Nucleofugality effects in the pyridine promoted formation of esters from 2-substituted ethanesulfonyl chlorides
| Autor: | John Henry Hillhouse, Kishan Chand Khemani, James Frederick King, Toyanne Marie Lauriston |
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| Rok vydání: | 1988 |
| Předmět: | |
| Zdroj: | Canadian Journal of Chemistry. 66:1109-1116 |
| ISSN: | 1480-3291 0008-4042 |
| DOI: | 10.1139/v88-182 |
| Popis: | The products of reaction of a series of 10 2-substituted ethanesulfonyl chlorides, X—CH2CH2SO2Cl (1), with neopentyl alcohol and pyridine-d5 in nitromethane-d3 showed three reaction pathways depending on the nucleofugality of the substituent, X. These routes lead, respectively, to (i) the corresponding neopentyl ester (4), via the sulfene (3) (low substituent nucleofugality); (ii) a mixture of ester 4 and neopentyl ethenesulfonate (5), by the same route except for a partial loss of the 2-substituent during trapping of the sulfene (3) (intermediate nucleofugality); and (iii) a mixture of the ethenesulfonate (5) and the pyridino-betylate (4g) esters, arising from initial elimination of HX to form ethenesulfonyl chloride (2) followed by its further reaction (high substituent nucleofugality). A set of nucleofugality values closely related to, and partly complementing, those derived by Stirling and co-workers can be estimated from the product ratios in those reactions proceeding (at least in part) by route (ii) above. Old reports of anomalous products from 1,2-ethanedisulfonyl chloride (1i) and 2-chloroethanesulfonyl chloride (1j) are simply accounted for on the basis of the initial conversion to ethenesulfonyl chloride (2). |
| Databáze: | OpenAIRE |
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