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http://dx.doi.org/10.5012/jkcs.2015.59.5.373

Studies of Solvolyses of Di-n-butyl Phosphorochloridate by Extended Grunwald-Winstein Equation  

Kang, Min Sung (Department of Chemistry, Chonbuk National University)
Kim, Cheul Ju (Department of Chemistry, Chonbuk National University)
Kang, Suk Jin (Department of Science Education, Jeonju National University of Education.)
Koh, Han Joong (Department of Science Education, Jeonju National University of Education.)
Publication Information
Journal of the Korean Chemical Society / v.59, no.5, 2015 , pp. 373-378 More about this Journal
Abstract
The solvolysis rate constants of di-n-butyl phosphorochloridate ((CH3CH2CH2CH2O)2POCI, 1) in 28 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with the sensitivities values of 1.40 and 0.42 for l and m, respectively. These l and m values can be considered to support an SN2 reaction pathway. This interpretation is further supported by the activation parameters, i.e., relatively small positive ΔH≠ (8.0 to 15.9 kcal·mol−1 ) values and large negative ΔS≠ (−25.8 to −53.1 cal·mol−1 ·K−1 ) values, the Kivinen’s n values (0.9~1.7), and the solvent kinetic isotope effect (1.62).
Keywords
Di-n-butyl phosphorochloridate; Extended Grunwald-Winstein equation; $S_N2$ mechanism; Kivinen’ s equation;
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