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KMID : 1059519890330010031
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Journal of the Korean Chemical Society
1989 Volume.33 No. 1 p.31 ~ p.36
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The Nucleophilic Substitution Reactions of the Nitrate Group. The Kinetics of Substituted Benzyl Nitrates with Anilines in Acetonitrile
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Kim Wang-Ki
Sohn Chang-Kook
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Abstract
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The second-order rate constants for the nucleophilic substitution reactions of para-substituted benzyl nitrates with para-substituted anilines in acetonitrile were conductometrically determined. Hammett ρx and ρy values and BrΦnsted β values were obtained from these kinetic data. The reactions of Benzyl nitrates with the series of anilines showed linear Hammett plots with negative slopes. For the change of substituents in the benzyl nitrates, nonlinear Hammett plots with a concave upwards curve were obtained. We applied the potential energy surface and the quantum mechanical models in order to examine the transition state variations caused by changes in substituents on the nucleophile and the substrate. The results showed that the reaction was proceeded via the SN2-type reaction mechanism in which the extent of bond-formation was greatly changed depending on the property of the substituents in substrate.
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