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 Field | Value | Language |
---|---|---|
dc.contributor.author | Um, Ik-Hwan | - |
dc.contributor.author | Park, Kyoung-Ho | - |
dc.date.accessioned | 2021-06-22T13:41:38Z | - |
dc.date.available | 2021-06-22T13:41:38Z | - |
dc.date.issued | 2017-10 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.issn | 1229-5949 | - |
dc.identifier.uri | https://scholarworks.bwise.kr/erica/handle/2021.sw.erica/8941 | - |
dc.description.abstract | Second-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.extent | 5 | - |
dc.language | 영어 | - |
dc.language.iso | ENG | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
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.publisher.location | 독일 | - |
dc.identifier.doi | 10.1002/bkcs.11242 | - |
dc.identifier.scopusid | 2-s2.0-85028917289 | - |
dc.identifier.wosid | 000413356700010 | - |
dc.identifier.bibliographicCitation | BULLETIN OF THE KOREAN CHEMICAL SOCIETY, v.38, no.10, pp 1169 - 1173 | - |
dc.citation.title | BULLETIN OF THE KOREAN CHEMICAL SOCIETY | - |
dc.citation.volume | 38 | - |
dc.citation.number | 10 | - |
dc.citation.startPage | 1169 | - |
dc.citation.endPage | 1173 | - |
dc.type.docType | Article | - |
dc.identifier.kciid | ART002274379 | - |
dc.description.isOpenAccess | N | - |
dc.description.journalRegisteredClass | sci | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.description.journalRegisteredClass | kci | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Multidisciplinary | - |
dc.subject.keywordPlus | O,O-DIETHYL 2,4-DINITROPHENYL PHOSPHATE | - |
dc.subject.keywordPlus | VARYING RESONANCE DEMAND | - |
dc.subject.keywordPlus | GAS-PHASE ACIDITIES | - |
dc.subject.keywordPlus | REACTION-MECHANISM | - |
dc.subject.keywordPlus | ELECTROPHILIC CENTER | - |
dc.subject.keywordPlus | IONIC LIQUIDS | - |
dc.subject.keywordPlus | LEAVING-GROUP | - |
dc.subject.keywordPlus | CARBOCATIONIC SYSTEMS | - |
dc.subject.keywordPlus | ALKALINE-HYDROLYSIS | - |
dc.subject.keywordPlus | TRANSITION-STATE | - |
dc.subject.keywordAuthor | O-Phenyl O-Y-substituted-phenyl thionocarbonates | - |
dc.subject.keywordAuthor | 1,8-Diazabicyclo[5.4.0]undec-7-ene | - |
dc.subject.keywordAuthor | Steric hindrance | - |
dc.subject.keywordAuthor | Forced concerted mechanism | - |
dc.subject.keywordAuthor | Bronsted-type plot | - |
dc.identifier.url | https://onlinelibrary.wiley.com/doi/10.1002/bkcs.11242 | - |
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