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dc.contributor.author엄익환-
dc.date.accessioned2016-08-28T12:08:56Z-
dc.date.available2016-08-28T12:08:56Z-
dc.date.issued2008-
dc.identifier.issn0253-2964-
dc.identifier.otherOAK-4759-
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/219991-
dc.description.abstractSecond-order rate constants (kN) have been measured spectrophotometrically for reactions of Y-substituted phenyl benzoates (1a-h) with azide ion (N3-) in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The Brønsted-type plot for the azidolysis exhibits a downward curvature, i.e., the slope (βlg) changes from -0.97 to -0.20 as the basicity of the leaving group decreases. The pKao (defined as the pKa at the center of the Brønsted curvature) is 4.8, which is practically identical to the pK a of the conjugate acid of N3- ion (4.73). Hammett plots correlated with σo and σ- constants exhibit highly scattered points for the azidolysis. On the contrary, the corresponding Yukawa-Tsuno plot results in an excellent linear correlation with ρ = 2.45 and r = 0.40, indicating that the leaving group departs in the rate-determining step. The curved Brønsted-type plot has been interpreted as a change in the rate-determining step in a stepwise mechanism. The microscopic rate constants (k1 and k2/k-1 ratio) have been calculated for the azidolysis and found to be consistent with the proposed mechanism.-
dc.languageEnglish-
dc.titleKinetics and mechanism of azidolysis of Y-substituted phenyl benzoates-
dc.typeArticle-
dc.relation.issue3-
dc.relation.volume29-
dc.relation.indexSCI-
dc.relation.indexSCIE-
dc.relation.indexSCOPUS-
dc.relation.indexKCI-
dc.relation.startpage580-
dc.relation.lastpage584-
dc.relation.journaltitleBulletin of the Korean Chemical Society-
dc.identifier.wosidWOS:000255229900012-
dc.identifier.scopusid2-s2.0-41549159297-
dc.author.googleUm I.-H.-
dc.author.googleKim E.-H.-
dc.author.googleHan H.J.-
dc.contributor.scopusid엄익환(7006725706;6506759437)-
dc.date.modifydate20230411105538-
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자연과학대학 > 화학·나노과학전공 > Journal papers
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