Full metadata record
DC Field | Value | Language |
---|---|---|
dc.contributor.author | 엄익환 | - |
dc.date.accessioned | 2016-09-21T01:09:23Z | - |
dc.date.available | 2016-09-21T01:09:23Z | - |
dc.date.issued | 2016 | - |
dc.identifier.issn | 0253-2964 | - |
dc.identifier.issn | 1229-5949 | - |
dc.identifier.other | OAK-19300 | - |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/232287 | - |
dc.description.abstract | Pseudo-first-order rate constants (k(obsd)) for nucleophilic substitution reaction of O-2-pyridyl thionobenzoate (7) with a series of secondary amines in MeCN at 25.0 +/- 0.1 degrees C have been measured spectrophotometrically. The plots of k(obsd) vs. [amine] curve upward, indicating that the reaction proceeds through a stepwise mechanism with a zwitterionic tetrahedral intermediate (T-+/-), which decomposes to the products through uncatalyzed and catalyzed routes. It has been proposed that the uncatalyzed reaction proceeds through a six-membered cyclic transition state (TS), in which expulsion of the leaving group occurs in the rate-determining step. The catalyzed reaction from T-+/- proceeds through a concerted mechanism with a six-membered cyclic TS rather than via a stepwise pathway with an anionic intermediate T-. This is in contrast to the report that the corresponding reaction of 2-pyridyl benzoate (6, a CO analogue of 7) proceeds through a forced concerted mechanism. Comparison of the second-order rate constants for the uncatalyzed reaction of 7 with those reported previously for the corresponding reaction of 6 has revealed that 7 is much more reactive than 6. Factors that affect the reactivity and reaction mechanism are discussed in detail. | - |
dc.language | English | - |
dc.publisher | WILEY-V C H VERLAG GMBH | - |
dc.subject | Aminolysis | - |
dc.subject | O-2-Pyridyl thionobenzoate | - |
dc.subject | Catalyzed reaction | - |
dc.subject | Bronsted-type plot | - |
dc.subject | Cyclic transition state | - |
dc.title | Kinetic Study on Aminolysis of O-2-Pyridyl Thionobenzoate in Acetonitrile: Effect of Changing Electrophilic Center from C=O to C=S on Reactivity and Reaction Mechanism | - |
dc.type | Article | - |
dc.relation.issue | 9 | - |
dc.relation.volume | 37 | - |
dc.relation.index | SCIE | - |
dc.relation.index | SCOPUS | - |
dc.relation.index | KCI | - |
dc.relation.startpage | 1401 | - |
dc.relation.lastpage | 1405 | - |
dc.relation.journaltitle | BULLETIN OF THE KOREAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1002/bkcs.10875 | - |
dc.identifier.wosid | WOS:000383775400005 | - |
dc.identifier.scopusid | 2-s2.0-84985914432 | - |
dc.author.google | Kim, Min-Young | - |
dc.author.google | Um, Ik-Hwan | - |
dc.contributor.scopusid | 엄익환(7006725706;6506759437) | - |
dc.date.modifydate | 20230411105538 | - |