Friedel–Crafts Substitutions
Two electrophilic substitutions are named for
the chemists Charles Friedel and James
Crafts.
•Friedel–Crafts acylation places an acyl group on
a benzene ring.
•Friedel–Crafts alkylation places an alkyl group
on a benzene ring.
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Friedel–Crafts Alkylation
Alkyl halide
An alkyl halide is the source of the alkyl
group.
A Lewis acid (AlCl3) is required.
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Generation of the Electrophile for
Friedel–Crafts Alkylation
A carbocation is the electrophile.
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The Mechanism for
Friedel–Crafts Alkylation
•The electrophile adds to the benzene ring.
•A base in the reaction mixture removes the
proton from the carbon that formed the bond
with the electrophile.
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Friedel–Crafts Alkylation
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Friedel–Crafts Alkylation
A carbocation is the super electrophile.
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Friedel–Crafts Alkylation
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Friedel–Crafts Acylation
The electrophile (acylium ion) is formed
by the reaction of an acyl chloride (acid
anhydride) with AlCl3, a Lewis acid.
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Friedel–Crafts Acylation
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Friedel–Crafts Acylation
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Friedel–Crafts Acylation
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Generating the Electrophile for
Friedel–Crafts Acylation
The acylium ion is the electrophile.
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The Mechanism for
Friedel–Crafts Acylation
•The electrophile adds to the benzene ring.
•A base in the reaction mixture removes the
proton from the carbon that formed the bond
with the electrophile.
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AlCl3 Reacts with the Product of
Friedel–Crafts Acylation
More than one equivalent of AlCl3 must be
used in a Friedel–Crafts acylation.
AlCl3 forms a complex with the carbonyl
group in the product.
Water is added to the reaction mixture
to liberate the product from the complex.
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The Gatterman–Koch Reaction
Benzaldehyde cannot be made by a Friedel–
Crafts acylation because the needed acyl
chloride (formyl chloride) is unstable.
Formyl chloride is generated in the
reaction mixture (in situ).
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There are Limits to Friedel–
Crafts Alkylation
The alkylated benzene product is more reactive
than benzene.
Therefore, a large excess of benzene is
needed to avoid multiple alkylations of
the ring.
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Carbocation Rearrangement Leads to
an Undesired Product
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Carbocation Rearrangement Leads to
an Undesired Product
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Carbocation Rearrangement Leads to
an Undesired Product
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Carbocation Rearrangement Leads to
an Undesired Product
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How to avoid carbocation
rearrangement?
Start with a Friedel-Crafts Acylation Reaction
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How to avoid carbocation rearrangement? Cont.
Reduce the acyl group to an alkyl group.
Clemmensen
reduction
Catalytic
Hydrazine hydrogenation
Wolff-Kishner
reduction
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Putting a Straight Chain Alkyl Group
on a Ring
•Add the correct number of carbons with a
Friedel–Crafts acylation reaction.
•Reduce the carbonyl group to a methylene
group.
(Catalytic hydrogenation reduces only a
carbonyl group adjacent to a benzene ring.)
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Other Ways to Convert a Carbonyl Group
to a Methylene Group
These methods reduce ALL ketone
carbonyl groups to a methylene group, not
just those adjacent to benzene rings.
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The Mechanism for the
Wolff–Kishner Reduction
• The ketone forms a hydrazone following the mechanism for
imine formation.
• A hydroxide ion removes a proton from the weakly acidic NH2
group.
• Reprotonation occurs at carbon.
• Another deprotonation, loss of N2, and reprotonation forms the
product.
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