Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-27T02:08:17Z | - |
dc.date.available | 2016-08-27T02:08:17Z | - |
dc.date.issued | 1998 | - |
dc.identifier.issn | 0008-4042 | - |
dc.identifier.other | OAK-98 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/215267 | - |
dc.description.abstract | Second-order rate constants have been measured spectrophotometrically for the reactions of X-C6H4CO2C6H4-Y with a series of primary amines in H2O containing 20 mol% DMSO at 25.0 +/- 0.1 degrees C. The reactivity increases as the substituent (X and Y) becomes a stronger electron-withdrawing group. The sigma(+) constants give better Hammett correlation than sigma constants for the reactions of 4-nitrophenyl X-substituted benzoates with glycylglycine (glygly) and hydrazine (NH2NH3, indicating that the ground-state stabilization effect is unusually significant on the reaction rates. The reactions of X-C6H4CO2C6H4-Y with glygly and NH2NH2 appear to proceed through the same mechanism, but the degree of leaving-group departure and the negative charge developed in the acyl moiety at the rate-determining TS is considered to be more significant for the glygly system than the NH2NH2 system based on beta(1g) and rho(x) values. The magnitude of the alpha-effect is observed to be not always dependent on the beta(nuc) value but dependent on the electronic nature of the substituent X and Y, i.e., an electron-donating substituent increases the alpha-effect, while an electron-withdrawing one decreases the alpha-effect. The present study has led to the conclusion that the ground-state effect is important for the reaction rates but it is not solely responsible for the alpha-effect, and the intramolecular H-bonding interactions (4) are proposed for the cause of the increasing or decreasing a-effect trends observed in the present system. | - |
dc.language | English | - |
dc.publisher | NATL RESEARCH COUNCIL CANADA | - |
dc.subject | alpha-effect | - |
dc.subject | intramolecular H-bonding interaction | - |
dc.subject | ground-state stabilization effect | - |
dc.title | An unusual ground-state stabilization effect and origins of the alpha-effect in aminolyses of Y-substituted phenyl X-substituted benzoates | - |
dc.type | Article | - |
dc.relation.issue | 6 | - |
dc.relation.volume | 76 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 729 | - |
dc.relation.lastpage | 737 | - |
dc.relation.journaltitle | CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE | - |
dc.identifier.doi | 10.1139/cjc-76-6-729 | - |
dc.identifier.wosid | WOS:000076396000016 | - |
dc.identifier.scopusid | 2-s2.0-0031765069 | - |
dc.author.google | Um, IH | - |
dc.author.google | Chung, EK | - |
dc.author.google | Lee, SM | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |