Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T11:08:16Z | - |
dc.date.available | 2016-08-28T11:08:16Z | - |
dc.date.issued | 1999 | - |
dc.identifier.issn | 0008-4042 | - |
dc.identifier.other | OAK-261 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/218540 | - |
dc.description.abstract | Apparent second-order rate constants (k(app)) have been measured spectrophotometrically for the reaction of 2,4-dinitrophenyl X-substituted benzoates with a series of alicyclic secondary amines in H2O containing 20 mol% DMSO at 25°C. The microconstants involved in the reaction (k-1/k2, k1, and k1k2/k-1) have also been calculated. The magnitude of k(app), k1, and k1k2/k-1 values increases with increasing amine basicity and with increasing acid strengthening ability of the acyl substituent X. The k-1/k2 value decreases from ca. 6.5 to 0.3 with increasing the amine basicity, but remains almost constant upon changing the acyl substituent X for a given amine, indicating that the rate-determining step is governed by the basicity of amine but not by the electronic nature of the acyl substituent X. The Bronsted-type plots for k(app) show a break at pK(a) = 9.1, supporting the assumption that a change in the rate-determining step occurs from rate-limiting breakdown to formation of the addition intermediate as amine basicity increases. The corresponding Bronsted-type plots for k-1/k2, k1, and k1k2/k-1 are linear but their β values are different. σ constants show better correlation with log k(app), log k1 and log k1k2/k-1 for the reaction with low basic amines (pK(a) < 9.1), while σ constants exhibit better correlation for the reaction with highly basic amines (pK(a) > 9.1). The magnitude of ρ1 is identical to that of ρ(app) and ρ(eq) for a given amine. | - |
dc.language | English | - |
dc.title | Structure-reactivity correlations in the reaction of 2,4-dinitrophenyl X-substituted benzoates with alicyclic secondary amines | - |
dc.type | Article | - |
dc.relation.issue | 5-6 | - |
dc.relation.volume | 77 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 659 | - |
dc.relation.lastpage | 666 | - |
dc.relation.journaltitle | Canadian Journal of Chemistry | - |
dc.identifier.wosid | WOS:000081612600020 | - |
dc.identifier.scopusid | 2-s2.0-0033306509 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Min J.-S. | - |
dc.author.google | Lee H.-W. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |