DOI QR코드

DOI QR Code

Effect of OHθ and o-lodosobenzoate Ions on Dephosphorylation of Organo Phosphororus Ester in CTAX Micelle

CTAX 미셀 용액속에서 유기인 에스테르 화학물의 탈인산화 반응에 대한 OHθ 및 o-lodosobenzoate 이온의 영향

Kim Jeung-Bea;Kim Hak-Yoon
김정배;김학윤

  • Published : 2005.02.01

Abstract

This study deals with micellar effects on dephosphorylation of diphenyl-4- nitrophenylphosphate (DPNPPH), diphenyl-4-nitrophenylphosphinate (DPNPlN) and isopropylphenyl-4-nitrophenyl phosphinate (IPNPlN) mediated by $OH^\Theta$ or o-iodosobenzoate ion $(IB^\Theta)$ in aqueous and CTAX solutions. Dephosphorylation of DPNPPH, DPNPIN and IPNPIN mediated by $OH^\Theta$ or o-iodosobenzoate ion $(IB^\Theta)$ is relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, much accelerated because CTAX micelles can accommodate both reactants in their Stem layer in which they can easily react, while hydrophilic $OH^\Theta\;(or\;IB^\Theta)$ and hydrophobic substrates are not mixed in water. Even though the concentrations $(>10^{-3}\;M)\;of\;OH^\Theta\;(or\;IB^\Theta)$ in CTAX solutions are much larger amounts than those $(6\times10^{-6}\;M)$ of substrates, the rate constants of the dephosphorylations are largely influenced by the change of concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACI is more effective on the dephosphorylation of substrates than CTABr due to easier expelling of $Cl^\Theta$ ion by $OH^\Theta\;(or\;IB^\Theta)$ ion from the micelle, because of easier solvation of $Cl^\Theta$ ion by water molecules. The reactivity of IPNPlN with $OH^\Theta\;(or\;IB^\Theta)$ is lower than that of DPNPlN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles.

Keywords

Dephosphorylation;CTABr;Organo phosphorous ester;Micelle

References

  1. Fendler, J. H. and E. J. Fendler, 1975, Catalysis in micellar and macromolecular system, Academic press, New York, N.Y., 30-47pp
  2. Cook, R. D. and L. Rahhal-Arabi, 1986, The kinetics of the alkaline hydrolysis of aryl diphenylphosphinothioates: The significance for the mechanism of displacement at phosphorus, Tetrahedron Letters, 26, 3147-3150
  3. DeKeijzer, A. H., L. H. Koole, W. J. M. Van der Hofstad and H. M. Buckrate, 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 https://doi.org/10.1021/jo00267a044
  4. McBain, J. W., 1913, Micellar formation of aqueous solution, Trans. Faraday Soc., 9, 99-112
  5. Hartly, G. S., 1936, Aqueous solution of paraffin chain salt, Herman Paris Press, 125-258pp
  6. Cook, R. D., C. E. Diebert, W Schwarz, P. C. Turley and P. Haake, 1973, Mechanism of nucleophilic displacement at phosphorus in the alkaline hydrolysis of phosphinate Esters, J. Amer. Chem. Soc., 95, 8088-8096 https://doi.org/10.1021/ja00805a023
  7. Bunton, C. A., Y. S. Hong, L. S. Romsted and C. Quan, 1981, Catalysis by hydrophobic tetraalkylarnmonium ions; Dephosphorylation of p-nitrophenyl diphenyl phosphate, J. Amer. Chem. Soc., 103, 5788-5794 https://doi.org/10.1021/ja00409a029
  8. Bunton, C. A., G. Cerichelli, Y. Ihara and L. Sepulveda, 1979, Micellar Catalysis and reactant incorporation in dephosphorylation and nucleophilic substitution, J. Amer. Chem. Soc., 101, 2429-2435 https://doi.org/10.1021/ja00503a032
  9. Quina, F. H., H. Chaimovich, 1979, Ion exchange in micellar solutions 1; Conceptual framework for ion exchange in micellar solutions, J. Phys, Chem., 83(14), 1844-1850 https://doi.org/10.1021/j100477a010
  10. Bunton, C. A., F. DeBuzzaccarini and F. H. Hamed, 1983, Dephosphorylation in cationic micelles and microernulsions: Effects of added alcohols, J. Org. Chem., 48, 2457-2461 https://doi.org/10.1021/jo00163a003
  11. Bunton, C. A. and A. Cuenca, 1987, Abnormal micellar effects on reactions of azide and Nalkyl-Zebrornopyridiniurn ions, J. Org. Chem., 52(5), 901-907 https://doi.org/10.1021/jo00381a032
  12. Bunton, C. A. and J. R. Moffatt, 1985, Micellar reactions of hydrophilic ions; A coulombic model, J. Phys. Chem., 89(20), 4166-4169 https://doi.org/10.1021/j100266a003
  13. Hong, Y. S., C. S. Park and J. B. Kim, 1985, Chemical reactions in surfactant soution(1); Substituent effects of 2-alkylbenzimidazole ions on dephosphorylation in CT ABr solutions, J. Kor. Chem. Soc., 29(5), 522-532
  14. Bunton, C. A., M. M. Mhala and J. R. Moffatt, 1989, Nucleophilic reactions in zwitterionic micelles of amine oxide or betaine sulfonate surfactants, J. Phys. Chem., 93(2), 854-858 https://doi.org/10.1021/j100339a061
  15. Bourne, N., E. Chrystiuk, A. M. Davis and A. Williams, 1988, A single transition state in the reaction of aryl diphenylphosphinate esters with phenolate ions in aqueous solution, J. Amer. Chem. Soc., 110, 1890-1895 https://doi.org/10.1021/ja00214a037
  16. Bunton, C. A., M. M. Mhala, J. R. Moffatt, 1989, Reactions of anionic nucleophiles in anionic micelles; A quantitative treatment, J. Phys, Chem., 93(23), 7851-7856 https://doi.org/10.1021/j100360a025
  17. Bunton, C. A. and J. R. Moffatt, 1986, Ionic competition in micellar reactions; A quantitative treatment, J. Phys. Chem., 90(4), 538-541 https://doi.org/10.1021/j100276a006
  18. Bunton, C. A., Y. S. Hong, L. S. Romsted, and C. Quan, 1981, Micellar catalysis of dephosphorylation by benzimidazolide and naphth2,3-imidazolide ions, J. Amer. Chem. Soc., 103, 5784-5788 https://doi.org/10.1021/ja00409a028
  19. Bunton, C. A. and J. R. Moffatt, 1988, Micellar effects upon substitutions by nucleophilic anions, J. Phys. Chem., 92(10), 2896-2902 https://doi.org/10.1021/j100321a038