\[\lg\frac{k}{k_0} = s\,n\]
含义Meaning
SN2 反应中亲核试剂的相对亲核性 n(以水为 0,以 CH₃Br 为底物 s = 1)。
Relative nucleophilicity n in SN2 reactions (water n = 0; substrate CH₃Br s = 1).
符号说明Symbols
| 符号Symbol | 含义 Meaning | 单位 Unit |
|---|---|---|
| \(n\) | 亲核性常数(I⁻ 5.0,OH⁻ 4.2,Cl⁻ 3.0)nucleophilicity constant (I⁻ 5.0, OH⁻ 4.2, Cl⁻ 3.0) | 1 |
| \(s\) | 底物敏感度substrate sensitivity | 1 |
| \(k_0\) | 与水反应的速率常数rate constant with water | L·mol⁻¹·s⁻¹ |
推导Derivation
与哈米特方程类似:选定标准底物 CH₃Br(s = 1)测各亲核试剂相对水的速率,得 n。
Like Hammett: define s = 1 for CH₃Br and measure rates relative to water.
其他底物测定 s,即可预测任意组合的相对速率。
Determine s for other substrates to predict any combination.
适用条件与局限Assumptions & limitations
亲核性强烈依赖溶剂(质子溶剂中 I⁻ > Br⁻ > Cl⁻ > F⁻,非质子溶剂中顺序可反转)。
Strongly solvent-dependent (in protic solvents I⁻ > Br⁻ > Cl⁻ > F⁻; can reverse in aprotic solvents).