The Influence of a Terminal Chlorine Substituent on the Kinetics and the Mechanism of the Solvolyses of n-Alkyl Chloroformates in Hydroxylic Solvents
Author ORCID Identifier
Dennis Kevill:https://orcid.org/0000-0002-1921-7184
Publication Title
International Journal of Molecular Sciences
ISSN
16616596
E-ISSN
44001
Document Type
Article
Abstract
A previous study of the effect of a 2-chloro substituent on the rates and the mechanisms of the solvolysis of ethyl chloroformate is extended to the effect of a 3-chloro substituent on the previously studied solvolysis of propyl chloroformate and to the effect of a 4-chloro substituent on the here reported rates of solvolysis of butyl chloroformate. In each comparison, the influence of the chloro substituent is shown to be nicely consistent with the proposal, largely based on the application of the extended Grunwald–Winstein equation, of an addition-elimination mechanism for solvolysis in the solvents of only modest solvent ionizing power, which changes over to an ionization mechanism for solvents of relatively high ionizing power and low nucleophilicity, such as aqueous fluoroalcohols with an appreciable fluoroalcohol content.
First Page
1
Last Page
12
Publication Date
6-1-2020
DOI
10.3390/ijms21124387
PubMed ID
32575637
Keywords
3-chloropropyl chloroformate, 4- chlorobutyl chloroformate, Addition-elimination, Butyl chloroformate, Grunwald–Winstein equation, Ionization, Propyl chloroformate, Solvolysis
Recommended Citation
D’souza, Malcom J.; Wirick, Jeremy; Mahmoud, Osama; Kevill, Dennis N.; and Kyong, Jin Burm, "The Influence of a Terminal Chlorine Substituent on the Kinetics and the Mechanism of the Solvolyses of n-Alkyl Chloroformates in Hydroxylic Solvents" (2020). NIU Bibliography. 499.
https://huskiecommons.lib.niu.edu/niubib/499
Department
Department of Chemistry and Biochemistry