• Journal of the Korean Chemical Society
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• v.59 no.5
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• pp.373-378
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• 2015

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 N_T solvent nucleophilicity scale and Y_Cl 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 S_N2 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).