International Journal of Molecular Sciences | |
Influence of Sulfur for Oxygen Substitution in the Solvolytic Reactions of Chloroformate Esters and Related Compounds | |
Malcolm J. D’Souza2  Dennis N. Kevill1  | |
[1] Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115-2862, USA;Department of Chemistry, Wesley College, 120 N. State Street, Dover, DE 19901-3875, USA | |
关键词: chloroformate; chlorothioformate; chlorothionoformate; chlorodithioformate; carbamoyl chloride; thiocarbamoyl chloride; Grunwald-Winstein equation; addition-elimination; ionization; | |
DOI : 10.3390/ijms151018310 | |
来源: mdpi | |
【 摘 要 】
The replacement of oxygen within a chloroformate ester (ROCOCl) by sulfur can lead to a chlorothioformate (RSCOCl), a chlorothionoformate (ROCSCl), or a chlorodithioformate (RSCSCl). Phenyl chloroformate (PhOCOCl) reacts over the full range of solvents usually included in Grunwald-Winstein equation studies of solvolysis by an addition-elimination (A-E) pathway. At the other extreme, phenyl chlorodithioformate (PhSCSCl) reacts across the range by an ionization pathway. The phenyl chlorothioformate (PhSCOCl) and phenyl chlorothionoformate (PhOCSCl) react at remarkably similar rates in a given solvent and there is a dichotomy of behavior with the A-E pathway favored in solvents such as ethanol-water and the ionization mechanism favored in aqueous solvents rich in fluoroalcohol. Alkyl esters behave similarly but with increased tendency to ionization as the alkyl group goes from 1° to 2° to 3°.
【 授权许可】
CC BY
© 2014 by the authors; licensee MDPI, Basel, Switzerland.
【 预 览 】
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