Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.contributor.author | 박종윤 | - |
dc.date.accessioned | 2016-08-28T10:08:07Z | - |
dc.date.available | 2016-08-28T10:08:07Z | - |
dc.date.issued | 2013 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.other | OAK-10190 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223804 | - |
dc.description.abstract | A kinetic study is reported for the Michael-type reactions of X-substituted β-nitrostyrenes (1a-j) with a series of cyclic secondary amines in MeCN. The plots of pseudo-first-order rate constant kobsd vs [amine] curve upward, indicating that the reactions proceed through catalyzed and uncatalyzed routes. The dissection of kobsd into Kk2 and Kk 3 (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) revealed that Kk3 is much larger than Kk2, implying that the reactions proceed mainly through the catalyzed route when [amine] > 0.01 M. Strikingly, the reactivity of β-nitrostyrene (1g) toward piperidine decreases as the reaction temperature increases. Consequently, a negative enthalpy of activation is obtained, indicating that the reaction proceeds through a relatively stable intermediate. The Brønsted-type plots for the reactions of 1g are linear with βnuc = 0.51 and 0.61, and the Hammett plots for the reactions of 1a-j are also linear with ρX = 0.84 and 2.10 for the uncatalyzed and catalyzed routes, respectively. The reactions are concluded to proceed through six-membered cyclic transition states for both the catalyzed and uncatalyzed routes. The effects of the substituent X on reactivity and factors influencing βnuc and ρX obtained in this study are discussed. © 2013 American Chemical Society. | - |
dc.language | English | - |
dc.title | Kinetic study on michael-type reactions of β-nitrostyrenes with cyclic secondary amines in acetonitrile: Transition-state structures and reaction mechanism deduced from negative enthalpy of activation and analyses of LFERs | - |
dc.type | Article | - |
dc.relation.issue | 11 | - |
dc.relation.volume | 78 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 5604 | - |
dc.relation.lastpage | 5610 | - |
dc.relation.journaltitle | Journal of Organic Chemistry | - |
dc.identifier.doi | 10.1021/jo4007442 | - |
dc.identifier.wosid | WOS:000320298700048 | - |
dc.identifier.scopusid | 2-s2.0-84879290760 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Kang J.-S. | - |
dc.author.google | Park J.-Y. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.contributor.scopusid | 박종윤(15036487300) | - |
dc.date.modifydate | 20230411105538 | - |