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http://dx.doi.org/10.5012/bkcs.2014.35.8.2285

Rate and Product Studies of 5-Dimethylamino-Naphthalene-1-Sulfonyl Chloride under Solvolytic Conditions  

Koh, Han Joong (Department of Science Education, Jeonju National University of Education)
Kang, Suk Jin (Department of Science Education, Jeonju National University of Education)
Publication Information
Bulletin of the Korean Chemical Society / v.35, no.8, 2014 , pp. 2285-2289 More about this Journal
Abstract
The solvolysis rate constants of 5-dimethylamino-naphthalene-1-sulfonyl chloride ($(CH_3)_2NC_{10}H_6SO_2Cl$, 1) in 31 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale with sensitivity values of $0.96{\pm}0.09$ and $0.53{\pm}0.03$ for l and m, respectively; the correlation coefficient value was 0.955. These l and m values can be considered to support an $S_N2$ reaction pathway having a transition state (TS) structure similar to that of the benzenesulfonyl chloride reaction. This interpretation is further supported by the activation parameters, i.e., relatively small positive ${\Delta}H^{\neq}$ (12.0 to $15.9kcal{\cdot}mol^{-1}$) and large negative ${\Delta}S^{\neq}$ (-23.1 to $-36.3cal{\cdot}mol^{-1}{\cdot}K^{-1}$) values, and the solvent kinetic isotope effects (SKIEs, 1.34 to 1.88). Also, the selectivity values (S = 1.2 to 2.9) obtained in binary solvents are consistent with the proposed mechanism.
Keywords
5-Dimethylamino-naphthalene-1-sulfonyl chloride; Extended Grunwald-Winstein equation; $S_N2$ mechanism; Solvent kinetic isotope effect; Product selectivity;
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