Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T12:08:13Z | - |
dc.date.available | 2016-08-28T12:08:13Z | - |
dc.date.issued | 2011 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.other | OAK-7949 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/221937 | - |
dc.description.abstract | Second-order rate constants (k N) were measured for aminolyses of Y-substituted-phenyl 2-methoxybenzoates 2a-i and 4-nitrophenyl X-substituted-benzoates 3a-j in MeCN at 25.0 °C. The Brønsted-type plot for the reactions of 2a-i with piperidine curves downward, indicating that a change in rate-determining step (RDS) occurs. The Hammett plot for the reactions of 3a-j with piperidine consists of two intersecting straight lines, which might be taken as evidence for a change in RDS. However, the nonlinear Hammett plot has been suggested not to be due to a change in RDS but rather to the stabilization of the ground state of substrates possessing an electron-donating group (EDG) (e.g., 3a-c) through a resonance interaction, since the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with ρ = 0.54 and r = 1.54. The ρ value found for the reactions of 3a-j in MeCN is much smaller than that reported previously for the corresponding reactions in H 2O (i.e., ρ = 0.75). It is proposed that the reactions of 3a-j in MeCN proceed through a forced concerted mechanism due to instability of T ± in the aprotic solvent, while the reactions of 2a-i proceed through a stepwise pathway with a stabilized T ± through an intramolecular H-bonding interaction. © 2011 American Chemical Society. | - |
dc.language | English | - |
dc.title | Aminolysis of Y-substituted-phenyl 2-methoxybenzoates in acetonitrile: Effect of the o-methoxy group on reactivity and reaction mechanism | - |
dc.type | Article | - |
dc.relation.issue | 18 | - |
dc.relation.volume | 76 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 7510 | - |
dc.relation.lastpage | 7515 | - |
dc.relation.journaltitle | Journal of Organic Chemistry | - |
dc.identifier.doi | 10.1021/jo201387h | - |
dc.identifier.wosid | WOS:000294702000025 | - |
dc.identifier.scopusid | 2-s2.0-80052704928 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Bae A.R. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |