期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 67, 期 24, 页码 8475-8480出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo026339g
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A kinetic study is reported for the reaction of the anionic nucleophiles OH-, CN-, and N-3(-) with aryl benzoates containing substituents on the benzoyl as well as the aryloxy moiety, in 80 mol % H2O-20 mol % dimethyl sulfoxide at 25.0 degreesC. Hammett log k vs a plots for these systems are consistently nonlinear. However, a possible traditional explanation in terms of a mechanism involving a tetrahedral intermediate with curvature resulting from a change in rate-determining step is considered but rejected. The proposed explanation involves ground-state stabilization through resonance interaction between the benzoyl substituent and the electrophilic carbonyl center in the two-stage mechanism. Accordingly, the data are nicely accommodated on the basis of the Yukawa-Tsuno equation, which gives linear plots for all three nuceophiles. Literature reports of the mechanism of acyl transfer processes are reconsidered in this light.
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