Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Kinetics of the Solvolysis of 1-Adamantyl Fluoroformate under High Pressure

고압하에서 1-Adamantyl Fluoroformate의 가용매분해반응에 대한 속도론적 연구

  • Kyong Jin Burm (Department of Chemistry, Hanyang University) ;
  • Dennis N. Kevill (Dept. of Chemistry, Northern Illinois University) ;
  • Kim Jong Chul (Department of Chemistry, Hanyang University)
  • Published : 1993.01.20
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Abstract

Specific rates of solvolysis of 1-adamantyl fluoroformate in hydroxylic solvents have been measured by an electric conductivity method under various pressures. The activation parameters (${\Delta}V^{\neq}{_o},\;{\Delta}{\beta}^{\neq},\;{Delta}H^{\neq},\;{Delta}S^{\neq}$,/TEX>) and average pressure within the solvation-shell of activated complex (charge development) have been estimated from the rates. Also, the selectivities for the formation of solvolysis products in aqueous ethanol have been determined by response-calibrated GC. The values of ${\Delta}V^{\neq}{_o},\;and\;{\Delta}{\beta}^{\neq}$ are both negative, but ${Delta}H^{\neq}$ is positive and ${Delta}S^{\neq}$, is large negative. This behavior is discussed in terms of electrostriction of solvation. From these results, it could be postulated that the solvolysis of 1-adamantyl fluoroformate have two major reaction pathway.

메탄올 및 에탄올 수용액내에서 1-adamantyl fluoroformate의 가용매분해반응속도를 여러 압력하에서 전도도방법을 이용하여 측정하였다. 이들 속도상수로부터 활성화부피(${\Delta}V^{\neq}{_o}$), 활성화압축율계수(${\Delta}{\beta}^{\neq}$), 활성화엔탈피(${Delta}H^{\neq}$), 활성화엔트로피(${Delta}S^{\neq}$), 그리고 활성화 착물에서의 charge development(△P)를 구하였다. 또한 에탄올 수용액내에서 가용매분해반응으로 인한 생성물에 대한 selectivity를 GC를 이용하여 측정하였다. 그 결과 ${\Delta}V^{\neq}{_o}$와 ${\Delta}{\beta}^{\neq}$의 값은 모두 음의 값을 ${Delta}H^{\neq}$는 양의 값을 ${Delta}S^{\neq}$은 큰 음의 값을 얻었다. 이 현상을 용매구조변화에 대하여 논의하였다. 이들 결과로부터 본 반응은 acyl carbon을 공격하는 이분자성반응과 가용매분해과정(S-D)인 용매-분리이온쌍반응으로 추정할 수가 있었다.

Keywords

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