Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2018-05-02T08:15:48Z | - |
dc.date.available | 2018-05-02T08:15:48Z | - |
dc.date.issued | 2004 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.other | OAK-2099 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/242810 | - |
dc.description.abstract | Second-order rate constants have been measured for alkaline hydrolysis of O-aryl thionobenzoates (X-C6H4-CS-OC6H 4-Y) in 80 mol % H2O-20 mol % DMSO at 25.0 ± 0.1 °C. The Hammett plot for the reaction of O-4-nitrophenyl X-substituted thionobenzoates (X-C6H4-CS-OC6H 4-NO2, 1a-e) exhibits a downward curvature. However, a possible traditional explanation in terms of a change in the rate-determining step (RDS) has been considered but rejected. The proposed explanation involves stabilization of the ground-state (GS) through-resonance interaction between the electron-donating substituent X and the thionocarbonyl functionality on the basis of the linear Yukawa-Tsuno plot obtained for the same reaction. The Brønsted-type plot for the reaction of O-aryl thionobenzoates (C 6H5-CS-OC6H4-Y, 2a-i) is linear but exhibits many scattered points with a small βlg, (-0.35). The Hammett plot for the same reaction shows rather poor correlation with σ- constants but much better correlation with σ° constants. The alkaline hydrolysis of O-aryl thionobenzoates (1a-e and 2a-i) has been proposed to proceed through an addition intermediate in which bond formation is the RDS. | - |
dc.language | English | - |
dc.title | Curved Hammett Plot in Alkaline Hydrolysis of O-Aryl Thionobenzoates: Change in Rate-Determining Step versus Ground-State Stabilization | - |
dc.type | Article | - |
dc.relation.issue | 7 | - |
dc.relation.volume | 69 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 2436 | - |
dc.relation.lastpage | 2441 | - |
dc.relation.journaltitle | Journal of Organic Chemistry | - |
dc.identifier.doi | 10.1021/jo035854r | - |
dc.identifier.wosid | WOS:000220506200031 | - |
dc.identifier.scopusid | 2-s2.0-1842451690 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Lee J.-Y. | - |
dc.author.google | Kim H.-T. | - |
dc.author.google | Bae S.-K. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |