双语化学辞典Chem Lexicon
反应 · 有机化学 · 有机金属试剂 Organic chemistry · Organometallic reagents

格氏反应Grignard reaction

拼音Pinyin gé shì fǎn yìng　别名Also 格利雅反应； Grignard addition

定义Definition

格氏反应是有机镁卤化物（格氏试剂 RMgX）作为碳亲核试剂，加成到醛、酮、酯、CO₂、环氧化物等亲电试剂上形成新 C–C 键的反应，水解后得到醇或羧酸。

The Grignard reaction uses organomagnesium halides (Grignard reagents, RMgX) as carbon nucleophiles that add to aldehydes, ketones, esters, CO₂, epoxides and other electrophiles to form new C–C bonds; aqueous work-up gives alcohols or carboxylic acids.

试剂制备Preparing the reagent

卤代烃与镁屑在无水乙醚或 THF 中反应生成 RMgX，常加碘或 1,2-二溴乙烷引发。醚的氧与镁配位稳定试剂（溶液中存在施伦克平衡 2RMgX ⇌ R₂Mg + MgX₂）。必须严格无水、无质子溶剂：水、醇、羧酸会立即把它质子化为 R–H。

An alkyl or aryl halide reacts with magnesium turnings in dry ether or THF, often initiated with iodine or 1,2-dibromoethane. Ether oxygens coordinate and stabilise Mg (the Schlenk equilibrium 2RMgX ⇌ R₂Mg + MgX₂). Strictly anhydrous, aprotic conditions are essential: water, alcohols and acids protonate it to R–H at once.

产物规律Product patterns

甲醛 → 伯醇；其他醛 → 仲醇；酮 → 叔醇；酯与两分子试剂反应 → 叔醇；CO₂ → 羧酸；环氧乙烷 → 增加两个碳的伯醇；腈 → 酮（水解亚胺后）。

Formaldehyde → primary alcohols; other aldehydes → secondary; ketones → tertiary; esters consume two equivalents → tertiary alcohols; CO₂ → carboxylic acids; ethylene oxide → primary alcohols two carbons longer; nitriles → ketones after hydrolysis.

由来Origin

法国化学家维克多·格利雅在导师巴比耶工作基础上于 1900 年发现，1912 年因此获诺贝尔化学奖。它是最早、最常用的碳–碳键形成方法之一。

Discovered in 1900 by the French chemist Victor Grignard, building on his mentor Barbier’s work; he received the 1912 Nobel Prize in Chemistry. It remains one of the most used C–C bond-forming methods.

反应Reactions

R–MgX + R′2C=O ⟶ R′2C(R)–OMgX H3O+⟶ R′2C(R)–OH

无水乙醚或 THF，0 °C 至回流，氮气保护；稀酸（NH₄Cl 饱和溶液）后处理

Dry ether or THF under N₂, 0 °C to reflux; quench with dilute acid or saturated NH₄Cl

  1. 镁插入 C–X 键生成 RMgX。

    Mg inserts into C–X to give RMgX.

  2. 碳负离子性的 R 进攻羰基碳，形成烷氧基镁盐。

    The carbanion-like R attacks the carbonyl carbon, forming a magnesium alkoxide.

  3. 酸性水解得到醇。

    Acidic work-up gives the alcohol.

PhMgBr + CO2 ⟶ PhCOOMgBr H3O+⟶ PhCOOH

制备苯甲酸。

Preparation of benzoic acid.

CH3MgI + (CH3)2CO ⟶ (CH3)3COH

制备叔丁醇。

Preparation of tert-butanol.

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

C–Mg 键电子（碳负性）进攻羰基碳

The C–Mg bond electrons (carbanion-like) attack the carbonyl carbon

2

烷氧基镁盐，酸性水解

Magnesium alkoxide, then acidic work-up

H₃O⁺
3

叔丁醇

tert-Butanol

年表Timeline

  • 1899

    巴比耶报道镁介导的一锅加成

    Barbier reports a one-pot magnesium-mediated addition

  • 1900

    格利雅分离出有机镁试剂

    Grignard prepares the organomagnesium reagent separately

  • 1912

    格利雅获诺贝尔化学奖

    Grignard receives the Nobel Prize