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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

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dc.contributor.authorUm, Ik-Hwan-
dc.contributor.authorPark, Kyoung-Ho-
dc.date.accessioned2021-06-22T13:41:38Z-
dc.date.available2021-06-22T13:41:38Z-
dc.date.issued2017-10-
dc.identifier.issn0253-2964-
dc.identifier.issn1229-5949-
dc.identifier.urihttps://scholarworks.bwise.kr/erica/handle/2021.sw.erica/8941-
dc.description.abstractSecond-order rate constants (k(N)) 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 degrees 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 pK(a) units less basic nucleofuge than the latter. The Bronsted-type plot for the reactions of 4b-4k is linear with beta(lg)=-0.50, a typical beta(lg) value for reactions reported to proceed through a concerted mechanism. The Hammett plot correlated with sigma(-)(Y) constants for the reactions of 4b-4k results in a better linear correlation than that correlated with sigma(o)(Y) constants. Besides, the Yukawa-Tsuno plot exhibits an excellent linear correlation with rho(Y)=2.12, r=0.68 and R-2=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.-
dc.format.extent5-
dc.language영어-
dc.language.isoENG-
dc.publisherWILEY-V C H VERLAG GMBH-
dc.titleKinetic 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.typeArticle-
dc.publisher.location독일-
dc.identifier.doi10.1002/bkcs.11242-
dc.identifier.scopusid2-s2.0-85028917289-
dc.identifier.wosid000413356700010-
dc.identifier.bibliographicCitationBULLETIN OF THE KOREAN CHEMICAL SOCIETY, v.38, no.10, pp 1169 - 1173-
dc.citation.titleBULLETIN OF THE KOREAN CHEMICAL SOCIETY-
dc.citation.volume38-
dc.citation.number10-
dc.citation.startPage1169-
dc.citation.endPage1173-
dc.type.docTypeArticle-
dc.identifier.kciidART002274379-
dc.description.isOpenAccessN-
dc.description.journalRegisteredClasssci-
dc.description.journalRegisteredClassscie-
dc.description.journalRegisteredClassscopus-
dc.description.journalRegisteredClasskci-
dc.relation.journalResearchAreaChemistry-
dc.relation.journalWebOfScienceCategoryChemistry, Multidisciplinary-
dc.subject.keywordPlusO,O-DIETHYL 2,4-DINITROPHENYL PHOSPHATE-
dc.subject.keywordPlusVARYING RESONANCE DEMAND-
dc.subject.keywordPlusGAS-PHASE ACIDITIES-
dc.subject.keywordPlusREACTION-MECHANISM-
dc.subject.keywordPlusELECTROPHILIC CENTER-
dc.subject.keywordPlusIONIC LIQUIDS-
dc.subject.keywordPlusLEAVING-GROUP-
dc.subject.keywordPlusCARBOCATIONIC SYSTEMS-
dc.subject.keywordPlusALKALINE-HYDROLYSIS-
dc.subject.keywordPlusTRANSITION-STATE-
dc.subject.keywordAuthorO-Phenyl O-Y-substituted-phenyl thionocarbonates-
dc.subject.keywordAuthor1,8-Diazabicyclo[5.4.0]undec-7-ene-
dc.subject.keywordAuthorSteric hindrance-
dc.subject.keywordAuthorForced concerted mechanism-
dc.subject.keywordAuthorBronsted-type plot-
dc.identifier.urlhttps://onlinelibrary.wiley.com/doi/10.1002/bkcs.11242-
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