Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2022-06-02T16:31:07Z | - |
dc.date.available | 2022-06-02T16:31:07Z | - |
dc.date.issued | 2022 | - |
dc.identifier.issn | 0008-4042 | - |
dc.identifier.other | OAK-31446 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/261215 | - |
dc.description.abstract | A kinetic study is reported for reactions of 2,4-dinitrophenyl X-substituted-benzenesulfonates (1a–1f) and Y-substituted-phenyl benzenesulfonates (2a–2f) with Z-substituted-pyridines. The reactions proceed through S–O and C–O bond scissions competitively. The Yukawa–Tsuno plot for the reactions of 1a–1f with 4-oxypyridine (S–O bond fission) exhibits an excellent linearity. The Brønsted-type plot for the reactions of 2,4-dinitrophenyl benzenesulfonate (1d) with pyridines (S–O bond fission) is also linear with bnuc = 0.62. The Brønsted-type plot for the reactions of 2a–2f with 4-oxypyridines (S–O bond fission) is linear with blg = –1.17. Thus, the reactions have been concluded to proceed through a concerted mechanism, in which leaving-group expulsion is significantly more advanced than bond formation between the electrophilic center and nucleophile at the transition state. The Hammett plot for the reactions of 1a–1f with 4-oxypyridine (C–O bond fission) exhibits scattered points with rX = 0.98. The Brønsted-type plot for the reactions of 1d with Z-substituted-pyridines (C–O bond fission) results in an excellent linear correlation with bnuc = 0.38. Thus, the reactions (C–O bond fission) have been concluded to proceed through a stepwise mechanism with a Meisenheimer complex, in which expulsion of the leaving group occurs after the rate-determining step. Factors governing regioselectivity and reaction mechanism are discussed. © Canadian Science Publishing. All rights reserved. | - |
dc.language | English | - |
dc.publisher | Canadian Science Publishing | - |
dc.subject | aryl benzenesulfonates | - |
dc.subject | Brønsted-type plot | - |
dc.subject | reaction mechanism | - |
dc.subject | regioselectivity | - |
dc.subject | resonance stability | - |
dc.title | Kinetic study on pyridinolysis of aryl benzenesulfonates: factors governing regioselectivity and reaction mechanism | - |
dc.type | Article | - |
dc.relation.issue | 5 | - |
dc.relation.volume | 100 | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 378 | - |
dc.relation.lastpage | 385 | - |
dc.relation.journaltitle | Canadian Journal of Chemistry | - |
dc.identifier.doi | 10.1139/cjc-2021-0287 | - |
dc.identifier.wosid | WOS:000790341200001 | - |
dc.identifier.scopusid | 2-s2.0-85129329399 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Jung Y.J. | - |
dc.author.google | Dust J.M. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |