Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2017-12-27T16:30:49Z | - |
dc.date.available | 2017-12-27T16:30:49Z | - |
dc.date.issued | 2017 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.other | OAK-21513 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/239374 | - |
dc.description.abstract | Second-order rate constants (kN) for nucleophilic substitution reactions of O-phenyl O-Y-substituted-phenyl thionocarbonates (4a–4k) with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in MeCN at 25.0 ± 0.1°C are reported. The reactivity of 4a–4k decreases as basicity of the leaving group increases except O-2,4-dinitrophenyl O-phenyl thionocarbonate (4a), which is less reactive than O-3,4-dinitrophenyl O-phenyl thionocarbonate (4b) although the former possesses 2 pKa units less basic nucleofuge than the latter. The Brønsted-type plot for the reactions of 4b–4k is linear with βlg = −0.50, a typical βlg value for reactions reported to proceed through a concerted mechanism. The Hammett plot correlated with σY − constants for the reactions of 4b–4k results in a better linear correlation than that correlated with σY o constants. Besides, the Yukawa-Tsuno plot exhibits an excellent linear correlation with ρY = 2.12, r = 0.68 and R2 = 0.990, indicating that a negative charge develops partially on the O atom of the leaving group in the rate-determining step (RDS). Thus, the reactions have been concluded to proceed through a forced concerted mechanism. Effects of steric hindrance on reactivity and reaction mechanism are also discussed in detail. © 2017 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim | - |
dc.language | English | - |
dc.publisher | Wiley Blackwell | - |
dc.subject | 1,8-Diazabicyclo[5.4.0]undec-7-ene | - |
dc.subject | Brønsted-type plot | - |
dc.subject | Forced concerted mechanism | - |
dc.subject | O-Phenyl O-Y-substituted-phenyl thionocarbonates | - |
dc.subject | Steric hindrance | - |
dc.title | Kinetic Study on Nucleophilic Substitution Reactions of O-Phenyl O-Y-substituted-Phenyl Thionocarbonates with 1,8-Diazabicyclo[5.4.0]undec-7-ene in Acetonitrile | - |
dc.type | Article | - |
dc.relation.issue | 10 | - |
dc.relation.volume | 38 | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 1169 | - |
dc.relation.lastpage | 1173 | - |
dc.relation.journaltitle | Bulletin of the Korean Chemical Society | - |
dc.identifier.doi | 10.1002/bkcs.11242 | - |
dc.identifier.wosid | WOS:000413356700010 | - |
dc.identifier.scopusid | 2-s2.0-85028917289 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Park K.-H. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |