Friedel-Crafts Reaction — Notes &
Mechanisms
Introduction:
Friedel-Crafts reactions are a type of electrophilic aromatic
substitution reaction in which an aromatic compound reacts
with an alkyl halide or acyl halide in the presence of a Lewis
acid catalyst like AlCl₃ to form alkylated or acylated aromatic
compounds.
There are two main types:
1. Friedel-Crafts Alkylation
2. Friedel-Crafts Acylation
1. Friedel-Crafts Alkylation
General Reaction: Aromatic compound + Alkyl halide → Alkyl
aromatic compound
(in presence of AlCl₃ catalyst)
Example: Benzene + CH₃Cl → Toluene
Mechanism:
Step 1: Formation of the electrophile
Step 2: Attack of the aromatic ring The benzene ring donates
a pair of π electrons to the methyl carbocation, forming a
resonance-stabilized arenium ion (carbocation
intermediate).
Step 3: Loss of a proton A proton is removed by AlCl₄⁻,
restoring aromaticity.
2. Friedel-Crafts Acylation
General Reaction: Aromatic compound + Acyl halide →
Aromatic ketone
(in presence of AlCl₃ catalyst)
Example: Benzene + CH₃COCl → Acetophenone
Mechanism:
Step 1: Formation of the acylium ion (electrophile)
CH_3COCl + AlCl_3 → CH_3CO^+ + AlCl_4^-
Step 2: Attack of the aromatic ring The benzene ring donates
a pair of π electrons to the acylium ion, forming a resonance-
stabilized carbocation intermediate.
Step 3: Loss of a proton A proton is abstracted by AlCl₄⁻,
restoring the aromatic ring.
C_6H_5COCH_3 + H^+ + AlCl_4^-
Important Notes:
Alkylation Limitations: Can lead to polyalkylation and
carbocation rearrangements.
Acylation Advantage: No rearrangement, and usually only
one product forms.
Applications:
Synthesis of aromatic ketones, pharmaceuticals, dyes, and
perfumes.
Industrial preparation of toluene, ethylbenzene, and
acetophenone.
Perkin Reaction and Its
Mechanism
Introduction
The Perkin reaction is a classic organic reaction discovered
by William Henry Perkin in 1868. It is an important method
for the synthesis of α,β-unsaturated aromatic acids by the
condensation of an aromatic aldehyde with an acid
anhydride in the presence of a base, typically a salt of the
acid like sodium acetate.
This reaction has significance in both industrial and
laboratory-scale syntheses for the preparation of various
aromatic cinnamic acid derivatives, dyes, and fragrances.
General Reaction
Aromatic Aldehyde + Acid Anhydride + Base (usually Sodium
Acetate) → α,β-Unsaturated Aromatic Acid
Example:
Benzaldehyde + Acetic anhydride → Cinnamic acid
Equation:
C₆H₅CHO + (CH₃CO)₂O → C₆H₅CH=CHCOOH
Mechanism of the Perkin Reaction
The mechanism of the Perkin reaction involves several key
steps:
Step 1: Formation of Enolate Ion
The base (sodium acetate) abstracts a proton from the
methyl group of the acid anhydride to form an enolate ion.
(CH₃CO)₂O + CH₃COO⁻ → CH₂⁻COO(COCH₃)
Step 2: Nucleophilic Attack on the Aldehyde
The enolate ion attacks the carbonyl carbon of the aromatic
aldehyde to form a β-hydroxy intermediate.
CH₂⁻COO(COCH₃) + Ar-CHO → Ar-CH(OH)-CH₂-
COO(COCH₃)
Step 3: Elimination of Acetic Acid
The β-hydroxy intermediate undergoes elimination of acetic
acid to form an α,β-unsaturated acid anhydride
intermediate.
Ar-CH(OH)-CH₂-COO(COCH₃) → Ar-CH=CH-COO(COCH₃) +
CH₃COOH
Step 4: Hydrolysis
The anhydride intermediate is hydrolyzed during work-up
(acidic or basic hydrolysis) to yield the final α,β-unsaturated
aromatic acid.
Ar-CH=CH-COO(COCH₃) + H₂O → Ar-CH=CH-COOH