双语化学辞典Chem Lexicon
研究生Graduate 结构、立体化学与物理有机 Structure, stereochemistry & physical organic chemistry

斯温–斯科特方程Swain–Scott equation

\[\lg\frac{k}{k_0} = s\,n\]

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 sensitivity1
\(k_0\)与水反应的速率常数rate constant with waterL·mol⁻¹·s⁻¹

推导Derivation

  1. 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.

  2. 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).