An investigation of temperature effects upon first-order rate constants in the micellar pseudophase for decarboxylation of 6-nitrobenzisoxazole- 3-carboxylate (6-NBIC) and its 5-methyl derivative (6-NBIC-5-Me) was carried out. Surfactants used were cationic cetyltrialkylammonium bromide with alkyl = methyl (CTABr), ethyl (CTEABr), n-propyl (CTPABr), and n-butyl (CTBABr). The investigation shows that micelles speed up reactions by decreasing enthalpies of activation. Increase in head group bulk further speeds reactions still by a small decrease in the enthalpies, for both substrates. Values of deltaH# and deltaS# for 6-NBIC in the various surfactants give linear isokinetic plot, with CTBABr as outlier.
Temperature effects upon micellar-assisted decarboxylation of 6-nitrobenzisoxazole-3-carboxylate and its 5-methyl derivative
SPRETI, Nicoletta;
2006-01-01
Abstract
An investigation of temperature effects upon first-order rate constants in the micellar pseudophase for decarboxylation of 6-nitrobenzisoxazole- 3-carboxylate (6-NBIC) and its 5-methyl derivative (6-NBIC-5-Me) was carried out. Surfactants used were cationic cetyltrialkylammonium bromide with alkyl = methyl (CTABr), ethyl (CTEABr), n-propyl (CTPABr), and n-butyl (CTBABr). The investigation shows that micelles speed up reactions by decreasing enthalpies of activation. Increase in head group bulk further speeds reactions still by a small decrease in the enthalpies, for both substrates. Values of deltaH# and deltaS# for 6-NBIC in the various surfactants give linear isokinetic plot, with CTBABr as outlier.Pubblicazioni consigliate
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