Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Kinetic Study on Nucleophilic Substitution of 1-Anthracenesulfonyl Chloride with Anilines

1-염화안트라센 술포닐의 치환아닐린과의 친핵성치환반응의 속도론적 연구

  • Kim Hyong Tae (Department of the Chemical Education, Busan National University) ;
  • Yoh Soo Dong (Department of Chemical Education, Kyungpook National University)
  • 김형태 (부산대학교 사범대학 화학교육과) ;
  • 여수동 (경북대학교 사범대학 화학교육과)
  • Published : 1985.04.20
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Abstract

1-Anthracenesulfonyl chloride used as a substrate has been prepared from anthra-quinone, and its melting point ($124^{circ}C$) was confirmed to be considerably different from the literature value ($90^{circ}C$). Rates of nucleophilic substitution reactions of this substrate with some p-substituted anilines in dry acetone were determined by electroconductometric method, and their mechanism has been discussed. As a result, it has been found that these reactions proceed in parallel catalyzed by anilines together with noncatalyzed process, and that their catalytic activities are electrophilic. Judging from $Br{\phi}nsted\;{\beta}$ (0.77), Hammett ${\rho}$(-3.2), and activation parameters which were determined from the temperature dependence of noncatalyzed second order rate constants, it appears most appropriate that their mechanism should be discussed in terms of an associative $S_N2$ involving sulfonylammonium intermediate.

기질로 사용한 1-염화안트라센 술포닐(융점$124^{circ}C$)을 안트라키논으로 부터 합성하여 확인한 결과, 그 융점이 문헌치($90^{circ}C$)와 상당한 차이를 나타내었다. 이 기질과 치환아닐린이 무수 아세톤 속에서 일어나는 친핵성 치환반응의 메카니즘을 전기전도도법을 써서 속도론적으로 고찰하였다. 이 반응은 무촉매 과정과 아닐린류에 의한 촉매 과정이 병행하여 일어나며 촉매작용은 친전자적임을 알았다. $Br{\phi}nsted\;{\beta}$ (0.77), Hammett ${\rho}$(-3.2) 및 무촉매반응 속도상수의 온도 의존성에서 결정한 활성화 파라미터로 부터 이 반응은 술포닐암모늄 중간체를 거치는 associative $S_N2$로 논의하는 것이 가장 적절하였다.

Keywords

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