Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Kinetics of Methanolysis of Arenesulfonyl Chloride in the Presence of Pyridines

치환 피리딘 존재하에서의 염화아렌 슬포닐의 가메탄올 분해반응의 속도론적 연구

  • Kim Hyong Tae (Department of Chemical Education, Pusan National University) ;
  • Lee Ik Choon (Department of Chemistry, Inha University) ;
  • Myung Soo Rim (Department of Chemical Education, Pusan National University)
  • 김형태 (부산대학교 사범대학 화학교육과) ;
  • 이익춘 (인하대학교 이과대학 화학과) ;
  • 임명수 (부산대학교 사범대학 화학교육과)
  • Published : 1989.10.20
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Abstract

Kineties for the reactions of pyridines with 1-anthracenesulfonyl chloride (1-ASC) and 3-phenanthrenesulfonyl chloride (3-PSC) was investigated in methanol as solvent. Structural variation in pyridine followed $Br{\o}$ nsted and Hammett relations for both 1-ASC and 3-PSC; the corresponding coefficients, {\beta}\;and\;{\rho}\;at\;20^{\circ}C$ were 0.55, -3.5 for 1-ASC, and 0.43, -2.6 for 3-PSC respectively. Reactivity-selectivity principle was checked in competition system 1-ASC/3-PSC. As a result, this principle was found to hold at experimental temperatures, whereas to break down over in the range of isoselective temperature ($34.3^{\circ}C$). Judging from the above results and activation parameters, we concluded that these reactions proceeded by synchronous $S_n2$ mechanism in rate-determining step.

여러가지 피리딘 존재하에서 1-염화안트라센술포닐(1-ASC) 및 3-페난트렌술포닐(3-PSC)이 메탄올 속에서 각각 일으키는 반응의 메카니즘을 속도론적으로 논의하였다. 이들 반응에 대한 Bronsted계수(${\beta}$)는 $20^{\circ}C$에서 1-ASC : 0.55, 3-PSC : 0.43였고 Hammett 반응상수(${\rho}$ 온도에서 1-ASC : -3.5, 3-PSC : -2.6이었다. 두 반응계에 대한 반응성-선택성 원리를 검토한 결과, 등선택성 온도는 $34.3^{\circ}C$였으며 이보다 높은 온도에서는 이 원리가 성립하지 않음을 알았다. 활성화 파라미터와 함께 위의 결과로부터 이들 반응은 속도 결정단계에서 synchronous $S_n2$메카니즘에 의해 진행되는 것으로 결론 지어졌다.

Keywords

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