Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-10-20T02:10:31Z | - |
dc.date.available | 2016-10-20T02:10:31Z | - |
dc.date.issued | 2009 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.other | OAK-5538 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/232473 | - |
dc.description.abstract | A kinetic study is reported for aminolysis of X-substituted phenyl diphenylphosphinates (1a-i) in 80 mol % H 2O/20 mol % dimethyl sulfoxide at 25.0 ±0.1 °C. The Brønsted-type plot for the reactions of 2,4-dinitrophenyl diphenylphosphinate (1a) with primary amines is linear withβ nuc = 0.53. The reactions of 1a-i with ethylamine also result in a linear Brønsted-type plot with β lg = -0.81. These β nuc and β lg values are slightly larger than those reported previously for the reactions of 1a with secondary amines (β nuc = 0.38) and for those of 1a-i with piperidine (β lg = -0.66) but typical for reactions that proceed through a concerted mechanism. It has been concluded that aminolysis of 1a-i proceed through a concerted mechanism and the nature of amines does not affect the reaction mechanism. However, the reactions with primary amines have been suggested to proceed through a later transition state (i.e., more bond formation and bond rupture in the transition state) on the basis of the larger β nuc and β lg values. The concerted mechanism has been further supported from the fact that the Yukawa-Tsuno plot for the reactions of 1a-i with ethylamine exhibits an excellent linear correlation with ρ = 2.24 and r = 0.22. Weakly basic primary amines are less reactive than secondary amines of similar basicity. However, strongly basic ethylamine is ca. 2-fold more reactive than piperidine toward 1a, although the former is 0.35 pK a units less basic than the latter. © 2009 American Chemical Society. | - |
dc.language | English | - |
dc.title | Aminolysis of X-substituted phenyl diphenylphosphinates: Effect of amine nature on reactivity and transition-state structure | - |
dc.type | Article | - |
dc.relation.issue | 8 | - |
dc.relation.volume | 74 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 3073 | - |
dc.relation.lastpage | 3078 | - |
dc.relation.journaltitle | Journal of Organic Chemistry | - |
dc.identifier.doi | 10.1021/jo900219t | - |
dc.identifier.wosid | WOS:000265073700020 | - |
dc.identifier.scopusid | 2-s2.0-65249118978 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Han J.-Y. | - |
dc.author.google | Shin Y.-H. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |