The Mechanism for Hydrolysis of Primary Alkyl Chlorosulfates in Water. The Kinetic Solvent Isotope Effect and the Secondary Deuterium Isotope Effect

Autor:	R. E. Robertson, E. C. F. Ko
Rok vydání:	1972
Předmět:	chemistry.chemical_classification Primary (chemistry) Organic Chemistry Inorganic chemistry Enthalpy General Chemistry Kinetic energy Catalysis Solvent Hydrolysis chemistry Deuterium Kinetic isotope effect Alkyl
Zdroj:	Canadian Journal of Chemistry. 50:434-437
ISSN:	1480-3291 0008-4042
DOI:	10.1139/v72-063
Popis:	The temperature coefficients of the enthalpy of activation [Formula: see text] for the hydrolysis of the three chlorosulfates, methyl, ethyl, and β-chloro, are shown to have values of −50,−55, and −60 cal deg−1 mol−1; values in the same range as previously reported for the hydrolysis of the sulfonyl chlorides. The corresponding value for the β-methoxy isomer was −40 cal deg−1 mol−1, about the same as found for the p-methoxybenzenesulfonyl chloride. The kinetic solvent isotope effect, however, was significantly lower than reported for the sulfonyl chloride series, being about the same as found for the hydrolysis of the alkyl halides. While some degree of nucleophilic overlap is probably required in the activation process, the requirement here is reduced to about the same level as that for the primary halides, and there is no need to postulate a different mechanism on passing from the methyl to the ethyl member of the series, confirming the earlier conclusion of Buncel and Millington.
Databáze:	OpenAIRE
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