Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2017-12-27T16:31:13Z | - |
dc.date.available | 2017-12-27T16:31:13Z | - |
dc.date.issued | 2017 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.other | OAK-21370 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/239442 | - |
dc.description.abstract | Second-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.language | English | - |
dc.publisher | Wiley Blackwell | - |
dc.subject | Brønsted-type plot | - |
dc.subject | Concerted mechanism | - |
dc.subject | O-Phenyl O-Y-substituted-phenyl thionocarbonates | - |
dc.subject | Quinuclidinolysis | - |
dc.subject | Steric hindrance | - |
dc.title | Kinetic 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.type | Article | - |
dc.relation.issue | 9 | - |
dc.relation.volume | 38 | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 1091 | - |
dc.relation.lastpage | 1096 | - |
dc.relation.journaltitle | Bulletin of the Korean Chemical Society | - |
dc.identifier.doi | 10.1002/bkcs.11227 | - |
dc.identifier.wosid | WOS:000412554000019 | - |
dc.identifier.scopusid | 2-s2.0-85027967464 | - |
dc.author.google | Koh H.-J. | - |
dc.author.google | Um I.-H. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |