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Liquid‐phase autooxidation of retinyl polyenes
Author(s) -
Finkelshtein E. I.,
Rubchinskaya Yu. M.,
Kozlov E. I.
Publication year - 1984
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550160503
Subject(s) - chemistry , autoxidation , retinyl acetate , reaction rate constant , oxygen , photochemistry , radical , kinetics , organic chemistry , vitamin , retinol , biochemistry , physics , quantum mechanics
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 + O 2 → R· + HO 2 ·): k io = (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 × 10 3 L/mol · s. A probable propagation sequence was proposed for the autooxidation of retinyl acetate.