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

Department

Department of Chemistry and Biochemistry

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