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KMID : 1059519850290050522
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Journal of the Korean Chemical Society
1985 Volume.29 No. 5 p.522 ~ p.532
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Chemical Reactions in Surfactant Solution (I). Substituent Effects of 2-Alkylbenzimidazolide ions on Dephosphorylation in CTABr Solutions
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Hong Young-Seuk
Park Chan-Sik
Kim Jeung-Bae
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Abstract
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The reactions of p-nitrophenyldiphenylphosphate (p-NPDPP) with anions of benzimidazole (BI) and its 2-alkyl derivatives (R-BI) are strongly catalyzed by the micelles of cetyltrimethyl ammonium bromide (CTABr). On the other hand, the first order rate constants (k'R-BI-) and the second order rate constants (km(R-BI-)) of the reactions mediated by R-BI-in the micellar pseudophase are much smaller than those mediated by BI-. In order to explain the slower rates of the micellar reactions mediated by R-BI-, we compared the concentration-ratios ([R-BI-]/[BI-]) with the first order rate constant-ratios (k'R-BI-/k'BI-) and the second order constant-ratios (km(R-BI-)/km(BI-)) for the reactions taking place in the micellar pseudophase. The rate constant-ratios were much smaller than the concentration-ratios. For example in a 5 × 10-4M butyl-BI solution, the two ratios were 0.089 and 0.430 (for the first order) respectively, and in a 10-4M butyl-BI solution the former was 0.100 (for the second order). This predicts that the reactivities of R-BI- in the micellar pseudophase are much smaller than that of BI-. Based on the values of several kinetic parameters measured for dephosphorylation of p-NPDPP mediated by R-BI-, a schemetic model is proposed. Due to the hydrophobicity and the steric effect of the alkyl substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long cetyl groups of CTABr. Consequently, the movements of R-BI- bound to the micelle should be restricted, leading to decreased collison frequencies between the nucleophiles and p-NPDPP. We refer this as an "anchor effect". This effect became more predominent when a larger alky group in R-BI was employed and when a greater concentration of R-BI was used.
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KEYWORD
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