Chapter 4: AROMATIC COMPOUNDS

The content includes:

4.1. Structure of Benzene

4.2. Aromaticity-Hückel’s Rule

4.3. Nomenclature of benzene Derivatives

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4.4. Physical properties

4.5. Reaction of aromatic compounds:

4.5.1. Electrophilic aromatic substitution reactions

4.5.2. Reactions of side-chain of alkyl benzene

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4.1. Structure of Benzene

H H
H H H H

H H H H
H H
Kekule benzene: two forms are in rapid equilibrium
154 pm 134 pm

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- All bonds are 140 pm (intermediate between C-C and

C=C)
- C–C–C bond angles are 120°
- Structure is planar, hexagonal

 A Resonance Picture of Bonding in Benzene

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6 -electron delocalized

over 6 carbon atoms

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The aromatic system of benzene consists of six p-

orbitals (atomic orbitals). Benzene must have six
molecular orbitals.

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4.2. Aromaticity-Hückel’s Rule

For aromaticity, a molecule must:

- Cyclic, Planar

- Completely conjugated

- The number of pi electrons in the cyclic system is: 4n +2

( n is an integer, commonly 0, 1, 2 and so forth)

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Identify the number of p electrons in each of the following

compounds:

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4.3. Nomenclature

Mono-substituted benzenes :

Br CH2CH3
NO2

bromobenzene ethylbenzene (1-methylethyl)benzene nitrobenzene

(isopropylbenzene)

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Large number of non-systematic names that can serve

as the parent name

O H O OH
CH3 OH OCH3 NH2

benzene toluene phenol anisole aniline styrene benzaldehyde benzoic acid

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Two or more substituted benzene:

• Choose numbers to get lowest possible values

• List substituents alphabetically with hyphenated numbers

• Non-systematic names, such as “toluene” can serve as

parent

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4.4. Physical properties

The compounds are insoluble in water, but quite soluble

in non-polar solvents. They are almost less dense than
water…

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4.5. Reactions of aromatic compounds:

4.5.1. Electrophilic aromatic substitution reactions

4.5.1.1: A General mechanism for electrophilic aromatic

substitution.

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Step 1: Attack on the electrophile forms the sigma complex.

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Step 2: Loss of a proton regains aromaticity and gives the

substitution product.

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4.5.1.2. Effects of substituent on electrophilic aromatic

substitution

a) Relative rate:

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The following compound has four Aromatic rings.

Rank them in terms of increasing reactivity toward
electrophilic aromatic substitution.

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b) Directing effects of substitution

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4.5.1.3. Nitration reaction

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Preliminary steps: Formation of the nitronium ion:

Step 1: Attack on the electrophile forms the sigma complex

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Step 2: Loss of a proton gives nitrobenzene.

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4.5.1.4. Sulfonation reaction

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Step 1: Attack on the electrophile forms the sigma complex.

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Step 2: Loss of a proton regenerates an aromatic ring.

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Step 3: The sulfonate group may become protonated in

strong acid.

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4.5.1.5 Halogenation reaction

Step 1: Formation of a stronger electrophile.

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Step 2: Electrophilic attack and formation of the sigma

complex.

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Step 3: Loss of a proton gives the products.

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4.5.1.6. Friedel–Crafts alkylation.

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Step 1: Formation of a carbocation.

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Step 2: Electrophilic attack forms a sigma complex.

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Step 3: Loss of a proton regenerates the aromatic ring

and gives the alkylated product

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4.5.1.7: Friedel–Crafts acylation.

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Step 1: Formation of an acylium ion.

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Steps 2 and 3: Electrophilic attack forms a sigma complex,

and loss of a proton regenerates the aromatic system.

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Step 4: The product complex must be hydrolyzed (by

water) to release the free acylbenzene.

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4.5.2. Reactions of side-chain of alkyl benzene

4.5.2.1. The Clemmensen Reduction

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4.5.2.2. Permanganate Oxidation

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4.5.2.3. Side-Chain Halogenation

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