Nucleophilic Displacement of Sulfur Center, Part Ⅵ - Halide Exchange Kinetics of Methanesulfonyl Chloride in Acetone, Acetonirile and Methanol

The rates and activation parameters for the halide exchange reactions of methanesulfonyl chloride in dry acetone, acetonitrile, and methanol have been determined. It was found that nucleophilic order is Cl->Br->I-. The rate of chloride exchange with methanesulfonyl chloride decreases in the order of solvent; ($CH_3$)$_2$CO>$CH_3$CN》MeOH. Results are intrpreted in terms of easiness of the initial state desolvation and solvation stabilization of the transition state.

염화 메탄 슬포닐의 할로겐 교환반응을 무수아세톤, 아세토니트릴, 메타놀 용매중에서 행하여 반응속도상수와 활성화파라메터를 구하였다. 친핵성도는 Cl->Br>I- 순서로 감소하였으며, 용매변화에 따른 염소이온과의 반응 속도는 ($CH_3$)$_2$CO>$CH_3$CN》$CH_3$OH의 순서로 감소하였다. 실험결과를 초기상태 탈용매화의 용이함과 천이상태 용매화의 안정성으로 설명하였다.