An investigation of temperature effects upon first-order rate constants in the micellar pseudophase for decarboxylation of 6-nitrobeilzisoxazole-3-carboxylate (6-NBIC) and its 5-methyl derivative (6-NBIC-5-Me) was carried out. Surfactants used were cationic cetyltrialkyl ammonium 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 enthalpics, for both substrates. Values of Delta H-# and Delta S-# for 6-NBIC in the various surfactants give linear isokinetic plot, with CTBABr as outlier. (c) 2005 Elsevier Inc. All rights reserved.
Temperature effects upon aqueous micellar-assisted decarboxylation of 6-nitrobenzisoxazole-3-carboxylate and its 5-methyl derivative
DI PROFIO, Pietro
2006-01-01
Abstract
An investigation of temperature effects upon first-order rate constants in the micellar pseudophase for decarboxylation of 6-nitrobeilzisoxazole-3-carboxylate (6-NBIC) and its 5-methyl derivative (6-NBIC-5-Me) was carried out. Surfactants used were cationic cetyltrialkyl ammonium 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 enthalpics, for both substrates. Values of Delta H-# and Delta S-# for 6-NBIC in the various surfactants give linear isokinetic plot, with CTBABr as outlier. (c) 2005 Elsevier Inc. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
