Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2017-01-05T02:01:19Z | - |
dc.date.available | 2017-01-05T02:01:19Z | - |
dc.date.issued | 2003 | - |
dc.identifier.issn | 0022-3263 | - |
dc.identifier.other | OAK-1518 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/233716 | - |
dc.description.abstract | Second-order rate constants have been measured for the reaction of 2,4-dinitrophenyl X-substituted benzenesulfonates with a series of primary amines. The nucleophilic substitution reaction proceeds through competitive S-O and C-O bond fission pathways. The S-O bond fission occurs dominantly for reactions with highly basic amines or with substrates having a strong electron-withdrawing group in the sulfonyl moiety. On the other hand, the C-O bond fission occurs considerably for the reactions with low basic amines or with substrates having a strong electron-donating group in the sulfonyl moiety, emphasizing that the regioselectivity is governed by both the amine basicity and the electronic effect of the sulfonyl substituent X. The apparent second-order rate constants for the S-O bond fission have resulted in a nonlinear Brønsted-type plot for the reaction of 2,4-dinitrophenyl benzenesulfonate with 10 different primary amines, suggesting that a change in the rate-determining step occurs upon changing the amine basicity. The microscopic rate constants (k1 and k2/k-1 ratio) associated with the S-O bond fission pathway support the proposed mechanism. The second-order rate constants for the S-O bond fission result in good linear Yukawa-Tsuno plots for the aminolyses of 2,4-dinitrophenyl X-substituted benzenesulfonates. However, the second-order rate constants for the C-O bond fission show no correlation with the electronic nature of the sulfonyl substituent X, indicating that the C-O bond fission proceeds through an SNAR mechanism in which the leaving group departure occurs rapidly after the rate-determining step. | - |
dc.language | English | - |
dc.title | Regioselectivity and the nature of the reaction mechanism in nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates with primary amines | - |
dc.type | Article | - |
dc.relation.issue | 13 | - |
dc.relation.volume | 68 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 5180 | - |
dc.relation.lastpage | 5185 | - |
dc.relation.journaltitle | Journal of Organic Chemistry | - |
dc.identifier.doi | 10.1021/jo034190i | - |
dc.identifier.wosid | WOS:000183669800022 | - |
dc.identifier.scopusid | 2-s2.0-0038548286 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Hong J.-Y. | - |
dc.author.google | Kim J.-J. | - |
dc.author.google | Chae O.-M. | - |
dc.author.google | Bae S.-K. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |