Stoichiometric Solvation Effects. Solvolysis of Trifluoromethanesulfonyl Chloride

Bulletin of the Korean chemical society

In Sun Koo¹  Jun Mi Cho¹  Ikchoon Lee¹  Jong Kuen Park¹  Mi Young Woo¹  Kiyull Yang¹  Jong Pal Lee¹ 

关键词: Dispersion;    Stoichiometric solvation effects;    Kinetic solvent isotopic effects;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

Solvolyses of trifluoromethanesulfonyl chloride (TFMSC) in water and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25, 35 and 45 ^oC. The Grunwald-Winstein plot of first-order rate constants for the solvolytic reaction of TFMSC with Y_Cl (based on 2-adamantyl chloride) shows marked dispersions into three separate curves for three aqueous mixtures. The extended Grunwald-Winstein plots for the solvolysis of TFMSC show better correlation. The large negative ツS^× and relatively small positive ツH^× reveals that the solvolytic reaction proceeds via a typical bimolecular reaction mechanism. The l and m values determined in various solvents are consistent with the proposed mechanism of the general base catalysis S_AN/ S_N2 reaction mechanism for TFMSC solvolyses based on mass law and stoichiometric solvation effect studies.

【 授权许可】

Unknown