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Exercises · 9.24

Q.Suggest the name of a Lewis acid other than anhydrous aluminium chloride which can be used during ethylation of benzene.

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Friedel–Crafts alkylation requires a Lewis acid to generate the electrophile; ferric chloride (FeClX3\ce{FeCl3}) is a common alternative to AlClX3\ce{AlCl3} for ethylation of benzene.

Why Lewis acids matter in Friedel–Crafts alkylation

Benzene is electron-rich but stable; its π-cloud resists direct attack by weak electrophiles like ethyl chloride. The role of a Lewis acid is to accept a lone pair from the halogen in CHX3CHX2Cl\ce{CH3CH2Cl}, polarising the C–Cl bond so strongly that it either forms a carbocation (CHX3CHX2X+\ce{CH3CH2+}) or a highly activated complex. This electrophile is reactive enough to attack the benzene ring.

Anhydrous aluminium chloride is the textbook choice because it's a powerful Lewis acid (the small, highly charged AlX3+\ce{Al^{3+}} creates a strong electron deficiency). But several other metal halides share this property.

Alternative Lewis acids for ethylation

The key requirement: the metal centre must have an incomplete octet or accessible empty orbitals to accept electron pairs. Common alternatives include:

  1. Ferric chloride, FeClX3\ce{FeCl3} Iron(III) has empty 3d orbitals and accepts the chloride lone pair readily. It's slightly weaker than AlClX3\ce{AlCl3} but still very effective for alkylation. The mechanism is identical:

CHX3CHX2Cl+FeClX3→CHX3CHX2X++FeClX4X−\ce{CH3CH2Cl + FeCl3 -> CH3CH2^+ + FeCl4^-}

(or a polarised complex CHX3CHX2Xδ+−ClXδ−−FeClX3\ce{CH3CH2^{\delta+}—Cl^{\delta-}—FeCl3}).

  1. Boron trifluoride, BFX3\ce{BF3}

    Boron has only six valence electrons; BFX3\ce{BF3} is a classic Lewis acid. Often used with a co-catalyst or in liquid form.

  2. Zinc chloride, ZnClX2\ce{ZnCl2} …

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