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- W2065882912 abstract "Apart from the well documented BAC 2 mechanism, alkaline hydrolysis of esters also proceeds by the ElcB mechanism which operates in systems having acidic α-H atoms. The differential solvent effects of protic and dipola aprotic solvents (such as DMSO) on the rate of alkaline hydrolysis of esters have been used as a mechanistic probe to differentiate these two mechanisms [1]. The results of the alkaline hydrolysis of arylphenylacetates(I) and aryl 4-nitrophenylacetates(II) in ethanol-water and DMSO-water systems are presented in this present paper. For the hydrolysis of I the rate of liberation of phenoxide ion is first order with respect to ester rate to change of solvent to D2O(kH2O/kD2O ≈ 1) and the high Hammett reaction constant (ϱ = + 1.4) for variation of the leaving group point to the operation of ElcB mechanism. The introduction of a nitro group in acyl moiety causes instantaneous formation of the carbanion in the case of II. The rate of the hydroxide ion concentration in the range employed (0.1–1 M). Increasing percentage of DMSO in the solvent increases the rate for both I and II. A comparison of the results of this investigation with those for the hydrolysis of aryl α-phenylmethanesulfonates(III) and aryl α-4-nitrophenylmethanesulfonates(IV) reveals a spectrum of ElcB reactivity [2]. These are rationalised in terms of the relative stabilization of the ground state and transition state by DMSO. Since the transition states are charge extended structures these may well be equally solvated by DMSO. Therefore, any difference in reactivity must stem from the ground state of stabilization. The rate retardation in the case of IV had been explained as due to the greater stabilization of the charge extended ground state anion by DMSO. But such an effect is operative to a much smaller extent in the case of II pointing to the relative instability of the carbanion on passing from IV to II. It is shown that I, II and III belong to one group of compounds reacting by ElcBion-pair mechanism while IV reacts by the Elanion mechanism in the ElcB spectrum." @default.
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- W2065882912 date "1980-01-01" @default.
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- W2065882912 title "Differential ground state and transition state stabilization by dimethylsulfoxide in ester hydrolysis by elcb. Pathway" @default.
- W2065882912 doi "https://doi.org/10.1016/s0020-1693(00)92281-3" @default.
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