Accession Number : ADA328696

Title :   Salt Effects on Solvolysis Reactions of p-Nitrophenyl Alkanoates Catalyzed by 4-(Dialkylamino)pyridine-Functionalized Polymer in Buffered Water and Aqueous Methanol Solutions.

Descriptive Note : Technical rept.,

Corporate Author : INDIANA UNIV-PURDUE UNIV AT INDIANAPOLIS DEPT OF CHEMISTRY

Personal Author(s) : Wang, Guang-Jia ; Ye, Donghao ; Fife, Wilmer K.

PDF Url : ADA328696

Report Date : 1996

Pagination or Media Count : 25

Abstract : Specific salting-in effects that lead to striking substrate selectivity were observed for the hydrolysis of p-nitrophenyl alkanoates 2 (n=2-16) catalyzed by 4-(dialkylamino)pyridine-functionalized polymer 1 in aqueous Tris buffer solution at pH 8.0 and 30 deg C. Macromolecule 1 was found to exhibit clear substrate preference for 2 (n=6) in 0.05 M aqueous Tris buffer solution, as contrasted with the corresponding reaction in 0.05 M aqueous phosphate or borate buffer solutions where the substrate selectivity is absent. The formation of a reactive catalyst-substrate complex, 1-2, appears to be promoted by the presence of tris(hydroxymethyl) methylammonium ion, an efficient salting-in agent, from the Tris buffer system. The salting-in effect on formation of 1-2 complex is presumed responsible for the substrate specificity. The salting-out effects of sodium chloride on the solvolysis of 2 catalyzed by 1 were also investigated in 1:1 (v/v) methanol-water solution at pH 8.0 and 30 deg C. The rate of 1-catalyzed solvolysis of 2 (n=10-16) was found to vary inversely with NaCl concentration (0 - 1.0 M). The magnitude of the salting-out effects is dependent on the alkyl chain length in 2 and the concentrations of 1 and NaCl. At 7.5 x 10(exp -5) unit mol/L 1 and 0-1.0 M NaCl the order of reactivity for 2 (n=10-16) was n=10> 12 > 14 > 16. However, at 5.0 x 10(exp -6) unit mol/L 1 a revised reactivity order 2 n=14 > 12 > 16, was obtained at NaCl < 0.15 M. A significant decrease in the substrate preference for 1-catalyzed solvolysis of 2 (n=10-16) was observed at higher NaCl concentrations. We suggest that the reduced catalytic efficiency and selectivity expressed by 1 in the presence of sodium chloride should be attributed to changes in the morphology and composition of aggregates containing 1 and 2 in aqueous methanol solution that lead to decreased dependence of aggregate

Descriptors :   *SODIUM CHLORIDE, *SOLVOLYSIS, BUFFERS, SUBSTRATES, AMINES, METHANOLS, CATALYSIS, HYDROLYSIS, PHENYL RADICALS, PYRIDINES, BORATES, HYDROPHOBIC PROPERTIES, ALKYL RADICALS, AQUEOUS SOLUTIONS.

Subject Categories : Industrial Chemistry and Chemical Processing
      Organic Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE