Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Mechanistic Studies of the Solvolyses of Cyclohexanesulfonyl Chloride

  • Kang, Suk Jin (Department of Science Education, Jeonju National University of Education) ;
  • Koh, Han Joong (Department of Science Education, Jeonju National University of Education)
  • Received : 2019.03.15
  • Accepted : 2019.04.03
  • Published : 2019.08.20
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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 $S_N2$ mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to $14.8kcal{\cdot}mol^{-1}$), the large negative activation entropy values (-29.7 to $-38.7cal{\cdot}mol^{-1}{\cdot}K^{-1}$) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the $S_N2$ mechanism.

Keywords

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Scheme 1. Reaction pathways for the solvolysis of benzenesulfonyl chloride.

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Figure 1. Plot of log (k/ko) for solvolyses cyclohexanesulfonyl chloride (1) in 31 solvents at 55.0 ℃ against YCl.

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Scheme 2. Push-pull reaction.

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Figure 2. Plot of log (k/ko) for solvolyses of cyclohexanesulfonyl chloride (1) in 31 solvents at 55.0 ℃ against (0.81NT + 0.41YCl).

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Scheme 3. Solvent kinetic isotope effect.

Table 1. Rate constants for the solvolyses of 1a in binary solvent mixtures at 55.0 ℃, and the NT and the YCl values for the solvents

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Table 2. Extended Grunwald-Winstein correlation of the kinetics of solvolytic displacement of chloride

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Table 3. Rate constants and activation parameters for the solvolyses of 1a at various temperatures

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Table 4. Solvent kinetic isotope effects (SKIEs) for the solvolyses of 1 at 55.0 ℃.

JCGMDC_2019_v63n4_233_t0004.png 이미지

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