Correlation of the Rates of Solvolysis of i-Butyl Fluoroformate and a Consideration of Leaving-Group Effects
- Authors
- Lee, Yelin; Park, Kyoung-Ho; Seong, Mi Hye; Kyong, Jin Burm; Kevill, Dennis N.
- Issue Date
- Nov-2011
- Publisher
- MDPI
- Keywords
- i-butyl fluoroformate; Grunwald-Winstein equation; leaving group effect; addition-elimination; solvolysis
- Citation
- INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES, v.12, no.11, pp 7806 - 7817
- Pages
- 12
- Indexed
- SCIE
SCOPUS
- Journal Title
- INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
- Volume
- 12
- Number
- 11
- Start Page
- 7806
- End Page
- 7817
- URI
- https://scholarworks.bwise.kr/erica/handle/2021.sw.erica/36486
- DOI
- 10.3390/ijms12117806
- ISSN
- 1661-6596
1422-0067
- Abstract
- The specific rates of solvolysis of isobutyl fluoroformate (1) have been measured at 40.0 degrees C in 22 pure and binary solvents. These results correlated well with the extended Grunwald-Winstein (G-W) equation, which incorporated the N-T solvent nucleophilicity scale and the Y-Cl solvent ionizing power scale. The sensitivities (l and m-values) to changes in solvent nucleophilicity and solvent ionizing power, and the k(F)/k(Cl) values are very similar to those observed previously for solvolyses of n-octyl fluoroformate, consistent with the additional step of an addition-elimination pathway being rate-determining. The solvent deuterium isotope effect value (k(MeOH)/k(MeOD)) for methanolysis of 1 was determined, and for solvolyses in ethanol, methanol, 80% ethanol, and 70% TFE, the values of the enthalpy and the entropy of activation for the solvolysis of 1 were also determined. The results are compared with those reported earlier for isobutyl chloroformate (2) and other alkyl haloformate esters and mechanistic conclusions are drawn.
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