Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Nucleophilic Displacement at Sulfur Center (XVII). Solvolysis of 2-Anthracenesulfonyl Chloride

황의 친핵성 치환반응 (제17보) 2-염화안트라센 술포닐의 가용매 분해반응

  • Hyong Tae Kim (Department of Chemical Education, Busan National University) ;
  • Soo Dong Yoh (Department of Chemical Education, Kyungpook National University) ;
  • Ikchoon Lee (Department of Chemistry, Inha University)
  • 김형태 (釜山大學校 師範大學 化學敎育科) ;
  • 여수동 (慶北大學敎 師範大學 化學敎育科) ;
  • 이익춘 (仁荷大學校 理科大學 化學科)
  • Published : 1983.06.20
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Abstract

The kinetics of 2-anthracenesulfonyl chloride in methanol-water, ethanol-water, acetone-water and acetonitrile-water has been studied by electroconductometric method. For media in which water has the same mole fraction, the rate was greater in protic solvent than in dipolar aprotic solvent and it was greater consistently in methanol-water than in ethanol-water over the whole range of solvent composition investigated, while the two rates in acetone-water and acetonitrile-water inverted at about 0.9 of mole fraction of water. Both m value, susceptibility of rate to the ionizing power and n value, solvent participation number in the transition state were much smaller in protic solvent. These values and the activation parameters show that solvolysis of 2-anthracenesulfonyl chloride proceeds by $ S_N2$ mechanism.

물-메탄올, 물-에탄올, 물-아세톤 및 물-아세토니트릴의 2-성분 혼합용매 속에서 2-염화안트라센 술포닐의 가용매 분해반응을 전기전도도법을 써서 속도론적으로 고찰하였다. 물의 몰분률이 같은 혼합용매속에서는 쌍극자성 반양성자 용매에서 보다 양성자성 용매에서 속도가 컸으며, 물-메탄올 혼합용매에서는 실험 농도의 전체 범위에 걸쳐 물-에탄올에서 보다 항상 속도가 컸으나 아세톤과 아세토니트링의 경우에는 몰분율 0.9에서 속도의 크기가 뒤바뀌었다. 용매의 이온화 능력에 대한 반응의 감도를 나타내는 m와 전이상태에서의 물의 관여차수 n값은 모두 쌍극자성 반양성자용매에서 컸다. 이들 값과, 속도상수에서 결정한 활성화 파라미터로부터 2-염화안트라센 술포닐의 가용매분해반응은$ S_N2$ 메카니즘으로 진행된다는 것을 알았다.

Keywords

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