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Aromatic Substitution

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18 views40 pages

Aromatic Substitution

Uploaded by

vikasdhumal6308
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Electrophilic Aromatic Substitution Reactions

Benzene is very unreactive.


• It reacts only with very reactive (usually cationic) electrophiles.
• It gives substitution and not addition products.

Electrophilic attack on benzene and on cyclohexene


Most common electrophilic aromatic substitution reactions

• Halogenation: A bromine (Br), a chlorine (Cl), or an


iodine (I) substitutes for a hydrogen.
• Nitration: A nitro group substitutes for a hydrogen.
Sulfonation: A sulfonic acid group substitutes for a
hydrogen.
• Friedel–Crafts acylation: An acyl group substitutes
for a hydrogen.
• Friedel–Crafts alkylation: an alkyl (R) group
substitutes for a hydrogen.
Halogenation of Benzene

Lewis acid is a compound that accepts a pair of electrons


Ferric bromide and ferric chloride: Moisture sensitive, generated in situ by adding iron
filings and bromine or chlorine to the reaction mixture.
Electrophilic iodine is obtained by treating I2 with an oxidizing agent such as nitric
acid.
Formation of reactive brominating agent
Nitration of Benzene
Aniline also cannot be nitrated because nitric acid is an oxidizing agent and primary
amines are easily oxidized.

Tertiary aromatic amine can be nitrated.


• Because the tertiary amino group is a strong activator, nitration is carried out with
nitric acid in acetic acid, a milder combination than nitric acid in sulfuric acid.
• About twice as much para isomer is formed as ortho isomer.
Sulfonation of Benzene

Fuming sulfuric acid (a solution of SO3 in sulfuric acid) or concentrated sulfuric acid is
used to sulfonate aromatic rings.
Sulfonation of benzene is a reversible reaction. If benzenesulfonic acid is heated in
dilute acid, the reaction proceeds in the reverse direction.
Friedel–Crafts alkylation
Carbocations generation
Disadvantages of Friedel–Crafts alkylation
Polyalkylation:

Rearrangment:
Friedel–Crafts Acylation of Benzene

Either an acyl halide or an acid anhydride can be used for Friedel–Crafts acylation.
Advantages of acylation over alkylation

• Two problems in Friedel–Crafts alkylation do not arise with


acylation.
– The acyl group in the product withdraws electrons from the pie system
making multiple substitutions harder.

– If the ring is too deactivated to start off with, Friedel–Crafts acylation


may not be possible at all—nitrobenzene is inert to Friedel–Crafts
acylation and is often used as a solvent for these reactions.

– Rearrangements are also no longer a problem because the


electrophile, the acylium cation, is already relatively stable.
If there is a meta director on the ring the ring will be too unreactive to
undergo either Friedel–Crafts acylation or Friedel–Crafts alkylation.

Aniline and N-substituted anilines also do not undergo Friedel–Crafts reacti ons.

Phenol and anisole undergo Friedel–Crafts reactions—orienting ortho and para—


because oxygen, being a weaker base than nitrogen, does not complex with the
Lewis acid.
Intramolecular Friedel–Crafts reaction
An important use of the Friedel–Crafts alkylation reaction is to effect ring closure.

Another way of effecting ring closure through Friedel–Crafts alkylation is to use a reagent
containing two groups
Effect of Substituents on Orientation
Any substituent that donates electrons inductively is an ortho–para director.
All substituents that donate electrons by resonance are ortho–para directors.
All substituents that withdraw electrons (except for the halogens, which are ortho–para
directors because they donate electrons by resonance) are meta directors.
Ortho–Para Ratio

More of the ortho product because there are two ortho positions available to the incoming
electrophile and only one para position
Selectivity between ortho and para positions is
determined by steric hindrance
the para isomer will be formed preferentially if either the substituent on the ring or the
incoming electrophile is large.
Making amines less reactive

Acylate the amine to form an amide


Halogens (F,Cl,Br, and I) both withdraw and donate electrons

halogens deactivate the ring towards electrophilic attack but direct ortho and para
Two or more substituents may cooperate or compete

The aldehyde directs meta and the OH group directs ortho so they both direct to
the same position.
The methyl and OH groups each direct ortho to themselves

Bromination of this amide goes ortho to the –NHCOMe group but meta to the methyl group.
Two methoxy groups that direct ortho and para and an aldehyde that directs meta.
Acylating agent: Acid anhydrides, acyl chlorides, carboxylic acids with polyphosphoric acid,
carboxylic acids dissolved in trifluoromethanesulfonic acid.

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