Organic sulfur mechanisms. 24. Preparation and reactions of 2-hydroxyethanesulfonyl chloride, the first hydroxyalkanesulfonyl chloride
| Autor: | James Frederick King, John Henry Hillhouse |
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| Rok vydání: | 1983 |
| Předmět: | |
| Zdroj: | Canadian Journal of Chemistry. 61:1583-1593 |
| ISSN: | 1480-3291 0008-4042 |
| DOI: | 10.1139/v83-275 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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