Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-08-28T10:08:15Z | - |
dc.date.available | 2016-08-28T10:08:15Z | - |
dc.date.issued | 2013 | - |
dc.identifier.issn | 0009-2673 | - |
dc.identifier.other | OAK-10291 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223895 | - |
dc.description.abstract | A kinetic study on nucleophilic displacement reactions of O-ethyl O-4-nitrophenyl phenylphosphonothioate (an insecticide called EPN) with alkali-metal ethoxides (EtOM; M = Li, Na, K, and K/18-crown-6-ether) is reported. Dissection of pseudo-first-order rate constant (kobsd) into the second-order rate constants for the reaction of EPN with the dissociated EtO- (kEtO-) and ion-paired EtOM (kEtOM) has revealed that the reactivity increases in the order kEtOLi < kEtO < kEtONa < kEtOK < k EtOK/18-crown-6-ether, indicating that Li+ inhibits the reaction while the other M+ ions behave as a Lewis acid catalyst in the order Na+ < K+ < 18C6-complexed K+. The contrasting M+ ion effects have been explained in terms of the hard and soft acids and bases (HSAB) principle, since EPN, as a polarizable P=S centered electrophile, would exert a weak interaction with Li+ (a hard acid) but a strong interaction with the 18C6-complexed K+ ion (a soft acid). M+ ions catalyze the current reaction by increasing the electrophilicity of the reaction center. EPN is less reactive than O-4-nitrophenyl diphenylphosphinothioate but is more reactive than O-4-nitrophenyl O,O-diethyl thiophosphate. Factors governing the reactivity of these P=S centered electrophiles are discussed. © 2013 The Chemical Society of Japan. | - |
dc.language | English | - |
dc.title | Alkali-metal ion catalysis and inhibition in nucleophilic displacement reaction of O-ethyl O-4-nitrophenyl phenylphosphonothioate with alkali-metal ethoxides | - |
dc.type | Article | - |
dc.relation.issue | 6 | - |
dc.relation.volume | 86 | - |
dc.relation.index | SCI | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.startpage | 736 | - |
dc.relation.lastpage | 741 | - |
dc.relation.journaltitle | Bulletin of the Chemical Society of Japan | - |
dc.identifier.doi | 10.1246/bcsj.20130015 | - |
dc.identifier.wosid | WOS:000321729900009 | - |
dc.identifier.scopusid | 2-s2.0-84879186388 | - |
dc.author.google | Um I.-H. | - |
dc.author.google | Kang J.-S. | - |
dc.author.google | Shin M. | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |