Kinetic Studies for the Nucleopilic Substitution Reactions under High Pressure

친핵성 치환반응에 관한 고압에서의 속도론적 연구

  • 김영철 (한양대학교 자연과학대학 화학과) ;
  • 김세경 (한양대학교 자연과학대학 화학과)
  • Published : 1993.06.20

Abstract

The reaction rates of para-substituted benzoyl chlorides with substituted pyridines have been measured employing the conductometry method in acetonitrile, and pseudo-first order and second order rate constants are determined at various pressures and temperatures. The activation parameters (${\Delta}V^\neq, {\Delta}{\beta}^{\neq}, {\Delta}H^{\neq}, {\Delta}S^{\neq} {\Delta}G^{\neq}$) and the Hammett ρ-values are determined from the values of rate constants. The values of △${\Delta}V^\neq, {\Delta}{\beta}^{\neq}and {\Delta}S^{\neq}$ are all negative. The Hammett ρ-values are negative for the nucleophile (ρ$_X$), and positive for the substrate (ρ$_Y$) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S$_N$2 reaction mechanism and in bond formation favored with elevating pressure.

Keywords

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