Abstract
The kinetics of the reaction of oximate ions with 2,4-dinitrophenyl p-toluenesulfonate, 4-nitrophenyl p-toluenesulfonate, diethyl 4-nitrophenyl phosphate, and ethyl 4-nitrophenyl ethylphosphonate in H2O-DMSO mixtures (0 to 95 vol % of DMSO) cannot be described in terms of a single Bro/nsted equation. Regardless of the nature of the reaction center and leaving group, both in water and in 80% DMSO fast leveling of the reactivity of oximate ions is observed, the α-effect decreases at pK a ≥ 9.0 and disappears at pK a ≥ 12.0 owing to difference in the solvation of weakly (pK a ≤ 9.0) and strongly basic (pK a ≥ 9.0) oximate ions rather than to change of the transition state. Just unfavorable solvation effects are responsible for the fact that the limiting nucleophilic reactivity of oximate ions (as typical α-nucleophiles) is not higher than the reactivity of strongly basic alkoxide ions.
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Prokop'eva, T.M., Simanenko, Y.S., Suprun, I.P. et al. Nucleophilic Substitution at a Four-Coordinate Sulfur Atom: VI. Reactivity of Oximate Ions. Russian Journal of Organic Chemistry 37, 655–666 (2001). https://doi.org/10.1023/A:1012487415041
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DOI: https://doi.org/10.1023/A:1012487415041