Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T12:08:51Z | - |
dc.date.available | 2016-08-28T12:08:51Z | - |
dc.date.issued | 2010 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.other | OAK-7038 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/221153 | - |
dc.description.abstract | Second-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.language | English | - |
dc.title | Kinetic and theoretical studies on pyridinolysis of 2,4-dinitrophenyl X-substituted benzoates: Effect of substituent X on reactivity and mechanism | - |
dc.type | Article | - |
dc.relation.issue | 9 | - |
dc.relation.volume | 31 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 2593 | - |
dc.relation.lastpage | 2597 | - |
dc.relation.journaltitle | Bulletin of the Korean Chemical Society | - |
dc.identifier.doi | 10.5012/bkcs.2010.31.9.2593 | - |
dc.identifier.wosid | WOS:000283953600030 | - |
dc.identifier.scopusid | 2-s2.0-77957095623 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Kim E.-H. | - |
dc.author.google | Im L.-R. | - |
dc.author.google | Mishima M. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |