Kinetics and mechanism of the reaction between ascorbic acid derivatives and an arenediazonium salt: cationic micellar effects.

ABSTRACT

The effects of tetradecyltrimethylammonium bromide, TTAB, and hexadecyl-trimethylammonium bromide, CTAB, micellar systems on the reaction of 3-methylbenzenediazonium, 3MBD, tetrafluoroborate with ascorbic acid, VC, and with the hydrophobic derivatives 6-O-dodecyl-L-ascorbic acid, VC12, and 6-O-palmitoyl-L-ascorbic acid, VC16, were investigated at different pH values by employing a combination of UV-vis spectroscopy and high-performance liquid chromatography, HPLC, techniques. Previous studies in the absence of surfactant showed that the reaction between 3MBD and VC derivatives takes place through a rate-limiting decomposition of a transient diazo ether, DE, formed from reaction between 3MBD and the monoanion form of ascorbic acid, VC-, in a rapid preequilibrium step. In the presence of a fixed [CTAB], the kinetics of the reaction of 3MBD with VC follows a saturation kinetics similar to that observed in its absence, but for the reaction with VC12 and VC16, only the first linear portions of the saturation profiles could be obtained because k(obs) values become too large. HPLC analyses of the reaction mixtures show that no unexpected products are detected, suggesting that cationic micelles do not modify the mechanism of the reaction. Analyses of the kinetic data allowed estimations of the rate constant for the decomposition of the diazo ether and of the equilibrium constant for the formation of DE in the presence of CTAB micelles, which is approximately 6 times higher than in its absence; this suggests that CTAB micelles promote diazo ether formation. At constant [antioxidant], the variations of k(obs) for the reactions with VC, VC12, or VC16 follow bell-shaped curves, with rate enhancements of up to 2-3-fold for VC with respect to the value in the absence of surfactant. The rate maximum for the reaction of 3MBD with VC is reached at [CTAB] = 0.02 M suggesting a CTAB-induced rate increase, i.e., micellar catalysis; meanwhile the rate maximum for the reaction with VC12 and VC16, which may behave as amphiphilic compounds, is reached at [CTAB] approximately 1 x 10(-4) M, a concentration about 10 times lower than its critical micelle concentration, cmc, in pure water, but only approximately 3 times lower than the cmc of VC16, suggesting the formation of reactive CTAB-VC12 and CTAB-VC16 premicellar aggregates. Kinetic and HPLC results are consistent with the predictions of the pseudophase model and are interpreted in terms of 3MBD ions sampling in the aqueous bulk phase and the micellar effects on the different equilibrium involved. The results should contribute to a better understanding of the role of compartmentalized systems on the efficiency with which hydrophilic and hydrophobic reductants such as ascorbic acid derivatives interact with potentially mutagenic and carcinogenic ArN2+ ions.