Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Cross Interaction Constants As a Measure of the Transition State Structure (Part 2). Nucleophilic Substitution Reactions of Phenacyl Bromides with Aniline in Methanol-Acetonitrile Mixtures

  • Published : 1988.06.20
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Abstract

Kinetics and mechanism of the nucleophilic substitution reactions of phenacyl bromides with anilines in methanol-acetonitrile mixtures at $45.0^{\circ}C$ are reported. The reaction is found to proceed via $S_N2$ process, but the magnitudes of cross interaction constants, ${\rho}_{XY}$, between substituents X in the nucleophile and Y in substrate were unusually small, even after allowing for the fall off due to non-conjugative intervening -CO group in the reactant. As in the other phenacyl derivatives, the resonance shunt phenomenon was invoked to explain the remarkable diminuation of the $|{\rho}_{XY}|$ values.

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