双语化学辞典Chem Lexicon
机理 · 有机化学 · 反应机理 Organic chemistry · Reaction mechanisms

消除反应Elimination reaction

拼音Pinyin xiāo chú fǎn yìng 别名Also β-消除;β- elimination

定义Definition

消除反应是从分子相邻的两个原子上各除去一个原子或基团,形成双键(或三键)的反应,最常见的是从卤代烃脱去 HX、从醇脱去 H₂O 生成烯烃。主要机理有 E1、E2 和 E1cB。

An elimination reaction removes an atom or group from each of two adjacent atoms to form a double (or triple) bond — commonly loss of HX from haloalkanes or H₂O from alcohols to give alkenes. The main mechanisms are E1, E2 and E1cB.

机理谱Mechanistic spectrum

E2:一步协同,速率 = k[底物][碱],需反式共平面;E1:先离去成碳正离子再失 β-H,一级动力学;E1cB:先失去酸性 β-H 成碳负离子再离去(需吸电子基稳定)。三者构成一个连续谱。

E2: concerted, rate = k[substrate][base], anti-periplanar; E1: ionisation first then β-H loss, first order; E1cB: β-H removal first to a carbanion, then loss of the leaving group (needs an acceptor). They form a continuum.

区域规则Regiochemistry

扎伊采夫规则:一般生成取代较多、更稳定的烯烃;大位阻碱(t-BuOK)或差离去基团(–NMe₃⁺、–F)时生成取代较少的霍夫曼烯烃。

Zaitsev: usually the more substituted, more stable alkene; bulky bases (t-BuOK) or poor leaving groups (–NMe₃⁺, –F) give the less substituted Hofmann alkene.

与取代的竞争Competition with substitution

强碱、高温、位阻大的底物和碱有利于消除;强亲核弱碱(I⁻、RS⁻)、低温有利于取代。叔卤代烃与强碱主要 E2,与弱亲核试剂在质子溶剂中 SN1/E1 混合。

Strong bases, heat and hindered substrates or bases favour elimination; good nucleophiles that are weak bases (I⁻, RS⁻) and low temperature favour substitution. Tertiary halides give E2 with strong bases and SN1/E1 mixtures in protic solvents.

反应Reactions

H–C–C–X + B− ⟶ C=C + H–B + X−

强碱(醇钠、t-BuOK)加热;或酸催化醇脱水

Strong base (alkoxides, t-BuOK) with heat, or acid-catalysed dehydration of alcohols

  1. 碱夺取 β-H(E2、E1cB)或离去基团先离去(E1)。

    Base removes the β-H (E2, E1cB) or the leaving group departs first (E1).

  2. 形成 π 键。

    The π bond forms.

CH3CHBrCH2CH3 + KOH(醇) ⟶ CH3CH=CHCH3主+ CH2=CHCH2CH3CH3CHBrCH2CH3 + KOH ⟶ CH3CH=CHCH3(major)+ CH2=CHCH2CH3

扎伊采夫产物为主。

Zaitsev product predominates.

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

碱夺取 β-H,同时形成 C=C 并赶走 Br⁻;H 与 Br 反式共平面

The base takes the β-H while C=C forms and Br⁻ leaves; H and Br anti-periplanar

2

一步完成,速率 = k[底物][碱]

One step; rate = k[substrate][base]

年表Timeline

  • 1875

    扎伊采夫提出消除规则

    Zaitsev formulates his elimination rule

  • 1851

    霍夫曼消除

    Hofmann elimination

  • 1940s

    英戈尔德系统阐明 E1/E2

    Ingold systematises E1/E2