Inhibition of the beta-cyclodextrin catalyzed dediazoniation of 4-nitrobenzenediazonium tetrafluoroborate. blocking effect of sodium dodecyl sulfate.
We have investigated the effects of sodium dodecyl sulfate, SDS, on the reaction between 4-nitrobenzenediazonium, 4NBD, ions and beta-cyclodextrin, beta-CD, under acidic conditions at T = 60 degrees C by employing a combination of spectrophotometric, chromatographic, and conductometric techniques. Previous studies under acidic conditions indicate that the secondary -OH groups of beta-CD solvate 4NBD ions, which are included in the beta-CD cavity, leading to the formation of a highly unstable transient diazo ether complex that undergoes homolytic fragmentation with an observed rate constant about 1700 times higher than that in pure aqueous acid solution (t(1/2) = 6 h at T = 60 degrees C) when [beta-CD]/[4NBD] = 40. Addition of SDS to a 4NBD/beta-CD system makes the k(obs) values decrease up to its value in a SDS micellar solution, which is similar to that in aqueous acid solution. Dediazoniation product distribution is significantly affected; the reaction between 4NBD and beta-CD ([beta-CD]/[4NBD] = 40), in the absence of SDS, proceeds exclusively through a homolytic mechanism leading to the quantitative formation of nitrobenzene, ArH, but addition of SDS turns over the mechanism by promoting the heterolytic mechanism. In addition, mixtures of 4-nitrophenol, ArOH, and ArH dediazoniation products are formed; their relative yields depend on the amount of added SDS so that at very high [SDS(T)], the heterolytic mechanism becomes the predominant one. Results are consistent with conductometric measurements showing that addition of beta-CD to an aqueous surfactant solution inhibits micelle formation and elevates CMC(app) values because CD encapsulation of surfactant monomers competes with the micellization process and are interpreted in terms of SDS monomers blocking the beta-CD cavity by forming a nonreactive complex, releasing 4NBD to the bulk solution.
Bravo-Diaz
Carlos
C
Departmento de Quimica Fisica, Facultad De Ciencias, Universidad De Vigo, 36200 Vigo, Pontevedra, Spain. cbravo@uvigo.es
Gonzalez-Romero
Elisa
E
D002384:Catalysis; D003979:Diazonium Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D004791:Enzyme Inhibitors / Q000737:chemistry / Q000494:pharmacology*; D008823:Micelles; D012967:Sodium Dodecyl Sulfate / Q000737:chemistry / Q000494:pharmacology*; D013329:Structure-Activity Relationship; D013997:Time Factors; D047392:beta-Cyclodextrins / Q000037:antagonists & inhibitors*
D003979:Diazonium Compounds; D004791:Enzyme Inhibitors; D008823:Micelles; D047392:beta-Cyclodextrins; D012967:Sodium Dodecyl Sulfate; C046321:4-nitrobenzene diazonium tetrafluoroborate