확장된 Grunwald-Winstein 식에 의한 Di-n-butyl Phosphorochloridate의 가용매 분해반응 연구
Studies of Solvolyses of Di-n-butyl Phosphorochloridate by Extended Grunwald-Winstein Equation
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초록
Di-n-butyl phosphorochloridate((CH3CH2CH2CH2O)2POCl, 1)의 가용매 분해반응의 속도상수를 여러 가지 용매 중에서 구하였다. 반응용매 28개의 속도상수를 이용하여 확장된 Grunwald-Winstein 식에 의하여 구한 용매의 친핵성도와 이온화력에 대한 기질의 민감도(l = 1.40, m = 0.42)는 SN2 반응임을 예상할 수 있다. 이를 뒷받침할 수 있는 추가 요소들은 상대적으로 작 은 양의 값의 ΔH≠(8.0 ~ 15.9 kcal·mol−1)와 큰 음의 값의 ΔS≠(−25.8~−53.1 cal·mol−1·K−1), Kivinen의 n 값(0.9~1.7) 그리고 용매 동위원소효과 값(1.69)이다.
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).
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