Phototransformations of non-toxic antioxidants, the derivatives of 1,2-dihydroquinolines, in homogeneous and micellar solutions
Reactions of transient species photogenerated from 6-R-2,2,4-trimethyl-1,2-dihydroquinolines (TMDQ) are very sensitive to medium variation. In anhydrous organic solvents, aminyl radicals were generated. They decay in the reaction of dimerization with the second-order rate constant decreasing in a ro...
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| Main Author: | |
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| Format: | Article |
| Language: | English |
| Published: |
Wiley
1999-01-01
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| Series: | International Journal of Photoenergy |
| Online Access: | http://dx.doi.org/10.1155/S1110662X99000069 |
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| Summary: | Reactions of transient species photogenerated from 6-R-2,2,4-trimethyl-1,2-dihydroquinolines
(TMDQ) are very sensitive to medium variation. In anhydrous organic solvents, aminyl radicals were generated.
They decay in the reaction of dimerization with the second-order rate constant decreasing in a row
heptane>benzene>2-propanol. When passing from organic solvents to water, methanol, and water-alcohol
solutions, the kinetics and the direction of the reaction crucially change. As a result of the photolysis, the
product of the addition of a solvent to the double bond of heterocycle, 4-hydroxy- or 4-methoxy-6-R-2,2,4-
tetramethyl-1,2,3,4-tetrahydroquinoline is formed in water and methanol, respectively. The transformation
is a complex reaction, and the formation of excited transient species is followed by a sequence of first-order
and pseudo-first-order reactions. Unlike the photolysis in anhydrous organic solvents, the reaction in water
and methanol does not involve aminyl radicals. In aqueous solutions, the first-order rate constants for the
decay of transient species are higher in acidic and neutral solutions. At the pH close to pKa of the transient
species, it drops, indicating that the neutral form is less reactive. The same product is formed over the whole
range of pH. For the anionic surfactant (SDS) in acidic and alkaline solutions, the apparent rate constant in
the micellar solutions is lower than that in the aqueous (negative micellar catalysis). At the medium pH, a
positive micellar catalysis is observed, and the rate constant of the decay depends linearly on the concentration
of TMDQ in the micelles, indicative of the direct reaction between TMDQ and the cationic transient
species. |
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| ISSN: | 1110-662X |