Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism

Jin Burm Kyong, Yelin Lee, Malcolm John D'Souza, Brian Patrick Mahon, Dennis Neil Kevill

Abstract


The “parent” tertiary alkyl chloroformate, tert-butyl chloroformate, is unstable, but the tert-butyl chlorothioformate (1) is of increased stability and a kinetic investigation of the solvolyses is presented. Analyses in terms of simple and extended Grunwald-Winstein equations are carried out. The original one-term equation satisfactorily correlates the data with 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.

3_3_267_272_800


Keyword(s)


Solvolysis; Ionization; Addition-elimination; Activation parameters; tert-Butyl chlorothioformate; Grunwald-Winstein equations

European Journal of Chemistry, 3 (3), (2012), 267-272

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DOI: http://dx.doi.org/10.5155/eurjchem.3.3.267-272.624