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http://dx.doi.org/10.5322/JES.2011.20.1.119

The Catalytic Effects of o-Iodosobenzoate Ion on Hydrolysis of p-Nitrophenylvalate in ETAMs Solution  

Kim, Jeung-Bea (Falculty of Environmental Studies, Keimyung University)
Publication Information
Journal of Environmental Science International / v.20, no.1, 2011 , pp. 119-126 More about this Journal
Abstract
In this study, reaction model and reactions rate accelerated by o-iodosobenzoate ion(IB$^{\ominus}$) on hydrolysis reaction of p-nitrophenyl valate(NPV) using ethyl tri-octyl ammonium mesylate(ETAMs) for quaternary ammonium salts, the phase transfer catalysis(PTC) reagent, were investigated. The effect of IB$^{\ominus}$ on hydrolysis reaction rate constant of NPV was weak without ETAMs solutions. Otherwise, in ETAMs solutions, the hydrolysis reactions exhibit higher first order kinetics with respect to the nucleophile, IB$^{\ominus}$, and ETAMs, suggesting that reactions are occurring in small aggregates of the three species including the substrate(NPV), whereas the reaction of NPV with OH$^{\ominus}$ is not catalyzed by ETAMs. Different concentrations of NPV were tested to measure the change of rate constants to investigate the effect of NPV as substrate and the results showed that the effect was weak. This means the reaction would be the first order kinetics with respect to the nucleophile. This behavior for the drastic rate-enhancement of the hydrolysis is referred as 'Aggregation complex model' for reaction of hydrophobic organic ester with o-iodosobenzoate ion(IB$^{\ominus}$) in hydrophobic quarternary ammonium salt(ETAMs) solutions.
Keywords
ETAMs; o-Iodosobenzoate ion; Aggregation complex model;
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1 Bunton, C. A., Cuenca, A., 1987, Abnormal micellar effects on reactions of azide and N-alkyl-2- bromopyridinium ions, J. Org. Chem., 52(5), 901-907.   DOI
2 Bunton, C. A., Moffatt, J. R., 1988, Micellar effects upon substitutions by nucleophilic anions, J. Phys. Chem., 92(10), 2896-2902.   DOI
3 Cook, R. D., Rahhal, A. L., 1986, The kinetics of the alkaline hydrolysis of aryl diphenylphosphinothioates; The significance for the mechanism of displacement at phosphorus, Tetrahedron Letters, 26, 3147-3150.   DOI
4 Dekeijzer, A. H., Koole, L. H., Van der Hofstad, W. J. M., Buckrate, H. M., 1988, Enhancement of nucleophilic substitution reactions in phosphate esters; Influence of conformational transmission on the rate of solvolysis in alkyl diphenylphosphinates, J. Org. Chem., 54, 1453-1456.   DOI
5 Fendler, J. H., Fendler, E. J., 1975, Catalysis in micellar and macromolecular system, Academic press, 4th ed., New York, 30-47.
6 Foroudian, H. J., Gillitt N. D., Bunton, C. A., 2002, Effects of nonionic micelles on dephosphorylation and aromatic nucleophilic substitution, J. Colloid and Interface Science, 250, 230-237.   DOI
7 Jarrouse, J., Gelod, C. R., 1951, Abnormal PTC effects on reactions of benzyl chloride and cyclohexanol, Seances Acad. Sci., Ser. C, 232, 1414-1417.
8 Kim, J. B., Kim, H. Y., 2004, Effect of OH and o-iodosobenzoate ions on dephosphorylation of organo phosphororus ester in CTAX micelle, J. of the Environmental Science, 14(2), 241-249.
9 Kim, J. B., 2005, Dephosphorylation of an organic phosphinate by nucleophile in anionic and cationic micellar solutions, J. of the Environmental Science, 15(5), 485-491.   DOI
10 Maximiano, F. A., H., Chaimovich, Cuccovia, I. M., 2006, Decarboxylation of 6-nitrobenzisoxazole-3-carboxylate in mixed micelles of zwitterionic and positively charged surfactants, Langmuir, 22, 8050-8055.   DOI
11 Bunton, C. A., Hong, Y. S., Romsted, L. S., Quan, C., 1981, Catalysis by hydrophobic tetraalkylammonium ions; Dephosphorylation of p-nitrophenyl diphenyl phosphate, J. Amer. Chem. Soc., 103, 5788-5794.   DOI
12 Rodriguez, A., Graciani, M., Moya, M., 1996, The surface tension for the salt solutions and aqueous solutions, Langmuir, 12, 4090-4095.   DOI
13 Romsted, I. R., Cordes, E. H., 1968, Secondary valence force catalysis.Ⅶ. Catalysis of hydrolysis of p-nitrophenyl hexanoate by micelle-forming cationic detergents, J. Amer. Chem. Soc., 90, 4404-4409.   DOI
14 Al-Lohedan, H., Bunton, C. A., Mhala, M. M., 1982, Micellar effects upon spontaneous hydrolyses and their relation to mechanism, J. Amer. Chem. Soc., 104, 6654-6660.   DOI
15 Bunton, C. A., Cerichelli, G., Ihara, Y., Sepulveda, L., 1979, Micellar catalysis and reactant incorporation in dephosphorylation and nucleophilic substitution, J. Amer. Chem. Soc., 101, 2429-2435.   DOI