European Journal of Chemistry 2012, 3(3), 267-272. doi:https://doi.org/10.5155/eurjchem.3.3.267-272.624

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


Jin Burm Kyong (1) , Yelin Lee (2) , Malcolm John D'Souza (3,*) , Brian Patrick Mahon (4) , Dennis Neil Kevill (5)

(1) Department of Chemistry and Applied Chemistry, Hanyang University, Ansan-si, Gyeonggi-Do, 426-791, Korea
(2) Department of Chemistry and Applied Chemistry, Hanyang University, Ansan-si, Gyeonggi-Do, 426-791, Korea
(3) Department of Chemistry, Wesley College, Dover, DE, 19901, USA
(4) Department of Chemistry, Wesley College, Dover, DE, 19901, USA
(5) Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, 60115, USA
(*) Corresponding Author

Received: 24 Apr 2012, Accepted: 19 May 2012, Published: 30 Sep 2012

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


Keywords


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

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DOI: 10.5155/eurjchem.3.3.267-272.624

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Citations

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[1]. Malcolm D'Souza, Dennis Kevill
Influence of Sulfur for Oxygen Substitution in the Solvolytic Reactions of Chloroformate Esters and Related Compounds
International Journal of Molecular Sciences  15(10), 18310, 2014
DOI: 10.3390/ijms151018310
/


[2]. Dennis Neil Kevill, Chang-Bae Kim, Malcolm John D’Souza
Correlation of the rates of solvolysis of α-bromoisobutyrophenone using both simple and extended forms of the Grunwald-Winstein equation and the application of correlation analysis to related studies
European Journal of Chemistry  9(1), 1, 2018
DOI: 10.5155/eurjchem.9.1.1-6.1680
/


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How to cite


Kyong, J.; Lee, Y.; D'Souza, M.; Mahon, B.; Kevill, D. Eur. J. Chem. 2012, 3(3), 267-272. doi:https://doi.org/10.5155/eurjchem.3.3.267-272.624
Kyong, J.; Lee, Y.; D'Souza, M.; Mahon, B.; Kevill, D. Eur. J. Chem. Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism. 2012, 3(3), 267-272. doi:https://doi.org/10.5155/eurjchem.3.3.267-272.624
Kyong, J., Lee, Y., D'Souza, M., Mahon, B., & Kevill, D. (2012). Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism. European Journal of Chemistry, 3(3), 267-272. doi:https://doi.org/10.5155/eurjchem.3.3.267-272.624
Kyong, Jin, Yelin Lee, Malcolm John D'Souza, Brian Patrick Mahon, & Dennis Neil Kevill. "Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism." European Journal of Chemistry [Online], 3.3 (2012): 267-272. Web. 18 Jun. 2018
Kyong, Jin, Lee, Yelin, D'Souza, Malcolm, Mahon, Brian, AND Kevill, Dennis. "Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism" European Journal of Chemistry [Online], Volume 3 Number 3 (30 September 2012)

DOI: https://doi.org/10.5155/eurjchem.3.3.267-272.624

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