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pp.241-249
This study deals with micellar effects on dephosphorylation of diphenyl-4- nitrophenylphosphate (DPNPPH), diphenyl-4-nitrophenylphosphinate (DPNPIN) and isopropylphenyl-4-nitrophenyl phosphinate (IPNPIN) mediated by OH⊖ or o-iodosobenzoate ion (IB⊖) in aqueous and CTAX solutions. Dephosphorylation of DPNPPH, DPNPIN and IPNPIN mediated by OH⊖ or o-iodosobenzoate ion (IB⊖) 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 Stern layer in which they can easily react, while hydrophilic OH⊖ (or IB⊖) and hydrophobic substrates are not mixed in water. Even though the concentrations (>10-3 M) of OH⊖ (or IB⊖) in CTAX solutions are much larger amounts than those (6×10-6 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, CTACl is more effective on the dephosphorylation of substrates than CTABr due to easier expelling of Cl⊖ ion by OH⊖ (or IB⊖) ion from the micelle, because of easier solvation of Cl⊖ ion by water molecules. The reactivity of IPNPIN with OH⊖ (or IB⊖) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles.
