The Through-Bond Interaction of a Sulfur Lone Pair with Oxygenated Substituents in the Thiacyclohexane Framework

Laura Andrau; Jonathan M. White

doi:10.1071/CH05073

RESEARCH ARTICLE

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The Through-Bond Interaction of a Sulfur Lone Pair with Oxygenated Substituents in the Thiacyclohexane Framework

Laura Andrau ^A and Jonathan M. White ^A ^B

+ Author Affiliations

- Author Affiliations

^A School of Chemistry, University of Melbourne, Parkville VIC 3010, Australia.

^B Corresponding author. Email: whitejm@unimelb.edu.au

Australian Journal of Chemistry 58(7) 531-534 https://doi.org/10.1071/CH05073
Submitted: 11 March 2005 Accepted: 21 April 2005 Published: 21 July 2005

Abstract

Low-temperature X-ray crystal structures were determined on a range of derivatives of 4-thiacyclohexanol 5a of varying electron demand with a view to finding evidence for a through-bond interaction between the sulfur lone pair and the oxygenated substituent. In contrast to earlier suggestions, plots of C–OR bond distance versus pK_a (ROH) showed that any interaction between the sulfur and the OR group is unlikely to be of a through-bond origin. Furthermore, unimolecular solvolysis rate measurements on the nosylate ester derivative 5g showed that the sulfur actually retards the reaction slightly in comparison with the corresponding sulfur-free analogue 6.

References

The Through-Bond Interaction of a Sulfur Lone Pair with Oxygenated Substituents in the Thiacyclohexane Framework

Abstract

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