Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T12:08:07Z | - |
dc.date.available | 2016-08-28T12:08:07Z | - |
dc.date.issued | 2011 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.other | OAK-7251 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/221333 | - |
dc.description.abstract | Second-order rate constants (kOH-) have been measured spectrophotometrically for reactions of Y-substituted phenyl phenyl thionocarbonates (4a-i) with OH- in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The kOH- values for the reactions of 4a-i have been compared with those reported previously for the corresponding reactions of Y-substituted phenyl phenyl carbonates (3a-i) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and mechanism. Thionocarbonates 4a-i are less reactive than the corresponding carbonates 3a-i although 4a-i are expected to be more reactive than 3a-i. The Brønsted-type plot for reactions of 4a-i is linear with β1g = - 0.33, a typical β1g value for reactions reported to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step (RDS). Furthermore, the Hammett plot correlated with σ° constants results in much better linearity than that correlated with σ- constants, indicating that expulsion of the leaving group is not advanced in the RDS. Thus, alkaline hydrolysis of 4a-i has been concluded to proceed through a stepwise mechanism with formation of an intermediate being RDS, which is in contrast to the forced concerted mechanism reported for the corresponding reactions of 3a-i. Enhanced stability of the intermediate upon modification of the electrophilic center from C=O to C=S has been concluded to be responsible for the contrasting mechanisms. | - |
dc.language | English | - |
dc.title | Alkaline hydrolysis of Y-substituted phenyl phenyl thionocarbonates: Effect of changing electrophilic center from C=O to C=S on reactivity and mechanism | - |
dc.type | Article | - |
dc.relation.issue | 1 | - |
dc.relation.volume | 32 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 179 | - |
dc.relation.lastpage | 182 | - |
dc.relation.journaltitle | Bulletin of the Korean Chemical Society | - |
dc.identifier.doi | 10.5012/bkcs.2011.32.1.179 | - |
dc.identifier.wosid | WOS:000286538600033 | - |
dc.identifier.scopusid | 2-s2.0-78951473086 | - |
dc.author.google | Kim S.-I. | - |
dc.author.google | Park H.-R. | - |
dc.author.google | Um I.-H. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |