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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 33, Number 5
JKCSEZ 33(5)
October 20, 1989 

 
Title
Kinetics of Methanolysis of Arenesulfonyl Chloride in the Presence of Pyridines

치환 피리딘 존재하에서의 염화아렌 슬포닐의 가메탄올 분해반응의 속도론적 연구
Author
Hyong Tae Kim,Ikchoon Lee, Myung Soo Rim

김형태, 이익춘, 임명수
Keywords
Abstract
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(β)는 20℃에서 1-ASC : 0.55, 3-PSC : 0.43였고 Hammett 반응상수(ρ)는 같은 온도에서 1-ASC : -3.5, 3-PSC : -2.6이었다. 두 반응계에 대한 반응성-선택성 원리를 검토한 결과, 등선택성 온도는 34.3℃였으며 이보다 높은 온도에서는 이 원리가 성립하지 않음을 알았다. 활성화 파라미터와 함께 위의 결과로부터 이들 반응은 속도 결정단계에서 synchronous Sn2메카니즘에 의해 진행되는 것으로 결론 지어졌다.

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 Brφ nsted and Hammett relations for both 1-ASC and 3-PSC; the corresponding coefficients,β and ρ at 20℃ 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℃). Judging from the above results and activation parameters, we concluded that these reactions proceeded by synchronous SN2 mechanism in rate-determining step.

Page
468 - 476
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