Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2019-01-02T16:30:19Z | - |
dc.date.available | 2019-01-02T16:30:19Z | - |
dc.date.issued | 2018 | - |
dc.identifier.issn | 0008-4042 | - |
dc.identifier.issn | 1480-3291 | - |
dc.identifier.other | OAK-24001 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/248091 | - |
dc.description.abstract | Upward curvature in the kinetic plots of pseudo first-order rate constants (k(obsd)) vs. [amine] for the aminolysis of aryl phenyl carbonates (5a-5j) in MeCN demonstrates that these reactions proceed via a zwitterionic tetrahedral intermediate (T-+/-) that partitions between catalyzed and uncatalyzed routes to give the products. Yukawa-Tsuno plots for the reactions of 5a-5j with piperidine result in excellent linear correlations with rho(Y) = 4.82 and r = 0.47 for the uncatalyzed reaction versus rho(Y) = 2.21 and r = 0.21 for the catalyzed reaction. Brensted plots for reactions of 4-(ethoxycarbonyl)-phenyl phenyl carbonate isp with a series of cyclic secondary amines exhibit excellent linear correlations with beta(nuc) = 0.87 and 0.58 for the uncatalyzed and catalyzed reactions, respectively. The Delta H-double dagger and Delta S-double dagger values are 0.92 kcal/mol and -50.1 cal/mol K, respectively, for the catalyzed reaction of 5f with piperidine. Deuterium kinetic isotope effects found for reactions of 5f with piperidine/deuterated piperidine are 0.84 (uncatalyzed) and 1.42 (catalyzed). Multi-parameter analysis supports a concerted catalytic pathway involving a six-membered cyclic transition state rather than a traditionally accepted stepwise pathway with an anionic intermediate. The current unexpected results, where P is the essential central intermediate in this aminolysis, contrast with previous calculation studies that deemed T +/- unstable in gas phase or MeCN. | - |
dc.language | English | - |
dc.publisher | CANADIAN SCIENCE PUBLISHING, NRC RESEARCH PRESS | - |
dc.subject | aminolysis | - |
dc.subject | aryl phenyl carbonates | - |
dc.subject | cyclic transition-state structure | - |
dc.subject | activation parameters | - |
dc.subject | deuterium kinetic isotope effects | - |
dc.title | Unexpected medium effect on the mechanism for aminolysis of aryl phenyl carbonates in acetonitrile and H2O: transition-state structure in the catalytic pathway | - |
dc.type | Article | - |
dc.relation.issue | 12 | - |
dc.relation.volume | 96 | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 1011 | - |
dc.relation.lastpage | 1020 | - |
dc.relation.journaltitle | CANADIAN JOURNAL OF CHEMISTRY | - |
dc.identifier.doi | 10.1139/cjc-2018-0204 | - |
dc.identifier.wosid | WOS:000450109800003 | - |
dc.author.google | Um, Ik-Hwan | - |
dc.author.google | Song, Ji-Hyun | - |
dc.author.google | Bae, Ae-Ri | - |
dc.author.google | Dust, Julian M. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |