caa a22 4500 475761413 CHVBK 20180406123552.0 cr unu---uuuuu 170329e20000801xx s 000 0 eng 10.1007/BF02495073 doi (NATIONALLICENCE)springer-10.1007/BF02495073 Oxidation of alcohols by dimethyldioxirane [Elektronische Daten] [S. Grabovskii, E. Suvorkina, N. Kabal'nova, S. Khursan, V. Shereshovets] 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=k[ROH][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. Kluwer Academic/Plenum Publishers, 2000 dimethyldioxirane nationallicence alcohols nationallicence rate constants nationallicence free radicals nationallicence Grabovskii S. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut Suvorkina E. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut Kabal'nova N. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut Khursan S. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut Shereshovets V. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/8(2000-08-01), 1332-1337 1066-5285 49:8<1332 2000 49 11172 https://doi.org/10.1007/BF02495073 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02495073 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Grabovskii S. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut NATIONALLICENCE 700 1- Suvorkina E. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut NATIONALLICENCE 700 1- Kabal'nova N. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut NATIONALLICENCE 700 1- Khursan S. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut NATIONALLICENCE 700 1- Shereshovets V. Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054, Ufa, Russian Federation aut NATIONALLICENCE 773 0- Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/8(2000-08-01), 1332-1337 1066-5285 49:8<1332 2000 49 11172 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer