Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T12:08:00Z | - |
dc.date.available | 2016-08-28T12:08:00Z | - |
dc.date.issued | 2009 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.other | OAK-6405 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/220646 | - |
dc.description.abstract | The amines studied in this study are less reactive toward ethyl propiolate (3) in MeCN than in H2O although they are 7 to 9 pKa units more basic in the aprotic solvent. The reactivity of morpholine and deuterated morpholine toward 3 is found to be identical, indicating that proton transfer occurs after rate-determining step (RDS). The fact that kinetic isotope effect is absent excludes a stepwise mechanism in which proton transfer occurs in RDS as well as a concerted mechanism in which nucleophilic attack and proton transfer occur concertedly through a 4-membered cyclic transition state (TS). Thus, the reactions have been concluded to proceed through a stepwise mechanism in which proton transfer occurs after RDS. Brønsted-type plots are linear with small βnuc values, i.e., βnuc = 0.29 in H2O and βnuc = 0.51 in MeCN, indicating that bond formation is not advanced significantly in RDS. The small βnuc value also supports the conclusion drawn from the study of kinetic isotope effect. | - |
dc.language | English | - |
dc.title | Kinetics and mechanism of michael-type reactions of ethyl propiolate with alicyclic secondary amines in H2O and MeCN: Solvent effect on reactivity and transition-state structure | - |
dc.type | Article | - |
dc.relation.issue | 12 | - |
dc.relation.volume | 30 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 2909 | - |
dc.relation.lastpage | 2912 | - |
dc.relation.journaltitle | Bulletin of the Korean Chemical Society | - |
dc.identifier.doi | 10.5012/bkcs.2009.30.12.2909 | - |
dc.identifier.wosid | WOS:000276083700017 | - |
dc.identifier.scopusid | 2-s2.0-76649103707 | - |
dc.author.google | Kim S.-I. | - |
dc.author.google | Baek H.-W. | - |
dc.author.google | Um I.-H. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |