|
KMID : 1059520150590050373
|
|
Journal of the Korean Chemical Society
2015 Volume.59 No. 5 p.373 ~ p.378
|
|
|
Studies of Solvolyses of Di-n-butyl Phosphorochloridate by Extended Grunwald-Winstein Equation
|
|
Kang Min-Sung
Kim Cheul-Ju
Kang Suk-Jin
Koh Han-Joong
|
|
|
Abstract
|
|
|
|
The solvolysis rate constants of di-n-butyl phosphorochloridate ((CH3CH2CH2CH2O)2POCl, 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).
|
|
|
KEYWORD
|
|
|
Di-n-butyl phosphorochloridate, Extended Grunwald-Winstein equation, SN2 mechanism, Kivinen’s equation
|
|
|
FullTexts / Linksout information
|
|
|
|
|
|
Listed journal information
|
|
|