双语化学辞典Chem Lexicon
化合物 · 有机化学 · 芳香烃 Organic chemistry · Aromatic hydrocarbons

苯Benzene

拼音Pinyin běn 别名Also 安息油;benzol; cyclohexa-1,3,5-triene

定义Definition

苯是分子式为 C₆H₆ 的最简单芳香烃,六个碳原子构成平面正六边形,六个 π 电子在环上离域,使其具有特殊的稳定性(芳香性)。常温下为无色、有特殊气味的易燃液体。

Benzene is the simplest aromatic hydrocarbon, C₆H₆. Its six carbon atoms form a planar regular hexagon with six π electrons delocalized around the ring, which gives it unusual stability (aromaticity). At room temperature it is a colourless, flammable liquid with a sweet odour.

结构与成键Structure and bonding

每个碳原子 sp² 杂化,形成 C–C 与 C–H σ 键骨架;剩余的 p 轨道垂直于环平面,侧面重叠成环状 π 体系。六个 C–C 键长相等(139 pm),介于单键(154 pm)与双键(134 pm)之间。苯的氢化热比假想的“环己三烯”低约 150 kJ/mol,这部分即共振能(离域能)。

Each carbon is sp² hybridized, forming the σ framework of C–C and C–H bonds; the remaining p orbitals stand perpendicular to the ring and overlap into a cyclic π system. All six C–C bonds are 139 pm, between a single (154 pm) and a double bond (134 pm). Benzene's heat of hydrogenation is about 150 kJ/mol lower than that of a hypothetical cyclohexatriene; this is the resonance (delocalization) energy.

发现与结构假说Discovery and the structural hypothesis

法拉第于 1825 年从照明煤气的油状残余物中分离出苯。苯的 C:H = 1:1 却难以发生加成反应,这一矛盾促使凯库勒在 1865 年提出单双键交替的六元环结构,并于 1872 年补充“振荡假说”,以解释邻位二取代苯只有一种。

Faraday isolated benzene in 1825 from the oily residue of illuminating gas. Its 1:1 C:H ratio paired with a reluctance to undergo addition was a puzzle. Kekulé proposed in 1865 a six-membered ring of alternating single and double bonds, and in 1872 added an oscillation hypothesis to explain why only one ortho-disubstituted benzene exists.

理论演变How the theory evolved

杜瓦、拉登堡等人曾提出杜瓦苯、棱晶烷等替代结构。1929 年朗斯代尔用 X 射线证明六甲基苯环是平面且键长相等。1930 年代鲍林以共振论描述苯,休克尔则用分子轨道法提出 4n+2 规则,将芳香性推广到离子与杂环体系。

Dewar, Ladenburg and others proposed alternative structures such as Dewar benzene and prismane. In 1929 Lonsdale's X-ray work showed the hexamethylbenzene ring to be planar with equal bonds. In the 1930s Pauling described benzene with resonance theory, while Hückel's molecular-orbital treatment gave the 4n+2 rule, extending aromaticity to ions and heterocycles.

用途与安全Uses and safety

苯是生产乙苯(苯乙烯)、异丙苯(苯酚、丙酮)、环己烷(尼龙)和硝基苯(苯胺)的基础原料。苯被 IARC 列为 1 类致癌物,长期接触可导致再生障碍性贫血和白血病,实验中常以甲苯替代。

Benzene is the feedstock for ethylbenzene (styrene), cumene (phenol and acetone), cyclohexane (nylon) and nitrobenzene (aniline). IARC classifies it as a Group 1 carcinogen; chronic exposure causes aplastic anaemia and leukaemia, so toluene is often used as a laboratory substitute.

反应Reactions

C6H6 + E+ ⟶ [C6H6E]+σ 络合物 ⟶ C6H5E + H+C6H6 + E+ ⟶ [C6H6E]+(σ ) ⟶ C6H5E + H+

典型反应为亲电芳香取代,需路易斯酸或强酸催化;加成反应只在剧烈条件下发生。

Its typical reaction is electrophilic aromatic substitution, catalysed by a Lewis or strong acid; addition happens only under forcing conditions.

C6H6 + HNO3 浓 H2SO4, 50–60 °C⟶ C6H5NO2 + H2OC6H6 + HNO3 conc. H2SO4, 50–60 °C⟶ C6H5NO2 + H2O

硝化:生成硝基苯

Nitration to nitrobenzene

C6H6 + Br2 FeBr3⟶ C6H5Br + HBr

卤代:生成溴苯

Bromination to bromobenzene

C6H6 + CH3Cl AlCl3⟶ C6H5CH3 + HCl

傅-克烷基化:生成甲苯

Friedel–Crafts alkylation to toluene

C6H6 + 3 H2 Ni, 加热加压⟶ C6H12C6H6 + 3 H2 Ni,⟶ C6H12

催化加氢:生成环己烷

Catalytic hydrogenation to cyclohexane

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

苯环 π 电子进攻硝酰阳离子 NO₂⁺

The ring π electrons attack the nitronium ion NO₂⁺

慢slow
2

σ 络合物(芳基正离子)失去质子,恢复芳香性

The σ-complex (arenium ion) loses H⁺ and regains aromaticity

快fast
3

硝基苯

Nitrobenzene

化学性质Chemical properties

易发生亲电取代(硝化、卤代、磺化、傅-克反应),难加成,不使酸性 KMnO₄ 褪色。

Undergoes electrophilic substitution (nitration, halogenation, sulfonation, Friedel–Crafts) readily, resists addition, and does not decolourise acidic KMnO₄.

燃烧时火焰明亮并伴有浓烟:2 C₆H₆ + 15 O₂ → 12 CO₂ + 6 H₂O。

Burns with a bright, sooty flame: 2 C₆H₆ + 15 O₂ → 12 CO₂ + 6 H₂O.

年表Timeline

  • 1825

    法拉第从照明煤气中分离出苯

    Faraday isolates benzene from illuminating gas

  • 1834

    米切利希由苯甲酸制得苯,并命名 benzin

    Mitscherlich makes it from benzoic acid and names it benzin

  • 1865

    凯库勒提出六元环结构

    Kekulé proposes the six-membered ring

  • 1929

    朗斯代尔用 X 射线衍射证明苯环为平面、键长均等

    Lonsdale's X-ray study shows a planar ring with equal bonds

  • 1931

    休克尔提出 4n+2 芳香性规则

    Hückel formulates the 4n+2 rule