Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T10:08:26Z | - |
dc.date.available | 2016-08-28T10:08:26Z | - |
dc.date.issued | 2012 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.other | OAK-8978 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/222815 | - |
dc.description.abstract | A kinetic study is reported for aminolysis of 4-pyridyl X-substituted-benzoates 5a-i. Plots of pseudo-first-order rate constants (k obsd) vs [amine] curve upward for the reactions of substrates possessing a strong electron-withdrawing group in the benzoyl moiety (5a-d) but are linear for the reactions of those bearing an electron-donating group (5e-i), indicating that the electronic nature of substituent X governs the reaction mechanism. The k 1k 2/k -1 and k 1k 3/k -1 values were calculated from the intercept and slope of the linear plots of k obsd/[amine] vs [amine], respectively. The Hammett plot for k 1k 2/k -1 consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ρ X = 0.41 and r = 1.58, implying that the nonlinear Hammett plot is not due to a change in rate-determining step but is caused by stabilization of substrates possessing an electron-donating group through resonance interactions. The small ρ X suggests that the k 2/k -1 ratio is little influenced by the nature of substituent X. The Brønsted-type plots for aminolysis of 4-pyridyl 3,5-dinitrobenzoate 5a are linear with β nuc = 0.98 and 0.79 for k 1k 2/k -1 and k 1k 3/k -1, respectively. The effect of amine basicity on the microscopic rate constants is also discussed. © 2012 American Chemical Society. | - |
dc.language | English | - |
dc.title | Electronic nature of substituent X governs reaction mechanism in aminolysis of 4-pyridyl X-substituted-benzoates in acetonitrile | - |
dc.type | Article | - |
dc.relation.issue | 13 | - |
dc.relation.volume | 77 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 5781 | - |
dc.relation.lastpage | 5787 | - |
dc.relation.journaltitle | Journal of Organic Chemistry | - |
dc.identifier.doi | 10.1021/jo300961y | - |
dc.identifier.wosid | WOS:000306049900034 | - |
dc.identifier.scopusid | 2-s2.0-84863615343 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Bae A.R. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |