Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2018-05-30T08:14:05Z | - |
dc.date.available | 2018-05-30T08:14:05Z | - |
dc.date.issued | 2006 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.other | OAK-3241 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/243506 | - |
dc.description.abstract | A kinetic study is reported for nucleophilic substitution reactions of 4-nitrophenyl phenyl carbonate (5) and 4-nitrophenyl phenyl thionocarbonate (6) with a series of primary amines. The thiono compound 6 is less reactive than its oxygen analogue 5 toward strongly basic amines but is more reactive toward weakly basic CF 3CH 2NH 2. The Brønsted-type plots obtained from the aminolyses of 5 and 6 are curved downwardly. The reactions are proposed to proceed through a stepwise mechanism with a change in the RDS on the basis of the curved Brønsted-type plots. The microscopic rate constants (k 1 and k 2/k -1 ratio) associated with the current aminolyses are consistent with the proposed reaction mechanism. The replacement of the C=O bond in 5 by a polarizable C=S group results in a decrease in the k 1 value but an increase in the k 2/k -1 ratio. Besides, such a modification of the electrophilic center causes a decrease in pK a c, defined as the pK a at the curvature center of curved Brønsted-type plots, but does not alter the reaction mechanism. The larger k 2/k -1 ratio for the reactions of 6 compared to those of 5 is proposed to be responsible for the decreased pK a c value. © 2006 American Chemical Society. | - |
dc.language | English | - |
dc.title | Aminolyses of 4-nitrophenyl phenyl carbonate and thionocarbonate: Effect of modification of electrophilic center from C=O to C=S on reactivity and mechanism | - |
dc.type | Article | - |
dc.relation.issue | 6 | - |
dc.relation.volume | 71 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 2302 | - |
dc.relation.lastpage | 2306 | - |
dc.relation.journaltitle | Journal of Organic Chemistry | - |
dc.identifier.doi | 10.1021/jo052417z | - |
dc.identifier.wosid | WOS:000236307300014 | - |
dc.identifier.scopusid | 2-s2.0-33645032588 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Kim E.Y. | - |
dc.author.google | Park H.-R. | - |
dc.author.google | Jeon S.-E. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |