Original scientific paper

Similarity Models for Solvation Effects on Reactivity. The Dissociative Reaction Channel for Solvolyses of Sulphonyl Chlorides in Binary Aqueous Mixtures

T. William Bentley ; Department of Chemistry, University College of Swansea, Singleton Park, Swansea SA2 8PP, Wales, U.K.
In Sun Koo ; Department of Chemistry, University College of Swansea, Singleton Park, Swansea SA2 8PP, Wales, U.K.
Gareth Llewellyn ; Department of Chemistry, University College of Swansea, Singleton Park, Swansea SA2 8PP, Wales, U.K.
Simon J. Norman ; Department of Chemistry, University College of Swansea, Singleton Park, Swansea SA2 8PP, Wales, U.K.

Abstract

Rate constants and product selectivities (S) are reported for solvolyses of pentamethylchroman and tri-isopropylbenzene sulphonyl chlorides in acetone/, ethanol/, and methanol/water mixtures, and rate constants for solvolyses of 1-adamantyl methanesulphonate are reported for aqueous binary mixtures with acetonitrile and dioxane. S values show maxima in plots versus % water in alcohol, consistent with the competing reaction channels discussed previously. YQMS derived from rate constants for solvolyses of 1-adam- antyl mesylate correlate with Grunwald-Winstein Y values; there is a small dispersion into separate correlation lines for the various binary mixtures, so the solvation requirements of the sulphonate group in these aqueous mixtures are similar to those for chloride.

Keywords

Hrčak ID:

137118

URI

https://hrcak.srce.hr/137118

Publication date:

15.10.1992.

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