Mechanistic Studies of the Solvolyses of Cyclohexanesulfonyl Chloride

다국어 초록 (Multilingual Abstract)

In this study, the solvolysis of cyclohexanesulfonyl chloride (1) was studied by kinetics in ethanol-water, methanol- water, acetone-water, and 2,2,2-trifluoroethanol (TFE)-water binary solvent systems. The rate constants were applied to the extended Grunwald-Winstein equation, to obtain the values of m = 0.41 and l = 0.81. These values suggested SN2 mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to 14.8 kcal·mol-1), the large negative activation entropy values (-29.7 to -38.7 cal·mol-1·K-1) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the SN2 mechanism.

참고문헌 (Reference)

1 Rogne, O J., 1294-, 1968

2 Robertson, R E., 4 : 213-, 1967

3 Ciuffarin, E, 2 : 268-, 1972

4 Bentley, T W., 98 : 7658-, 1976

5 Bentley, T W., 2 : 761-, 1994

6 Harris, J M., 96 : 4478-, 1974

7 D’Souza, M J., 9 : 914-, 2008

8 Kevill, D N., 20 : 431-, 2007

9 Kevill, D N., 20 : 431-, 2007

10 Grunwald, E., 70 : 846-, 1948

11 Bentley, T W., 57 : 2387-, 1992

12 Kevill, D N., 2 : 973-, 1995

13 고한중, "Rate and Product Studies on the Solvolyses of Allyl Chloroformate" 대한화학회 33 (33): 4117-4121, 2012

14 Han Joong Koh, "Rate and Product Studies of 5-Dimethylamino-Naphthalene-1-Sulfonyl Chloride under Solvolytic Conditions" 대한화학회 35 (35): 2285-2289, 2014

15 구인선, "Limitations of the Transition State Variation Model. Part 8. Dual Reaction Channels for Solvolyses of 3,4-Dimethoxybenzenesulfonyl Chloride" 대한화학회 28 (28): 2377-2381, 2007

16 고한중, "Correlation of Rates of Solvolysis of Diphenylacetyl Chloride Using Extended Grunwald–Winstein Equation" 대한화학회 36 (36): 2429-2433, 2015

17 고한중, "Application of the Extended Grunwald-Winstein Equation to the Solvolyses of Phenyl Methanesulfonyl Chloride in Aqueous Binary Mixtures" 대한화학회 32 (32): 1897-1901, 2011

18 고한중, "A Kinetic Study on Solvolysis of 9-Fluorenylmethyl Chloroformate" 대한화학회 32 (32): 3799-3801, 2011