Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T11:08:22Z | - |
dc.date.available | 2016-08-28T11:08:22Z | - |
dc.date.issued | 2000 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.other | OAK-356 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/218600 | - |
dc.description.abstract | The origin of the α-effect has been probed through a combination of calorimetric and kinetic studies involving butane-2,3-dione monoximate as α- nucleophile and p-chlorophenoxide as normal nucleophile in the reaction with p-nitrophenyl acetate in DMSO-H2O mixtures, which has been shown to exhibit a bell-shaped profile in the α-effect with solvent composition. The study, involving determination of enthalpies of solution and activation parameters, has allowed a dissection of contributions to the α-effect of ground-state destabilization and transition-state stabilization in these DMSO-H2O solvent media. It has been found that over the solvent composition 0-50 mol % DMSO desolvation of the α-nucleophile is the main driving factor to the increasing α-effect. However, in solvent mixtures covering 50-90 mol % DMSO the thermodynamic activation parameters suggest an interplay of factors that result in the bell-shaped α-effect profile. Discussion is presented that includes possible medium-dependent nonsynchronicity of nucleophile desolvation and bond formation for the α-nucleophile. | - |
dc.language | English | - |
dc.title | The origin of the α-effect: Dissection of ground-state and transition- state contributions | - |
dc.type | Article | - |
dc.relation.issue | 2 | - |
dc.relation.volume | 65 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 577 | - |
dc.relation.lastpage | 582 | - |
dc.relation.journaltitle | Journal of Organic Chemistry | - |
dc.identifier.doi | 10.1021/jo9915776 | - |
dc.identifier.wosid | WOS:000084905400046 | - |
dc.identifier.scopusid | 2-s2.0-0034723425 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Buncel E. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |