Organic sulfur mechanisms. 24. Preparation and reactions of 2-hydroxyethanesulfonyl chloride, the first hydroxyalkanesulfonyl chloride
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Published:1983-07-01
Issue:7
Volume:61
Page:1583-1593
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ISSN:0008-4042
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Container-title:Canadian Journal of Chemistry
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language:en
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Short-container-title:Can. J. Chem.
Author:
King James Frederick,Hillhouse John Henry
Abstract
2-Hydroxyethanesulfonyl chloride (1a) is readily made by reaction of an aqueous solution of 2-mercaptoethanol (4a) with chlorine. This is the first clearly proved preparation of a compound which is both an alcohol and a sulfonyl chloride. Reactions of 1a with water and alcohols evidently proceed largely by intramolecular cyclization to the transient β-sultone (2a), which then undergoes nuclcophilic ring opening to form the products. In the presence of tertiary amines a minor but significant part of the reaction is shown by deuterium labelling to proceed via hydroxymethylsulfene (14). the principal reaction of which is simply to add the alcohol or water; only a small part, if any, of the sulfene (14) loses the hydroxy¡ group to give the ethenesulfonate derivatives (13 or 22). Aqueous chlorination of 3-mercapto-1-propanol gave 3-chloro-1-propanesulfonyl chloride (5a) and 1,3-propane sultone (2b) with no sign of any 3-hydroxy-1-propanesulfonyl chloride (1b). A mechanism for the aqueous chlorination process invoking a cyclic chlorooxasulfoxoniuin ion (27) is discussed.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
18 articles.
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