactions show benzoylformic acid to be 106-fold more reactive than (1), and pyruvic acid ca. 105-fold more reactive relative to (2); an indication of the rate-controlling part played by the acidity of the hydrogen atom involved in the elimination process of the present compounds in this particular type of reaction. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 295-298, 1997.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 289-293 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rates, Arrhenius parameters, and Hammett substituent constants are obtained for the gas-phase thermal elimination of ethyl benzoate (1) and ethyl 2 - thienyl -  (2), 3 - thienyl -  (3), 2 - furyl -  (4), 3 - furyl -  (5), 4 - pyridyl -  (6), 3 - pyridyl -  (7), and 2 - pyridylcarboxylate (8) esters. The log A/s-1 and the Ea/kJ mol-1 values of these esters averaged 13.60 and 216.3, respectively. The present results are compared with data previously reported for the corresponding isopropyl and t-butyl analogues, and the findings are rationalized in terms of a plausible transition state for the elimination pathway. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 289-293, 1997.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Six analogues and derivatives (1-6) of 3-phenylhydrazonopentane-2,4-dione (7) were subjected to gas-phase thermolysis. The Arrhenius log A (s-1) and Ea (kJ mol-1) of the analogues (1-5) are, respectively: 10.42 and 140.8 for 1-cyano-1-phenyl-hydrazonopropanone (1), 11.19 and 135.4 for 1-cyano-1-(\documentclass{article}\pagestyle{empty}\begin{document}$ \underline{\rm{p}} $\end{document}-nitrophenylhydrazono)-propanone (2) , 10.68 and 144.9 for 1-cyano-1-(\documentclass{article}\pagestyle{empty}\begin{document}$ \underline{\rm{p}} $\end{document}-methoxyphenylhydrazono)propanone (3), 11.76 and 137.8 for 1-cyano-3-phenyl-1-phenylhydrazonopropanone (4), and 11.29 and 145.9 for 1-cyano-1-phenylhydrazonobutanone (5). The corresponding values for ethyl 3-oxo-2-phenylhydrazonobutanoate (6) are 11.90 s-1 and 143.3 kJ mol-1. The rates of reaction at 600 K are compared with those of the title diketone (7) and of pentane-2,4-dione (8) and rationalized in terms of a plausible elimination pathway involving a semiconcerted six-membered transition state. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 457-462, 1998
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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