Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T11:08:53Z | - |
dc.date.available | 2016-08-28T11:08:53Z | - |
dc.date.issued | 2005 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.other | OAK-2780 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/219579 | - |
dc.description.abstract | Second-order rate constants have been determined spectrophotometrically for the reactions of 4-nitrophenyl X-substituted 2-methylbenzoates (2a-e) and Y-substituted phenyl 2-methylbenzoates (3a-e) with alicyclic secondary amines in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The o-methyl group in the benzoyl moiety of 2a-e retards the reaction rate but does not influence the reaction mechanism. The Hammett plots for the reactions of 2a-e are nonlinear, while the corresponding Yukawa-Tsuno plots are linear with large r values (1.06-1.70). The linear Yukawa-Tsuno plots suggest that stabilization of the ground-state through resonance interaction between the electron donating substituent X and the carbonyl group is responsible for the nonlinear Hammett plots, while the large r values imply that the ground-state resonance interaction is significant. The reactions of 2a-e resulted in smaller ρX values but larger r values than the corresponding reactions of 4-nitrophenyl X-substituted benzoates (1a-e). The small ρX value for the reactions of 2a-e (e.g., ρX = 0.22) is suggested to be responsible for the large r value (e.g., r = 1.70). The reactions of 3a-e with piperidine are proposed to proceed in a stepwise manner with a change in the rate-determining step on the basis of the curved Brønsted-type plot obtained. Microscopic rate constants associated with the reactions of 3a-e are also consistent with the proposed mechanism. © 2005 American Chemical Society. | - |
dc.language | English | - |
dc.title | Effect of o-methyl group on rate, mechanism, and resonance contribution: Aminolysis of Y-substituted phenyl X-substituted 2-methylbenzoates | - |
dc.type | Article | - |
dc.relation.issue | 13 | - |
dc.relation.volume | 70 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 4980 | - |
dc.relation.lastpage | 4987 | - |
dc.relation.journaltitle | Journal of Organic Chemistry | - |
dc.identifier.doi | 10.1021/jo050172k | - |
dc.identifier.wosid | WOS:000229982900009 | - |
dc.identifier.scopusid | 2-s2.0-20844448745 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Lee J.-Y. | - |
dc.author.google | Lee H.W. | - |
dc.author.google | Nagano Y. | - |
dc.author.google | Fujio M. | - |
dc.author.google | Tsuno Y. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |