Quantitative Prediction of Leaving Group Orders fronı Aliphatic Carbon in Sjy2 Reactions

Quantitative Prediction of Leaving Group Orders fronı Aliphatic Carbon in Sjy2 Reactions

Two quantitative conelations of leaving groups effects from aliphatic car¬bon in bimolecular nucleophilic substitution reactions were given by using Ed- wards equation; k GH3Y + X" -> CH3 X + Y- logk/ko = a Ex + p Hx in which k and k0 are the reaction rate constants of the substrate with a nucleo- phile, X and water, respectively, at 25.0°C. Ex is the oxidative dimerization po- tential and Hxis the basicity of the nucleophile, relative to water. Leaving group reactivity order is a function of oxidation and basicity of the leaving group. In a serie of alkyl substrates, CH3Y, the substrate constant a depends linearly to the Ey_ and the substrate constant, log fi depends linearly to the Hy_. a - 1.11 EY_ + 0.87 log/? - 0.13 Hy_ — 1.36 Using these equations, new substrate constants and then the rate constants of bimolecular nucleophilic substitution reactions on CH3Y compounds in water, at 25.0°C can be estimated.

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  • Communications Faculty of Sciences University of Ankara Series B Chemistry and Chemical Engineering