Oxidation of alcohols by dimethyldioxirane |
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Authors: | S A Grabovskii E S Suvorkina N N Kabal'nova S L Khursan V V Shereshovets |
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Institution: | (1) Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054 Ufa, Russian Federation |
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Abstract: | The kinetics of oxidation of a series of monoatomic alcohols (methanol, 2-propanol, 2-butanol, 2-methyl-1-propanol, 2-chloroethanol,
1,3-dichloro-2-propanol, benzyl alcohol), hydroxyacetic acid, and 1,3-butandiol (ROH) by dimethyldioxirane (1) was studied. The reaction kinetics obeys the second order equationw=kROH]1]. The rate constants were measured in the range of 7–50†C, and the activation parameters were found. To describe the reaction
rate constants as a function of the ROH structure, the two-parametric Taft equation was used, which takes into account both
the polar and resonance substituent effects. Alcohol oxidation produces the corresponding carbonyl compounds,viz., ketones from secondary alcohols and aldehydes from primary alcohols, in yields of at least 80%. The results were explained
by the competition of the molecular (oxenoid) and radical mechanisms. The introduction of electron-withdrawing substituents
into the alcohol molecule increases the contribution of the radical channel of the reaction.
Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1338–1343, August, 2000. |
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Keywords: | dimethyldioxirane alcohols rate constants free radicals |
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