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- W2120329172 abstract "We report here the first observation of alkali-metal ion catalysis and inhibition in SNAr reactions. The plot of kobsd versus [alkali-metal ethoxide] exhibits downward curvature for the reactions of 1-(4-nitrophenoxy)-2,4-dinitrobenzene with EtOLi, EtONa, and EtOK, but upward curvature for the corresponding reaction with EtOK in the presence of 18-crown-6-ether (18C6). Dissection of kobsd into the second-order rate constants for the reactions with the dissociated EtO(-) and the ion-paired EtOM (i.e., k EtO - and kEtOM , respectively) has revealed that the reactivity increases in the order EtOLi<EtONa<EtOK<EtO(-)<EtOK/18C6. This indicates that the reaction is inhibited by Li(+), Na(+), and K(+) ions but is catalyzed by 18C6 K(+) ion. The reactions of 1-(Y-substituted-phenoxy)-2,4-dinitrobenzenes have been proposed to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs after the rate-determining step based on the kinetic result that σ(o) constants exhibit a much better Hammett correlation than σ(-) constants. Alkali-metal ion catalysis or inhibition has been discussed in terms of differential stabilization of ground-state and transition-state complexes through a qualitative energy profile. A π-complexed transition-state structure is proposed to account for the kinetic results." @default.
- W2120329172 created "2016-06-24" @default.
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- W2120329172 date "2014-08-29" @default.
- W2120329172 modified "2023-10-02" @default.
- W2120329172 title "Alkali-Metal Ion Catalysis and Inhibition in SNAr Displacement: Relative Stabilization of Ground State and Transition State Determines Catalysis and Inhibition in SNAr Reactivity" @default.
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- W2120329172 doi "https://doi.org/10.1002/chem.201404004" @default.
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