자동적정법에 의한 Alkyl Halogenoformate Esters의 가용매 분해반응에 대한 속도론적 연구
- Title
- 자동적정법에 의한 Alkyl Halogenoformate Esters의 가용매 분해반응에 대한 속도론적 연구
- Other Titles
- Kinetics and Mechanisms of Solvolyses of Alkyl Halogenoformate Esters
- Author
- 성미혜
- Alternative Author(s)
- Seong, Mi Hye
- Advisor(s)
- 경진범
- Issue Date
- 2010-02
- Publisher
- 한양대학교
- Degree
- Master
- Abstract
- The specific rates of the solvolyses of methyl fluoroformate (CH3OCOF) and ethyl fluoroformate (CH3CH2OCOF) in pure and several hydroxylic solvents have been measured at 40.0°C and 24.2°C using the titrimetric method. The extended Grunwald-Winstein equation has been applied to the solvolyses of methyl fluoroformate and ethyl fluoroformate. Analyses of the data using the extended Grunwald-Winstein equation to the specific rates of the solvolyses of methyl fluoroformate and ethyl fluoroformate lead to sensitivities toward changes in solvent nucleophilicity (l) of 1.33±0.09 and toward changes in solvent ionizing power (m) of 0.73±0.06, and to sensitivities toward changes in solvent nucleophilicity (l) of 1.34±0.14 and toward changes in solvent ionizing power of (m) 0.77±0.07, respectively. For four and five representative solvents, studies were made at several temperatures and activation parameters determined. For methanolysis, a solvent deuterium isotope effect of MeOH/MeOD is compatible with the incorporation of general-base catalysis into the substitution process. In conclusion, the solvolyses of methyl fluoroformate and ethyl fluoroformate are indicated to proceed by a bimolecular addition-elimination pathway in pure and several hydroxylic solvents considered. These observations are also compared with those previously reported for the corresponding chloroformate and fluoroformate esters.
- URI
- https://repository.hanyang.ac.kr/handle/20.500.11754/142845http://hanyang.dcollection.net/common/orgView/200000414113
- Appears in Collections:
- GRADUATE SCHOOL[S](대학원) > APPLIED CHEMISTRY(응용화학과) > Theses (Master)
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