Organic Chemistry Reactions of Aromatic Compounds

Diah Agustina Puspitasari, ST., MT Chemical Engineering Department Engineering Faculty Brawijaya University

Electrophilic Aromatic Substitution

Electrophile substitutes for a hydrogen on the benzene ring.

Mechanism

Example

Bromination of Benzene
Requires a stronger electrophile than Br2.

Use a strong Lewis acid catalyst, FeBr3.

Energy Diagram for Bromination

Chlorination and Iodination

Chlorination is similar to bromination. Use AlCl3 as the Lewis acid catalyst. Iodination requires an acidic oxidizing agent, like nitric acid, which oxidizes the iodine to an iodonium ion.
H
+

HNO3 + 1/2 I2

NO2 +

H2O

Nitration of Benzene Use sulfuric acid with nitric acid to form the nitronium ion electrophile.

Example

 Aromatic nitro groups are easly reduced to amino (-NH2) groups by trestment with an active metal suach as tin, zinc or iron in dilute acid.

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Sulfonation
Sulfur trioxide, SO3, in fuming sulfuric acid is the electrophile.

O S O O

_ O S+ _ O O _ O S + O O

S+ O O

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Example

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Desulfonation
All steps are reversible, so sulfonic acid group can be removed by heating in dilute sulfuric acid.

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Nitration of Toluene
Toluene reacts 25 times faster than benzene. The methyl group is an activator. The product mix contains mostly ortho and para substituted molecules.

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Sigma Complex
Intermediate is more stable if nitration occurs at the ortho or para position.

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Energy Diagram

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Activating, O-, PDirecting Substituents Alkyl groups stabilize the sigma complex by induction, donating electron density through the sigma bond. Substituents with a lone pair of electrons stabilize the sigma complex by resonance.
OCH3 + NO2 H H
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+ OCH3 NO2

Friedel-Crafts Alkylation
Synthesis of alkyl benzenes from alkyl halides and a Lewis acid, usually AlCl3. Reactions of alkyl halide with Lewis acid produces a carbocation which is the electrophile. Other sources of carbocations: alkenes + HF or alcohols + BF3.

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Examples of Carbocation Formation

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Limitations of Friedel-Crafts
Reaction fails if benzene has a substituent that is more deactivating than halogen. Carbocations rearrange. Reaction of benzene with n-propyl chloride and AlCl3 produces isopropylbenzene. The alkylbenzene product is more reactive than benzene, so poly alkylation occurs.

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Friedel-Crafts Acylation
Acyl chloride is used in place of alkyl chloride. The acylium ion intermediate is resonance stabilized and does not rearrange like a carbocation. The product is a phenyl ketone that is less reactive than benzene.

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Mechanism of Acylation

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