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Keywords = 4-chlorobutyl chloroformate

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12 pages, 2708 KB  
Article
The Influence of a Terminal Chlorine Substituent on the Kinetics and the Mechanism of the Solvolyses of n-Alkyl Chloroformates in Hydroxylic Solvents
by Malcolm J. D’Souza, Jeremy Wirick, Osama Mahmoud, Dennis N. Kevill and Jin Burm Kyong
Int. J. Mol. Sci. 2020, 21(12), 4387; https://doi.org/10.3390/ijms21124387 - 19 Jun 2020
Cited by 1 | Viewed by 5327
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Solution Chemical Kinetics 2.0)
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