Abstract
We have studied the nucleophilicity of the hydroperoxide anion relative to 4-nitrophenyl diethyl phosphonate (NPDEPS) in the presence of cetyltrimethylammonium bromide (water, 25 °C) while varying the acidity of the medium and the hydroperoxide anion concentration over a broad range. The increase in the reaction rate when the reaction is transferred to a micellar pseudophase is as high as ∼10-fold, which is explained by concentration effects. In CTAB micelles, as in water, the hydroperoxide ion is one of the most effective α-nucleophiles, and the size of the α-effect, characterized by the ratio of the second-order rate constants for reactions of HOO− and OH− anions with NPDEPS, remains practically constant and reaches a value of ∼50-fold.
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Translated from Teoreticheskaya i Éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 357–363, November–December, 2006.
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Solomoichenko, T.N., Sadovskii, Y.S., Prokop’eva, T.M. et al. Micellar effects of surfactants in cleavage of 4-nitro-phenyl diethyl phosphonate by hydroperoxide anion. Theor Exp Chem 42, 364–370 (2006). https://doi.org/10.1007/s11237-006-0067-7
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DOI: https://doi.org/10.1007/s11237-006-0067-7