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  • Physical Chemistry  (3)
  • 1H-19F-1H and 1H-19F-13C systems  (1)
  • Wiley-Blackwell  (4)
  • 1985-1989  (4)
  • 1
    Electronic Resource
    Electronic Resource
    Kinetics of the formation and hydrolysis of the schiff's base of 4-pyridinecarboxaldehyde with N-hexylamine in water-dioxan mixtures (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 51-61 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have carried out a kinetic study of the 4-pyridinecarboxaldehyde plus n-hexylamine system, at 25°C, in water-dioxan mixtures (0-60% v/v) and in the pH range pKa + 1.5 〉 pH 〉 pKa - 1.5, where pKa is the pK value of the conjugate acid of the amine. The results obtained could be interpreted in terms of a rate constant for Schiff's base hydrolysis and a rate constant for the reaction between the nonprotonated n-hexylamine and the nonhydrated form of 4-pyridinecarboxaldehyde. Both constants decrease sharply as the dioxan content of the solvent increases, in a manner consistent with Marshall's model [J. Phys. Chem., 74, 346 (1970)]. It is suggested that the transition state of the rate-limiting step (carbinolamine dehydration) is highly solvated by water molecules and has a high separation of charges.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550210105
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  • 2
    Electronic Resource
    Electronic Resource
    Indirect 1H—19F—1H and 1H—19F—13C nuclear overhauser enhancements: Anomalous intensity effects and applications in conformational analysis (1987)
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 25 (1987), S. 539-543 
    Details
    ISSN: 0749-1581
    Keywords: Indirect heteronuclear NOEs ; 1H-19F-1H and 1H-19F-13C systems ; Three-spin effects ; Anomalous intensity effects ; Conformational analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Indirect nuclear Overhauser enhancements through 19F have been determined for the three-spin systems 1H-19F-1H and 1H-19F-13C by steady-state presaturation of the appropriate proton, and applied to the conformational analysis of 5-bromo-2-fluoro-4-nitroacetanilide. The 1H NOE difference spectra at 400 MHz showed antiphase doublets for protons undergoing simultaneous dipolar relaxation with, and scalar coupling to, 19F. Similarly, in the 13C selective NOE difference spectrum at 100 MHz, the two lines of the fluorine-bearing carbon showed negative enhancement factors of different magnitude on presaturation of the appropriate proton. The use of these anomalous intensity effects in conformational analysis is illustrated.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mrc.1260250617
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the decomposition of N-bromoalcoholamines in aqueous solution (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1249-1258 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition reactions of N-bromodiethanolamine, N-bromoethylethanolamine, and N-bromomethylethanolamine in aqueous solution have been studied kinetically under various experimental conditions. The results support a proposed reaction mechanism in which the rate controlling step is assumed to be the formation of an imine which is then hydrolyzed to the final decomposition products.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181104
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics of the chlorination of secondary amines by N-chlorosuccinimide (1988)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 397-409 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chlorinations of dimethylamine, diethylamine, methylethanolamine, ethylethanolamine and diethanolamine by N-chlorosuccinimide have been found to be equilibrium reactions of order one with respect to both N-chlorosuccinimide and amine in the forward direction and of order one with respect to succinimide and the resulting N-chloramine in the other. These results are explained by postulating a mechanism in which the rate controlling step consists in direct exchange of positive chlorine between the N-chlorosuccinimide and the amine.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550200506
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