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  • 1
    Electronic Resource
    Electronic Resource
    Pyrolysis of β-hydroxyketones and α-ketoesters: Gas-phase elimination kinetics of 3-hydroxy-3-methyl-2-butanone and methyl benzoylformate (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 295-298 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 2
    Electronic Resource
    Electronic Resource
    Gas-phase pyrolytic reactions. Part 6. [1] Behavior of ethyl (hetero)arylcarboxylate esters in thermal elimination reactions (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 289-293 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 3
    Electronic Resource
    Electronic Resource
    Gas-phase kinetics of elimination reactions of pentane-2,4-dione derivatives. Part ii [1]. Thermolysis of derivatives and analogues of 3-phenylhydrazonopentane-2,4-dione (1998)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 457-462 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
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