{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T01:40:16Z","timestamp":1760319616412,"version":"build-2065373602"},"reference-count":71,"publisher":"Wiley","issue":"10","license":[{"start":{"date-parts":[[2011,2,2]],"date-time":"2011-02-02T00:00:00Z","timestamp":1296604800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2011,3]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Pseudo\u2010first\u2010order rate constants (<jats:italic>k<\/jats:italic><jats:sub>obsd<\/jats:sub>) for reactions of 4\u2010nitrophenyl salicylate (<jats:bold>7<\/jats:bold>) with alkali metal ethoxides (EtOM, M=K, Na, and Li) in anhydrous ethanol have been measured spectrophotometrically. Interestingly, the <jats:italic>k<\/jats:italic><jats:sub>obsd<\/jats:sub> value decreases significantly as the concentration of EtOM increases. Because the phenolic moiety of substrate <jats:bold>7<\/jats:bold> would be deprotonated and exist as an anionic form (i.e., <jats:bold>7<\/jats:bold><jats:sup>\u2212<\/jats:sup>) under kinetic conditions, the ground\u2010state stabilization of <jats:bold>7<\/jats:bold><jats:sup>\u2212<\/jats:sup> through formation of a six\u2010membered cyclic complex with M<jats:sup>+<\/jats:sup> (i.e., <jats:bold>8<\/jats:bold>) is proposed to be responsible for the decreasing <jats:italic>k<\/jats:italic><jats:sub>obsd<\/jats:sub> trend. The <jats:italic>k<\/jats:italic><jats:sub>obsd<\/jats:sub> value at a given concentration of EtOK increases steeply upon addition of [18]crown\u20106 ether (18C6) up to [18C6]\/[EtOK]=1 in the reaction mixture and then remains relatively constant thereafter. In contrast, <jats:italic>k<\/jats:italic><jats:sub>obsd<\/jats:sub> decreases upon addition of salts (e.g., LiClO<jats:sub>4<\/jats:sub> or KSCN) to the reaction mixture, which indicates that M<jats:sup>+<\/jats:sup> ions inhibit the reaction. However, in the presence of 18C6, the <jats:italic>k<\/jats:italic><jats:sub>obsd<\/jats:sub> value is independent of the concentration of EtOK but remains constant, which indicates that the reaction proceeds through a unimolecular mechanism in the presence of the complexing agent. Although two conceivable unimolecular pathways (formation of ketene <jats:bold>9<\/jats:bold> and lactone <jats:bold>10<\/jats:bold>) can account for the kinetic results, the reaction has been concluded to proceed via formation of ketene <jats:bold>9<\/jats:bold> as the reactive intermediate on the basis of theoretical calculations.<\/jats:p>","DOI":"10.1002\/chem.201002692","type":"journal-article","created":{"date-parts":[[2011,2,2]],"date-time":"2011-02-02T03:43:04Z","timestamp":1296618184000},"page":"3021-3027","source":"Crossref","is-referenced-by-count":11,"title":["Kinetic and Theoretical Studies on Alkaline Ethanolysis of 4\u2010Nitrophenyl Salicylate: Effect of Alkali Metal Ions on Reactivity and Mechanism"],"prefix":"10.1002","volume":"17","author":[{"given":"Ik\u2010Hwan","family":"Um","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jin\u2010A","family":"Seo","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Masaaki","family":"Mishima","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2011,2,2]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"volume-title":"Enzyme Structure and Mechanism","year":"1985","author":"Fersht A.","key":"e_1_2_6_2_2"},{"volume-title":"Biochemistry","year":"1988","author":"Stryer L.","key":"e_1_2_6_3_2"},{"volume-title":"The Biological Chemistry of the Elements","year":"1991","author":"Silva J. 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