The 2-Oxocyclobutanecarboxylic Acid Keto−Enol System in Aqueous Solution: A Remarkable Acid-Strengthening Effect of the Cyclobutane Ring
| Autor: | Vladimir V. Popik, James R. Keeffe, Y. Chiang, A. J. Kresge, V. A. Nikolaev, J. A. Chang |
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| Rok vydání: | 2006 |
| Předmět: | |
| Zdroj: | The Journal of Organic Chemistry. 71:4460-4467 |
| ISSN: | 1520-6904 0022-3263 |
| DOI: | 10.1021/jo060253w |
| Popis: | Flash photolysis of 2-diazocyclopentane-1,3-dione in aqueous solution produced 2-oxocyclobutylideneketene, which underwent hydration to the enol of 2-oxocyclobutanecarboxylic acid; the enol then isomerized to the keto form of this acid. Rates of the ketene and enol reactions were measured in acid, base, and buffer solutions across the acidity range [H+] = 10(-1)-10(-13) M, and analysis of these data, together with rates of enolization of the keto form of 2-oxocyclobutanecarboxylic acid determined by bromine scavenging, gave keto-enol equilibrium constants as well as acidity constants of the keto and enol forms. The keto-enol equilibrum constants proved to be 2 orders of magnitude less than those reported previously for the next higher homolog, 2-oxocyclopentanecarboxylic acid, reflecting the difficulty of inserting a carbon-carbon double bond into a small, strained carbocyclic ring. The acidity constant of the enol group of 2-oxocyclobutanecarboxylate ion, on the other hand, is greater, by 4 orders of magnitude, than that of the corresponding enol in the cyclopentyl system. This remarkable increase in acidity with diminishing ring size is consistent with the enhanced s character of the orbitals used to make the exocyclic bonds of the smaller cyclobutane ring. |
| Databáze: | OpenAIRE |
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