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  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 9 (1996), S. 411-418 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The autoxidation of various retinyl polyenes and carotenoids in chlorobenzene at 45°C and in thin solid films on a support at room temperature was investigated. The compounds used were β-carotene, canthaxanthin, retinyl acetate, methyl (all-E)-retinoate, methyl (13Z)-retinoate, retinal, C18 ketone, β-ionylidene acetaldehyde, ψ-ionone, β-ionone and ethyl sorbate as a model compound. It was shown that the isomerization of polyenyl peroxy radicals occurs during autoxidation of all the compounds studied, excepting β-ionone. A kinetic scheme for the polyene autoxidation process was considered and analysed. The conditions under which the rate constants of elementary reactions may be determined were defined and the rate constants of propagation and termination reactions for different polyenes were evaluated. The disappearance and formation of different functional groups were monitored by the spectroscopic investigation of autoxidation of polyene solid films. Mechanisms of the initial stages of the process are proposed for different polyenes.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 513-524 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The autooxidation of retinyl acetate and methyl retinoate was investigated in chlorobenzene at 45°C. The rates of thermal initiation in the retinyl acetate solutions were measured, and a value was determined of the rate constant for the reaction of oxygen with retinyl acetate (RH + O2 → R· + HO2·): kio = (1.3 ± 0.2) × 10-5 L/mol · s. The number of moles of oxygen absorbed per mole of polyene depends on the substrate concentration. A kinetic scheme for the methyl retinoate autooxidation was proposed which takes into account the isomerization of primary peroxy radicals, and the rate constants for different elementary reactions were estimated. The partial rate constant for “allylic” hydrogen abstraction from retinyl acetate was estimated to be ≥ 1.65 × 103 L/mol · s. A probable propagation sequence was proposed for the autooxidation of retinyl acetate.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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