STUDENT’S NOTE – BENZENE & AROMATICITY

Based on Cambridge International A level 9701 syllabus for 2025 – 2027

30 Hydrocarbons – Arenes

30.1 Formulas, functional groups and the naming of organic compounds

Toluene Benzaldehyde

Phenol Benzoic acid

Acetophenone Ortho-Xylene

Bromobenzene Propyl Benzene

Nitrobenzene Aniline

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 Benzyl group: C6H5CH2- group Phenyl group:

- Disubstituted benzenes are named using the prefixes ortho (o), meta (m), or para (p). An ortho-disubstituted benzene
has its two substituents in a 1,2 relationship on the ring, a meta-substituted benzene has its two substituents in a 1,3
relationship, and a para-disubstituted benzene has its substituents in a 1,4 relationship.

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Problems:

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30.2 Structure and Stability of Benzene

30.2.1 Shapes of aromatic organic molecules; σ and π bonds

1 describe and explain the shape of benzene and other aromatic molecules, including sp² hybridisation, in terms
of σ bonds and a delocalised π system

Benzene structure:

• Planar hexagonal ring.

• Each C is sp² hybridised → forms three σ bonds (two C–C, one C–H).

• Remaining p orbital overlaps sideways → delocalised π system above and below ring.

Explains equal bond lengths (intermediate between single and double bond) and stability (resonance).

30.2.2 Aromaticity and the Huckel 4n+2 Rule

Description of aromaticity: Huckel 4n+2 rule

A molecule is aromatic only if it has a planar, monocyclic system of conjugation and contains a total of 4n+2 𝜋 electrons,
where n is an integer (n 5 0, 1, 2, 3, . . .).

Only molecules with 4n 𝜋 electrons (4,8,12,16) cannot be aromatic, even though they may be cyclic

Benzene: has 6 pi electrons (4n+2 = 6 when n =1) and is aromatic

Cyclooctatetraene has eight p electrons and is not aromatic. The p electrons are localized into four double bonds rather
than delocalized around the ring, and the molecule is tub-shaped rather than planar

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30.4 Chemistry of Benzene: Electrophilic Aromatic Substitution

30.4.1 Electrophilic Aromatic Substitution Reaction

Describe the mechanism of electrophilic substitution in arenes:

• Step 1: Formation of the electrophile.
• Step 2: Attack of the electrophile on the benzene ring → formation of an arenium ion (carbocation
intermediate).
• Step 3: Loss of a proton (H⁺) → restoration of aromaticity.

(a) Substitution reactions with Cl ₂ and with Br₂ in the presence of a catalyst, AlCl₃ or
AlBr₃ (FeBr3), to form halogenoarenes (aryl halides)

To take place, a catalyst such as FeBr3 is needed. The catalyst makes the Br2 molecule more electrophilic by
polarizing it to give an FeBr4

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 Mechanism for the electrophilic bromination of benzene. The reaction occurs in 2 steps and involves a resonance -
stabilized carbocation intermediate
Step 1: Generation of the Electrophile (Br⁺)
?

Step 2: Attack on Benzene Ring

?

Restoration of Aromaticity
?

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(b) Aromatic Nitration
Nitration with a mixture of concentrated HNO₃ and concentrated H₂SO₄ at a temperature between 25 °C and 60 °C
Reagents: concentrated nitric and sulfuric acid HNO₃ + conc. H₂SO₄
Conditions: 25–60 °C (below 60 °C to avoid polysubstitution).
Reaction:
C₆H₆ + HNO₃ → C₆H₅NO₂ + H₂O
Nitrobenzene
Generation of the Electrophile (NO₂⁺)
?

Attack on Benzene Ring

?

Restoration of Aromaticity
?

Electrophilic nitration of an aromatic ring does not occur in nature but it particularly important in the laboratory
because the nitro-substituted produce can be reduced by reagents such iron, or SnCl2 to yield an arylamine

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30.4.2 Alkylation and Acylation of Aromatic Rings: The Friedel-Crafts Reaction

(a) Friedel–Crafts alkylation by CH₃Cl and AlCl ₃ and heat

Reagents: Alkyl halide, with AlCl₃ catalyst, heat.

Product: alkyl benzene
Reaction:
C₆H₆ + CH₃Cl → C₆H₅CH₃ + HCl
Mechanism:
- AlCl3 creates ion carbocation R+ to substitute to Benzene (how: Al in AlCl3 has 1 empty orbital, Cl in R-Cl have
3 lone pair electrons so it try to attack empty orbital p, stretching bond between R and Cl – break the bond) :
create complex AlCl4-)
?

- An electron pair from the aromatic ring attacks the carbocation, forming a C-C bond and yielding a new
carbocation intermediate
?

- Loss of a proton then gives the neutral alkylated substitution product.

?

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(d) Friedel–Crafts acylation by CH₃COCl and AlCl ₃ and heat

Reagents: CH₃COCl, AlCl₃ catalyst, heat.

Reaction:

Mechanism:
- The reactive electrophile acyl cation is generated by reaction between the acyl chloride and AlCl3
- The acyl cation is stabilized by interaction of the vacant orbital on carbon with lone-pair electrons on the neighbouring
oxygen.
?

Example: Predicting the product of a carbocation rearrangement

The Friedel–Crafts reaction of benzene with 2-chloro-3-methylbutane in the presence of AlCl3 occurs with a
carbocation rearrangement. What is the structure of the product?

