Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Park, Kyoung Ho | - |
dc.contributor.author | Seong, Mi Hye | - |
dc.contributor.author | Kyong, Jin Burm | - |
dc.contributor.author | Kevill, Dennis N. | - |
dc.date.accessioned | 2023-12-11T08:30:17Z | - |
dc.date.available | 2023-12-11T08:30:17Z | - |
dc.date.issued | 2021-07 | - |
dc.identifier.issn | 1661-6596 | - |
dc.identifier.issn | 1422-0067 | - |
dc.identifier.uri | https://scholarworks.bwise.kr/erica/handle/2021.sw.erica/116261 | - |
dc.description.abstract | A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald-Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)(+) (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis-decomposition pathway through the intermediate 1-Ad(+)Cl(-) ion pairs (carbocation) with the loss of carbonyl sulfide. In addition, the rate constants (k(exp)) for the solvolysis of 1 were separated into k through a product study and applied to the Grunwald-Winstein equation to obtain the sensitivity (m-value) to change in solvent ionizing power. For binary hydroxylic solvents, the selectivities (S) for the formation of solvolysis products were very similar to those of the 1-adamantyl derivatives discussed previously. The kinetic solvent isotope effects (KSIEs), salt effects and activation parameters for the solvolyses of 1 were also determined. These observations are compared with those previously reported for the solvolyses of 1-adamantyl chloroformate (1-AdOCOCl, 2). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions calculated using Gaussian 03. | - |
dc.format.extent | 13 | - |
dc.language | 영어 | - |
dc.language.iso | ENG | - |
dc.publisher | Multidisciplinary Digital Publishing Institute (MDPI) | - |
dc.title | Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions | - |
dc.type | Article | - |
dc.publisher.location | 스위스 | - |
dc.identifier.doi | 10.3390/ijms22147394 | - |
dc.identifier.scopusid | 2-s2.0-85109343617 | - |
dc.identifier.wosid | 000676582300001 | - |
dc.identifier.bibliographicCitation | International Journal of Molecular Sciences, v.22, no.14, pp 1 - 13 | - |
dc.citation.title | International Journal of Molecular Sciences | - |
dc.citation.volume | 22 | - |
dc.citation.number | 14 | - |
dc.citation.startPage | 1 | - |
dc.citation.endPage | 13 | - |
dc.type.docType | Article | - |
dc.description.isOpenAccess | Y | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Biochemistry & Molecular Biology | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.relation.journalWebOfScienceCategory | Biochemistry & Molecular Biology | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Multidisciplinary | - |
dc.subject.keywordPlus | TERT-BUTYL CHLORIDE | - |
dc.subject.keywordPlus | THIOCHLOROFORMATE ESTERS | - |
dc.subject.keywordPlus | SN2-SN1 SPECTRUM | - |
dc.subject.keywordPlus | CHLOROFORMATE | - |
dc.subject.keywordPlus | MECHANISM | - |
dc.subject.keywordPlus | KINETICS | - |
dc.subject.keywordPlus | SCALE | - |
dc.subject.keywordPlus | DECOMPOSITION | - |
dc.subject.keywordPlus | HYDROLYSIS | - |
dc.subject.keywordPlus | PATHWAYS | - |
dc.subject.keywordAuthor | 1-adamantyl chlorothioformate | - |
dc.subject.keywordAuthor | Grunwald-Winstein equation | - |
dc.subject.keywordAuthor | solvolysis | - |
dc.subject.keywordAuthor | solvolysis-decomposition | - |
dc.subject.keywordAuthor | ionization pathway | - |
dc.subject.keywordAuthor | carboxylium ion | - |
dc.identifier.url | https://www.scopus.com/record/display.uri?eid=2-s2.0-85109343617&origin=inward&txGid=be2d31d4bef4252ee64536e642fc0c76#indexed-keywords | - |
Items in ScholarWorks are protected by copyright, with all rights reserved, unless otherwise indicated.
55 Hanyangdeahak-ro, Sangnok-gu, Ansan, Gyeonggi-do, 15588, Korea+82-31-400-4269 sweetbrain@hanyang.ac.kr
COPYRIGHT © 2021 HANYANG UNIVERSITY. ALL RIGHTS RESERVED.
Certain data included herein are derived from the © Web of Science of Clarivate Analytics. All rights reserved.
You may not copy or re-distribute this material in whole or in part without the prior written consent of Clarivate Analytics.