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dc.contributor.author엄익환-
dc.date.accessioned2016-08-28T12:08:51Z-
dc.date.available2016-08-28T12:08:51Z-
dc.date.issued2010-
dc.identifier.issn0253-2964-
dc.identifier.otherOAK-7038-
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/221153-
dc.description.abstractSecond-order rate constants (k N) have been measured spectrophotometrically for reactions of 2,4-dinitrophenyl X-substituted benzoates (X = 4-MeO, H and 4-NO 2) with a series of Z-substituted pyridines in 80 mol % H 2O/20 mol % DMSO at 25.0 ± 0.1 °C. The Brønsted-type plots exhibit downward curvature (e.g., β 2 = 0.89 ∼ 0.96 when pK a < 9.5 while β 1 = 0.38 ∼ 0.46 when pK a > 9.5), indicating that the reaction proceeds through a stepwise mechanism with a change in rate-determining step (RDS). The pK a°, defined as the pK a at the center of Brønsted curvature, has been analyzed to be 9.5 regardless of the electronic nature of the substituent X in the benzoyl moiety. Dissection of k N into the microscopic rate constants k 1 and k 2/k -1ratio has revealed that k 1 is governed by the electronic nature of the substituent X but the k 2/k -1 ratio is not. Theoretical calculations also support the argument that the electronic nature of the substituent X in the benzoyl moiety does not influence the k 2/k -1 ratio.-
dc.languageEnglish-
dc.titleKinetic and theoretical studies on pyridinolysis of 2,4-dinitrophenyl X-substituted benzoates: Effect of substituent X on reactivity and mechanism-
dc.typeArticle-
dc.relation.issue9-
dc.relation.volume31-
dc.relation.indexSCIE-
dc.relation.indexSCOPUS-
dc.relation.indexKCI-
dc.relation.startpage2593-
dc.relation.lastpage2597-
dc.relation.journaltitleBulletin of the Korean Chemical Society-
dc.identifier.doi10.5012/bkcs.2010.31.9.2593-
dc.identifier.wosidWOS:000283953600030-
dc.identifier.scopusid2-s2.0-77957095623-
dc.author.googleUm I.-H.-
dc.author.googleKim E.-H.-
dc.author.googleIm L.-R.-
dc.author.googleMishima M.-
dc.contributor.scopusid엄익환(7006725706;6506759437)-
dc.date.modifydate20170601135413-
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자연과학대학 > 화학·나노과학전공 > Journal papers
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