title: Correlation of the rates of solvolysis oftert-butyl chlorothioformate and observations concerning the reaction mechanism.
abstract: The "parent" tertiary alkyl chloroformate,tert-butyl chloroformate, is unstable, but thetert-butyl chlorothioformate (1) is of increased stability and a kinetic investigation of the solvolyses is presented. Analyses in terms of the simple and extended Grunwald-Winstein equations are carried out. The original one-term equation satisfactorily correlates the data with a sensitivity towards changes in solvent ionizing power of 0.73 ±0.03. When the two-term equation is applied, the sensitivity towards changes in solvent nucleophilicity of 0.13 ± 0.09 is associated with a high (0.17) probability that the term that it governs is not statistically significant.
authors.affiliation: Department of Chemistry and Applied Chemistry, Hanyang University, Ansan-si, Gyeonggi-do 426-791, Korea.
authors.forename: Jin Burm
authors.initials: JB
authors.lastname: Kyong
authors.forename: Yelin
authors.initials: Y
authors.lastname: Lee
authors.forename: Malcolm John
authors.initials: MJ
authors.lastname: D'Souza
authors.forename: Dennis Neil
authors.initials: DN
authors.lastname: Kevill
authors.forename: Dennis Neil
authors.initials: DN
authors.lastname: Kevill
keywords: Activation parameters; Addition-elimination; Grunwald-Winstein equations; Ionization; Solvolysis; tert-Butyl chlorothioformate
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