Solvolysis of (1S)-(+)-Menthyl Chloroformate in Various Mixed Solvents
2
조회
0
다운로드
0
인용
0
참고문헌
키워드
초록
The solvolysis of (1s)-(+)-menthyl chloroformate (1) were studied kinetically in 28 pure and various mixed solvents. The analysis using the extended Grunwald-Winstein equation in the solvolysis of 1 obtained the l value of 2.46 ± 0.18, the m value of 0.91 ± 0.07, and the correlation coefficient of 0.950. The solvolysis of 1 might proceed via an associative SN2 mechanism enhancing bond making than bond breaking in the transition state (TS). The value of l/m is 2.7 within the ranges of value found in associative SN2 reaction. This interpretation is further supported by a relatively large solvent kinetic isotope effect (SKIE, 2.16).
Abstract
The solvolysis of (1s)-(+)-menthyl chloroformate (1) were studied kinetically in 28 pure and various mixed solvents. The analysis using the extended Grunwald-Winstein equation in the solvolysis of 1 obtained the l value of 2.46 ± 0.18, the m value of 0.91 ± 0.07, and the correlation coefficient of 0.950. The solvolysis of 1 might proceed via an associative SN2 mechanism enhancing bond making than bond breaking in the transition state (TS). The value of l/m is 2.7 within the ranges of value found in associative SN2 reaction. This interpretation is further supported by a relatively large solvent kinetic isotope effect (SKIE, 2.16).
참고문헌 (15)
- Berthelot, M, , Et Phys, 65, pp.385~ (1862)
- Hughes, E. D, "Structure and Mechanism in Organic Chemistry, Cornell Univ", Chem. Soc, 244 (1935)
- Koh, H. J, , Phosphorus, Sulfur, and Silicon, 185, pp.865~ (2010)
- 고한중, "Kinetic Studies of the Solvolyses of 2,2,2-Trichloro-1,1-Dimethylethyl Chloroformate", Bulletin of the Korean Chemical Society, 31(4), pp.835~839 (2010), 대한화학회
- Winstein, S, , J. Am. Chem. Soc, 73, pp.2700~ (1951)
- Kevill, D. N, , Org. Biomolecular Chem, 4, pp.1580~ (2006)
- Kyong, J. B., , J. Org. Chem, 65, pp.8051~ (2000)
- Yew, K. H., , Chem. Soc., Perkin Trans, 2, pp.2263~ (1995)
- Kyong, J. B., , Bull. Korean Chem. Soc., 21, pp.662~ (2000)
- 고한중, "Kinetic Studies of the Solvolyses of Phenyl 4-Methylphenoxy Thiophosphinyl Chloride", Bulletin of the Korean Chemical Society, 30(10), pp.2437~2439 (2009), 대한화학회
- Bentley, T. W., , J. Am. Chem. Soc, 104, pp.5741~ (1982)
- Bentley, T. W, , J. Chem. Soc., Perkin Trans (1989)
- Bentley, T. W, , J. Am. Chem. Soc., 98, pp.7658~ (1976)
- Eyring, H., "Basic Chemical Kinetics" (1980), Wiley-Interscience
- Guggenheim, E. A, , Philos. Mag, 2, pp.538~ (1926)