Axial:Equatorial Rate Ratios and the Mechanism of Formation of Sulfenes by Dehydrohalogenation of Alkanesulfonyl Chlorides

The method of axial:equatorial rate ratios has been applied to the study of the mechanism of formation of sulfenes via the reaction of alkanesulfonyl chlorides with base. The axial trans-2-decalinsulfonyl chloride ( 6 ) and the equatorial trans-2-decalinsulfonyl chloride ( 8 ) were synthesized. The...

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Bibliographic Details
Published in:Canadian journal of chemistry 1971-11, Vol.49 (22), p.3724-3732
Main Authors: King, J. F, Lee, T. W. S
Format: Article
Language:English
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Summary:The method of axial:equatorial rate ratios has been applied to the study of the mechanism of formation of sulfenes via the reaction of alkanesulfonyl chlorides with base. The axial trans-2-decalinsulfonyl chloride ( 6 ) and the equatorial trans-2-decalinsulfonyl chloride ( 8 ) were synthesized. The axial sulfonyl chloride 6 was found to react 71 times faster than the equatorial epimer 8 with triethylamine in the presence of aniline at −25°, a reaction which evidently proceeds via the sulfene 7 . With water at 50° without added base (a reaction believed to take place by direct attack on the sulfur atom) 8 reacts about 14 times faster than 6 . It is concluded that the formation of the sulfene 7 from 6 by the action of triethylamine cannot take place by a mechanism involving a slow S N 2 reaction followed by a fast bimolecular elimination, and that the most likely route for 6 , and other alkanesulfonyl chlorides as well, is the E2 reaction.
ISSN:0008-4042
1480-3291
DOI:10.1139/v71-620