双语化学辞典Chem Lexicon
反应 · 有机化学 · 还原反应 Organic chemistry · Reductions

沃尔夫-基斯纳还原Wolff–Kishner reduction

拼音Pinyin wò ěr fū jī sī nà huán yuán　别名Also 沃尔夫-基希纳-黄鸣龙还原；黄鸣龙还原； Wolff–Kishner–Huang Minlon reduction

定义Definition

沃尔夫-基斯纳还原是醛或酮先与肼生成腙，再在强碱、高温下放出氮气，使羰基还原为亚甲基的反应。黄鸣龙改良法（1946）使其成为简便的一锅操作。

In the Wolff–Kishner reduction an aldehyde or ketone forms a hydrazone with hydrazine, which loses nitrogen under strong base at high temperature, reducing C=O to CH₂. The Huang Minlon modification (1946) made it a convenient one-pot procedure.

机理Mechanism

羰基与肼缩合成腙；碱夺取 N–H 质子，碳原子质子化得重氮负离子前体；再次去质子化后放出 N₂ 生成碳负离子，被溶剂质子化得到烷烃。N₂ 的生成是不可逆驱动力。

The carbonyl condenses with hydrazine to the hydrazone; base removes an N–H and carbon is protonated; a second deprotonation expels N₂ to give a carbanion that is protonated by solvent. Loss of N₂ is the irreversible driving force.

由来与黄鸣龙改良Origin and the Huang Minlon modification

俄国的基斯纳（1911）和德国的沃尔夫（1912）分别独立报道，原法需封管加热和无水肼。中国化学家黄鸣龙 1946 年在哈佛大学改用水合肼、KOH 和高沸点溶剂二甘醇，先回流成腙、再蒸出水使温度升至约 200 °C 分解，产率高且可常压操作。这是第一个以中国人名字命名的有机反应。

Kishner in Russia (1911) and Wolff in Germany (1912) reported it independently, originally needing sealed tubes and anhydrous hydrazine. In 1946 at Harvard the Chinese chemist Huang Minlon used hydrazine hydrate, KOH and high-boiling diethylene glycol: reflux to form the hydrazone, distil off water, then heat to ~200 °C — high-yielding at atmospheric pressure. It is the first organic reaction named after a Chinese chemist.

适用范围Scope

适合对酸敏感但耐碱的底物，与克莱门森还原互补；不适用于对强碱敏感的酯、卤代烃等。

Suits base-stable, acid-sensitive substrates, complementing Clemmensen; esters and base-sensitive halides are problematic.

反应Reactions

R2C=O + N2H4 ⟶ R2C=NNH2 KOH, 200 °C⟶ R2CH2 + N2

黄鸣龙法：85% 水合肼、KOH、二甘醇，先回流 1 h，蒸出水后 190–200 °C 反应数小时

Huang Minlon: 85 % hydrazine hydrate, KOH and diethylene glycol; reflux 1 h, distil off water, then 190–200 °C for several hours

  1. 生成腙。

    Hydrazone formation.

  2. 碱促进的质子转移形成二亚胺型中间体。

    Base-mediated proton shifts give a diimide-type intermediate.

  3. 放出 N₂ 得碳负离子，质子化为烷烃。

    Loss of N₂ gives a carbanion that is protonated.

β-(对苯甲酰基)丙酸 ⟶ γ-苯基丁酸黄鸣龙法产率约 95%β- ⟶ γ-Phenyl group(Chemical yield≈ 95%)

黄鸣龙论文中的例子。

An example from Huang Minlon’s paper.

反应机理图Mechanism

红色弯箭头表示一对电子的移动方向：从电子来源（孤对电子或化学键）指向电子去向。Red curly arrows show where an electron pair moves: from its source (lone pair or bond) to its destination.

1

腙的 N–H 被夺取，负电荷推到碳上

The hydrazone N–H is removed; the charge moves onto carbon

2

碳被质子化

Carbon is protonated

3

再夺取 N–H，放出 N₂（驱动力）

A second N–H is removed and N₂ is released (the driving force)

H₂O
4

碳负离子质子化

The carbanion is protonated

5

C=O 被还原成 CH₂

C=O has become CH₂

年表Timeline

  • 1911

    基斯纳报道

    Kishner’s report

  • 1912

    沃尔夫报道

    Wolff’s report

  • 1946

    黄鸣龙改良法

    Huang Minlon modification