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 ✓ Problem: Which of the following alkyl halides would you expect to undergo Friedel–Crafts reaction with
rearrangement and which without? Explain

✓ Problem: Identify the carboxylic acid chloride that might be used in a Friedel–Crafts acylation reaction to
prepare each of the following acylbenzenes:

30.4.3 Complete oxidation of the side-chain using hot alkaline KMnO₄ and then dilute acid to give a benzoic
acid

Reagents: Hot alkaline KMnO₄, then dilute HCl.

Reaction: Alkyl side chain → benzoic acid (–COOH).

Mechanism: involve reaction of C-H bonds at the position next to the aromatic ring to form intermediate benzylic
radicals.
Tert-butylbenzene has no benzylic hydrogens – no reaction

Example:
C₆H₅CH₃ → C₆H₅COOH

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30.4.4 Hydrogenation of the benzene ring using H₂ and Pt/Ni catalyst and heat to form a cyclohexane ring

With Benzene
Reagents: H₂, Pt or Ni catalyst, heat.
Reaction:
C₆H₆ + 3H₂ → C₆H₁₂ (cyclohexane)
With Methyl Benzene: ?

With o-Xylene:

With 4-tert-butylphenol:

30.4.5 Substituent Effects in Electrophilic Substitutions

- Substituents affect the reactivity of the aromatic ring, making it more reactivity than benzene, and some deactivate
the ring, making it less reactive than benzene.

Eg: -NO2 substituent makes the ring more than 10 million times less reactivity than an -OH substituent

- Substituents affect the orientation of the reaction: there are 3 possible substituted products

- Substituents can be classified into 3 groups: ortho- and para-directing activators, ortho- and para-directing
deactivators, meta-directing deactivator.

4 Describe that in the electrophilic substitution of arenes, different substituents direct to different ring positions
(limited to the directing effects of –NH₂, –OH, –R, –NO₂, –COOH and –COR) (syllabus)
Based on electron-donating or electron-withdrawing effects

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 ❖ Activating and Deactivating Effects
Activating group: they donate electrons to the ring, thereby making the ring more electron-rich, stabilizing the
carbocation intermediate, and lowering the activation energy for its formation.
Deactivating group: they withdraw electrons from the ring, thereby making the ring more electron-poor, destabilizing
the carbocation intermediate – raising the activation energy.

a) Resonance electron withdrawing groups: Meta Directors (deactivate the ring)

Reason: strong -I (inductive) and/ or -M (mesomeric) withdrawing effect -> ring becomes less reactive
?

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Example: Nitrobenzene nitrated again -> mainly 3-nitro-nitrobenzene
?

b) Resonance electron donating groups (ortho/para directors): Increase electron density at positions 2,4,6 ->
substitution favored there.
lone pairs (+M effect for -OH, -NH2) or electron-donating groups push electron density into the ring
?

Example: Phenol + Br2 (aq) -> 2,4,6 – tribromophenol (white precipitate)

✓ Problem:

✓ Problem: Draw resonance structures for the intermediates from the reaction of an electrophile at the ortho,
meta, and para positions of nitrobenzene.
?

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30.5 Why substitution instead of Addition?
with regards to the effect of delocalisation (aromatic stabilisation) of electrons in arenes to explain the predomination
of substitution over addition
- Addition would destroy the localised pi system (lose resonance stabilisation)
- Substitution preserves aromaticity, which is energetically far more favourable

30.6 Predict whether halogenation will occur in the side-chain or in the aromatic ring in arenes
depending on reaction conditions

a) Halogenation in the Aromatic Ring: electrophilic substitution, catalyst required

Condition: Halogen (CL2/Br2)

Catalyst: AlCl3/ FeCl3 (for chlorination) / AlBr3/FeBr3 (for bromination)
Heat (room temperature or warm)
Mechanism: ?
Example:

b) Halogenation in the Side Chain: free radical substitution, UV light required

Condition: UV light, high temperature

Mechanism: ?

30.7 Tri-substituted Benzene: Additivity of Effects

Rule 1: If the directing effects of the 2 groups reinforce each other, the situation is straightforward

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Rule 2: If the directing effects of the 2 groups oppose each other, the more powerful activating groups has dominant
influence, but mixtures of products are often formed.

Rule 3: Further substitution rarely occurs between the 2 groups in a meta-substituted compound

✓ Problem: At what position would you expect electrophilic substitution to occur in each of the following
substances?

✓ Problem: Show the major products from reaction of the following substances with

Additional Exercise:

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 ✓ Problem: Reaction of Toluene (Methyl Benzene)

a) Substitution reaction with Br2, Cl2

b) Substitution reaction with HNO3 (condition: )

c) Fredel-Crafts alkylation by CH3Cl and AlCl3 and heat

d) Fredel-Crafts acylation by CH3COCl and AlCl3 and heat

e) Oxidation of side-chain using hot alkaline KMnO4

f) Hydrogenation using H2 and Pt/Ni catalyst

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30.6 Benzyne

Mechanism:

Addition Exercise:
1.

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 4

5 Using resonance structures of the intermediates, explain why bromination of biphenyl occurs at ortho and
para- positions rather than at meta

6 At what position and on what ring do you expect nitration of 4-bromo-biphenyl to occur? Explain, using
resonance structures of the potential intermediates

7 Triphenylmethane can be prepared by reaction of benzene and chloroform in the presence of AlCl3. Propose
a mechanism for the reaction

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 8 What position, on what ring that we expect the following substances to undergo electrophilic substitution?

9 How to synthesize the following substances starting from benzene?

10 Draw resonance structures of the intermediate carbocation in the bromination of naphthalene, and account
for the fact that naphthalene undergoes electrophile substitution at C1 rather than C2

11 Identify the reagents

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