双语化学辞典Chem Lexicon
反应 · 有机化学 · 芳香取代 Organic chemistry · Aromatic substitution

赖默-蒂曼反应Reimer–Tiemann reaction

拼音Pinyin lài mò dì màn fǎn yìng　别名Also 酚的甲酰化； ortho-formylation of phenols

定义Definition

赖默-蒂曼反应是苯酚在强碱水溶液中与氯仿反应，主要在羟基邻位引入醛基（–CHO）的反应，产物如水杨醛。活性中间体是二氯卡宾。

The Reimer–Tiemann reaction formylates phenols, mainly ortho to the hydroxyl, by treatment with chloroform in strong aqueous base, giving products such as salicylaldehyde. The reactive intermediate is dichlorocarbene.

机理Mechanism

OH⁻ 夺取氯仿的质子得 CCl₃⁻，α-消除失去 Cl⁻ 生成二氯卡宾 :CCl₂。富电子的酚氧负离子邻位进攻缺电子的卡宾，形成二氯甲基中间体，再经水解把 –CHCl₂ 转化为 –CHO。

Hydroxide deprotonates chloroform to CCl₃⁻, which loses Cl⁻ (α-elimination) to form dichlorocarbene. The electron-rich phenoxide attacks the electron-poor carbene at the ortho position, giving a dichloromethyl intermediate that is hydrolysed from –CHCl₂ to –CHO.

由来Origin

德国化学家卡尔·赖默和费迪南德·蒂曼于 1876 年报道。

Reported in 1876 by the German chemists Karl Reimer and Ferdinand Tiemann.

特点Features

邻位选择性常归因于酚氧负离子与卡宾之间的静电及钠离子的作用；产率一般中等。反应在两相体系中进行，可加相转移催化剂改进。吡咯、吲哚等富电子杂环也能反应，吡咯还会发生扩环（生成 3-氯吡啶）。

Ortho selectivity is attributed to electrostatic interaction between phenoxide and carbene and to the counter-ion; yields are usually moderate. The reaction is biphasic and phase-transfer catalysts help. Electron-rich heterocycles such as pyrrole and indole also react; pyrrole can ring-expand to 3-chloropyridine (Ciamician–Dennstedt).

反应Reactions

C6H5OH + CHCl3 + 3 NaOH ⟶ o-HOC6H4CHO + 3 NaCl + 2 H2O

浓 NaOH 水溶液，60–70 °C，再酸化

Concentrated aqueous NaOH, 60–70 °C, then acidification

  1. CHCl₃ 脱质子并 α-消除生成 :CCl₂。

    CHCl₃ is deprotonated and α-eliminates to :CCl₂.

  2. 酚氧负离子邻位进攻二氯卡宾。

    Phenoxide attacks dichlorocarbene at the ortho carbon.

  3. 互变异构恢复芳香性，–CHCl₂ 水解为 –CHO。

    Tautomerisation restores aromaticity and –CHCl₂ hydrolyses to –CHO.

苯酚 ⟶ 水杨醛主+ 对羟基苯甲醛少Phenol ⟶ (major)+ Hydroxy groupBenzaldehyde(minor)

以邻位产物为主。

The ortho product dominates.

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

OH⁻ 夺取氯仿的 H

OH⁻ removes the proton of chloroform

2

α-消除失去 Cl⁻，生成二氯卡宾

α-Elimination of Cl⁻ gives dichlorocarbene

3

酚氧负离子的邻位进攻缺电子的卡宾

The ortho carbon of the phenoxide attacks the electron-poor carbene

质子转移、水解H⁺ shifts, hydrolysis
4

二氯甲基在碱中水解成醛基

The CCl₂ group is hydrolysed to CHO in base

5

水杨醛

Salicylaldehyde

年表Timeline

  • 1876

    赖默与蒂曼报道该反应

    Reimer and Tiemann report the reaction

  • 1950s

    二氯卡宾中间体被确认

    The dichlorocarbene intermediate is established