Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-29T12:08:50Z | - |
dc.date.available | 2016-08-29T12:08:50Z | - |
dc.date.issued | 2016 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.issn | 1229-5949 | - |
dc.identifier.other | OAK-19207 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/231845 | - |
dc.description.abstract | A kinetic study is reported for nucleophilic substitution reactions of X-substituted-phenyl diphenylphosphinates (3a-3f) with butane-2,3-dione monoximate (Ox(-)) and a series of Y-substituted-phenoxide (Y-PhO-) ions in 50 mol % H2O/50 mol % DMSO at 25.0 +/- 0.1 degrees C. The reactions of 3a-3f with Ox(-) and 4-chlorophenoxide (4-ClPhO-) result in linear BrOnsted-type plots with (lg) = -0.70 and -0.64, respectively, a typical (lg) value for reactions reported previously to proceed through a concerted mechanism. The BrOnsted-type plots for the reactions of 4-chloro-2-nitrophenyl diphenylphosphinate (3a), 4-nitrophenyl diphenylphosphinate (3b), and 4-acetylphenyl diphenylphosphinate (3d) with Y-PhO- are also linear with (nuc) = 0.15-0.35. The current reactions have been concluded to proceed through a concerted mechanism in which the bond formation is much less advanced than the bond rupture in the TS on the basis of the (lg) and (nuc) values. The -effect observed in this study is very small (i.e., the kOx-/kp-ClPhO- ratio = 16.4 - 43.5) and is independent of the leaving-group basicity. It has been concluded that the -effect shown by Ox(-) in the current reactions is mainly due to desolvation of Ox(-) in the reaction medium (ground-state contribution) rather than stabilization of the transition-state (TS contribution) on the basis of the kinetic results. | - |
dc.language | English | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
dc.subject | The alpha-effect | - |
dc.subject | Ground-state contribution | - |
dc.subject | Transition-state contribution | - |
dc.subject | Concerted mechanism | - |
dc.subject | BrOnsted-type plot | - |
dc.title | Kinetic Study on Nucleophilic Substitution Reactions of Aryl Diphenylphosphinates with Butane-2,3-dione Monoximate and Aryloxide Anions: Reaction Mechanism and Origin of the -Effect | - |
dc.type | Article | - |
dc.relation.issue | 8 | - |
dc.relation.volume | 37 | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 1180 | - |
dc.relation.lastpage | 1184 | - |
dc.relation.journaltitle | BULLETIN OF THE KOREAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1002/bkcs.10836 | - |
dc.identifier.wosid | WOS:000381037000005 | - |
dc.identifier.scopusid | 2-s2.0-84982806730 | - |
dc.author.google | Um, Ik-Hwan | - |
dc.author.google | Han, Jeong-Yoon | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |