Journal of the American Chemical Society p. 7680 - 7684 (1985)
Update date:2022-08-11
Topics:
Fan, Wei-Qiang
Jiang, Xi-Kui
Hydrolytic rate constants (kobsd) were determined for 13 para- and meta-substituted phenyl esters of n-hexadecanoates (16-Y) in 55:45 (v/v) (Φ=0.55), 60:40 (Φ=0.60), 65"35 (Φ=0.65), and 70:30 (Φ=0.70) Me2SO-H2O solvent mixtures.Rates of 7 n-octanoates (8-Y) were also measured in solvents with Φ=0.55, 0.60, 0.65.Results reveal that the nature of the substituent effect depends on solvent composition.At Φ=0.70, the log kob's correlate with Hammett's ? constants, whereas at Φ=0.55, they correlate with Rekker's hydrophobic f constants.In between at Φ=o.65 and 0.60, the rate constants can be expressed in terms of a two-parameter equation: log k=?ρ + hf + C.The n-octanoates, as expected, follow only the Hammett correlation in disregard of the solvent composition.The present work is the first example of a successful correlation of hydrophobic-lipophilic substituent constants for substrates with different types of substituents and withuot the involvement of "third-parties", e.g., added host or surfactant molecules.It provides further insights into the effect of hydrophobic-lipophilic interactions on chemical reactivity and yet another new line of evidence for the phenomena of aggregation and self-coiling.
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