Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T12:08:26Z | - |
dc.date.available | 2016-08-28T12:08:26Z | - |
dc.date.issued | 2012 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.other | OAK-8825 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/222683 | - |
dc.description.abstract | Second-order rate constants (kN) have been measured spectrophotometrically for the reactions of benzyl 2- pyridyl carbonate 7 and t-butyl 2-pyridyl carbonate 8 with a series of alicyclic secondary amines in l 2O at 25.0 ° C. Substrate 8 is less reactive than 7. Steric hindrance exerted by the bulky t-Bu group of 8 has been suggested to be responsible for the decreased reactivity. The Brønsted-type plots for the reactions of 7 and 8 are linear with ß nuc = 0.49 and 0.44, respectively, which is typical for reactions reported previously to proceed through a concerted mechanism. Aminolyses of 7 and 8 were expected to proceed through a zwitterionic tetrahedral intermediate T± , which would be stabilized through an intramolecular H-bonding interaction. However, the kinetic results suggest that the reactions proceed through a concerted mechanism. The H-bonding interaction in T± has been suggested to accelerate the rate of leaving-group expulsion from T± . Another factor that might accelerate expulsion of the leaving group is the "push" provided by the RO group in T± through resonance interactions. Thus, it has been concluded that the enhanced nucleofugality through the H-bonding interaction and the "push" provided by the RO group forces the reactions to proceed through a concerted mechanism. Copyright © 2005 KCSNET. | - |
dc.language | English | - |
dc.title | Kinetics and reaction mechanism of aminolyses of benzyl 2-pyridyl carbonate and t-butyl 2-pyridyl carbonate: Effect of nonleaving group on reactivity and reaction mechanism | - |
dc.type | Article | - |
dc.relation.issue | 5 | - |
dc.relation.volume | 33 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 1551 | - |
dc.relation.lastpage | 1555 | - |
dc.relation.journaltitle | Bulletin of the Korean Chemical Society | - |
dc.identifier.doi | 10.5012/bkcs.2012.33.5.1551 | - |
dc.identifier.wosid | WOS:000304432100021 | - |
dc.identifier.scopusid | 2-s2.0-84861391171 | - |
dc.author.google | Kang J.-S. | - |
dc.author.google | Lee J.-I. | - |
dc.author.google | Um I.-H. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |