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dc.contributor.author엄익환-
dc.date.accessioned2017-12-27T16:31:13Z-
dc.date.available2017-12-27T16:31:13Z-
dc.date.issued2017-
dc.identifier.issn0253-2964-
dc.identifier.otherOAK-21370-
dc.identifier.urihttps://dspace.ewha.ac.kr/handle/2015.oak/239442-
dc.description.abstractSecond-order rate constants (kquin) for reactions of O-3,4-dinitrophenyl O-phenyl thionocarbonate (2a) with a series of quinuclidine derivatives and for those of O-phenyl O-Y-substituted-phenyl thionocarbonates (2a–2h) with quinuclidine in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1°C are reported. Comparison of the kquin values in this study with those reported previously for the corresponding reactions of O-3,4-dinitrophenyl thionobenzoate (1a) and O-Y-substituted-phenyl thionobenzoates (1a–1j) has revealed that 2a is more reactive than 1a toward all the quinuclidine derivatives studied, while the thionocarbonate esters possessing a weak electron-withdrawing group in the leaving group (e.g., 2g and 2h) are less reactive than the corresponding thionobenzoate esters (e.g., 1g and 1h) toward quinuclidine. The Brønsted-type plots for the reactions of 2a with quinuclidine derivatives and for those of 2a–2h with quinuclidine are linear with βnuc = 0.67 and βlg = −0.85, respectively, indicating that the reactions proceed through a concerted mechanism with a loose transition state (TS). This is in contrast to the report that the corresponding reactions of 1a–1j proceed through a forced concerted mechanism with a tight TS on the basis of the linear Brønsted-type plots with βnuc = 0.89 and βlg = −0.37. Factors that control the reactivity of these esters toward quinuclidine are discussed in detail. © 2017 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim-
dc.languageEnglish-
dc.publisherWiley Blackwell-
dc.subjectBrønsted-type plot-
dc.subjectConcerted mechanism-
dc.subjectO-Phenyl O-Y-substituted-phenyl thionocarbonates-
dc.subjectQuinuclidinolysis-
dc.subjectSteric hindrance-
dc.titleKinetic Study on Quinuclidinolysis of O-Phenyl O-Y-substituted-Phenyl Thionocarbonates: Effects of Changing Nonleaving Group from Thionobenzoyl to Phenyloxythionocarbonyl on Reactivity and Transition-State Structure-
dc.typeArticle-
dc.relation.issue9-
dc.relation.volume38-
dc.relation.indexSCOPUS-
dc.relation.indexKCI-
dc.relation.startpage1091-
dc.relation.lastpage1096-
dc.relation.journaltitleBulletin of the Korean Chemical Society-
dc.identifier.doi10.1002/bkcs.11227-
dc.identifier.wosidWOS:000412554000019-
dc.identifier.scopusid2-s2.0-85027967464-
dc.author.googleKoh H.-J.-
dc.author.googleUm I.-H.-
dc.contributor.scopusid엄익환(7006725706;6506759437)-
dc.date.modifydate20180104081001-
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자연과학대학 > 화학·나노과학전공 > Journal papers
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