Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions
- Title
- Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions
- Author
- 박경호
- Keywords
- Grunwald-Winstein equation; 1-adamantyl chlorothioformate; solvolysis; solvolysis-decomposition; ionization pathway; carboxylium ion
- Issue Date
- 2021-07
- Publisher
- Multidisciplinary Digital Publishing Institute (MDPI)
- Citation
- International Journal of Molecular Sciences, v. 22, NO. 14, article no. 7394, Page. 1.0-13.0
- 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.
- URI
- https://www.scopus.com/record/display.uri?eid=2-s2.0-85109343617&origin=inward&txGid=be2d31d4bef4252ee64536e642fc0c76#indexed-keywordshttps://repository.hanyang.ac.kr/handle/20.500.11754/187970
- ISSN
- 1661-6596;1422-0067
- DOI
- 10.3390/ijms22147394
- Appears in Collections:
- COLLEGE OF SCIENCE AND CONVERGENCE TECHNOLOGY[E](과학기술융합대학) > CHEMICAL AND MOLECULAR ENGINEERING(화학분자공학과) > Articles
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- 109322_박경호.pdfDownload
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