Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T10:08:38Z | - |
dc.date.available | 2016-08-28T10:08:38Z | - |
dc.date.issued | 2013 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.other | OAK-9881 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223540 | - |
dc.description.abstract | Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Ysubstituted- phenyl carbonates 7a-g with butane-2,3-dione monoximate (Ox-) in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The α-nucleophile Ox- is 53-95 times more reactive than the corresponding normalnucleophile 4-ClPhO- toward 7a-g, indicating that the α-effect is operative. The magnitude of the α-effect (e.g., the kOx/k4-ClPhO ratio) is independent of the electronic nature of the substituent Y. The cause of the α- effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which Ox- behaves a general acid/base catalyst. This idea is further supported by the result that OH- exhibits negative deviation from the linear Brønsted-type plot composed of a series of aryloxides, while Ox- deviates positively from the linearity. Differential solvation of the GS of Ox- and 4-ClPhO- has been suggested to be responsible for the α-effect exerted by Ox-. | - |
dc.language | English | - |
dc.title | Nucleophilic substitution reactions of phenyl y-substituted-phenyl carbonates with butane-2,3-dione monoximate and 4-chlorophenoxide: Origin of the α-effect | - |
dc.type | Article | - |
dc.relation.issue | 1 | - |
dc.relation.volume | 34 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 49 | - |
dc.relation.lastpage | 53 | - |
dc.relation.journaltitle | Bulletin of the Korean Chemical Society | - |
dc.identifier.doi | 10.5012/bkcs.2013.34.1.49 | - |
dc.identifier.wosid | WOS:000316430100009 | - |
dc.identifier.scopusid | 2-s2.0-84872907871 | - |
dc.author.google | Kim M.-Y. | - |
dc.author.google | Min S.-W. | - |
dc.author.google | Um I.-H. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |