OC04 Arenes H2 Chemistry 9729

4 Arenes
SUMMARY
Complete the following table

Reactions common to both benzene and methylbenzene

Reaction Reagent Condition Product for

Type
Benzene Methylbenzene

Electrophilic Cl2, Room temp Cl CH3 CH3

substitution anhydrous Cl
FeCl3
+ HCl + + HCl

Cl

CH3CH2Br, Room temp CH2CH3 CH3 CH3

anhydrous CH2CH3
AlBr3
+ HBr + + HBr

CH2CH3

Conc. 55°C for NO2 CH3 CH3

HNO3, benzene, 30°C NO2
conc. for
H2SO4 methylbenzene* + H2O + + H2O

NO2

*What is the reason for the difference in conditions?

This is due to the electron-donating methyl group, which increases the electron density in the ring,
making methylbenzene more reactive and readily attacked by electrophiles.

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Reactions for methylbenzene only

Reaction Reagent Condition Reactant Product

Type

Free radical Br2 uv light Methylbenzene CH2Br CHBr2 CBr3

substitution

Side chain KMnO4-/H+ (aq) Heat under COOH

reflux
oxidation

1 For the following compounds given by their IUPAC name, draw their condensed
structural formula.

(i) 2,4-dichloro-1-methylbenzene (ii) 1-phenylpropene

Cl
CH CHCH3

Cl

CH3

(iii) (2-bromoethyl)benzene (iv) 4-phenylbenzoic acid

CH2CH2Br COOH

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2 Draw the skeletal formula for all arenes with the molecular formula C9H12 (Hint: 8
isomers).

CH3 CH3 CH3

CH3 CH3 CH3

CH3 CH3

CH3

CH3 CH3 CH3

CH3

CH3

CH3

H3C CH3

CH3

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3 Which property of benzene may be directly attributed to the stability

associated with its delocalised electrons?
A It has a low boiling point
B It does not conduct electricity
C Its enthalpy change of formation is positive
D It is susceptible to attack by nucleophilic reagent
E It tends to undergo substitution rather than addition reactions.

4 Which property does benzene have as a consequence of the delocalisation of

electrons in the benzene molecule?
A Benzene is a good conductor of electricity.
B The carbon-carbon bond lengths are between those of C−C bonds and
C=C bonds.
C Addition reactions of benzene take place more easily than substitution.
D Substitution in benzene takes place at one particular carbon atom.

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5 Deuterium, D, is a heavy isotope of hydrogen. Deuteriobenzene is reacted with a

mixture of nitric acid and sulfuric acid under controlled conditions, so that only
mononitration takes place.
Assuming that the carbon-deuterium bond is broken as easily as a carbon-
hydrogen bond, which proportion of the nitrated products will be 3-
nitrodeuteriobenzene?

D D

NO2
deuteriobenzene 3-nitrodeuteriobenzene

A 16 % B 20 % C 33 % D 45 %

Problem Solving Skill Set (PS3) for Q5

1. What type of reaction is nitration? Electrophilic substitution
2. Draw the structural formula of possible mononitrated products besides 3- nitrodeuteriobenzene.

NO2 D D D
NO2

NO2
NO2

3. What is the probability of obtaining 3-nitrodeuteriobenzene amongst the other possible

products?

Substitution can occur at any of the 6 ring carbon atoms.

No. of positions that can lead to the desired product = 2
Therefore, proportion of desired product = 2/6 x 100% = 33 %

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6 When methylbenzene is nitrated by a mixture of concentrated nitric acid and

concentrated sulfuric acid, the product consists largely of two isomers of formula
C7H7NO2.
(a) Draw the structural formulae of the two isomers.
CH3

CH3

NO2

and NO2

(b) Briefly outline the mechanism of this reaction for one of the isomers.
Electrophilic substitution
HNO3 + 2H2SO4 ⇌ NO2+ + H3O+ + 2HSO4‾‾

H NO2

+ NO2+
slow
+

CH3 CH3

H NO2 NO2

.. -
HSO4 + + fast
+ H2SO 4

CH3 CH3

(c) What is the reason for adding concentrated sulfuric acid to concentrated nitric
acid in the preparation of nitrobenzene?
To act as a Brønsted-Lowry acid (so as to protonate HNO3) resulting in the
production of NO2+ which is a stronger electrophile than HNO3.

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7 During the nitration of benzene, a nitro group substitutes at a carbon atom. Which
one of the following gives the arrangement of the bonds at this carbon atom
during the reaction?
at the start of the in the intermediate at the end of the
reaction complex reaction
A Planar Planar Planar
B Planar Tetrahedral Planar
C Planar Planar Tetrahedral
D Tetrahedral Tetrahedral Tetrahedral

Problem Solving Skill Set (PS3) for Q7

1. In the table below, draw the structure of benzene, intermediate complex and nitrated product.
2. State the hybridisation of the carbon atoms in benzene, intermediate complex and nitrated
product.
3. State the no. of lone pairs and bond pairs for benzene, intermediate complex and nitrated
product.
benzene Intermediate Nitrated product
structure H NO2 NO2

+
hybridisation sp2 sp3 sp2
No. of lone 3 bond pairs 4 bond pairs 3 bond pairs
pairs and 0 lone pair 0 lone pair 0 lone pair
bond pairs

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8 Which compound cannot be made directly from methylbenzene?

A CH3 B CH2Cl

Cl

Methyl substituent is 2,4- Free radical substitution of

directing. However, Cl is methyl side chain
substituted at the 3-position.

C CH3 D COOH
Br

Electrophilic substitution Oxidation in the acidic medium

9 Methylbenzene can be used as an additive in unleaded petrol. Some chemical

transformations of methylbenzene are given below.

I CO2H

II
CH3 CH2Cl

III

CH3

Cl
A

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(a) Fill in the table:

Reaction I II III
KMnO4(aq), Cl2(g), uv light Cl2(g), anhydrous
Reagents and
H2SO4(aq), heat AlCl3
conditions
under reflux
Side chain Free radical Electrophilic
Type of reaction oxidation substitution substitution

(b) There are two other positional isomers of A. Draw their structural formulae and
suggest which one is more likely to be formed along with A in reaction III.

CH3 CH3

Cl
Cl
minor product major product

(c) Give an outline of the mechanism of reaction III.

Electrophilic substitution

AlCl3 + Cl2 ⇌ AlCl4‾‾ + Cl+

slow
+ Cl+ + H

Cl
CH3 CH3

.. fast
+ H + AlCl 4
-
+ HCl + AlCl 3

Cl Cl
CH3 CH3

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(d) The reaction in (c) can only take place under anhydrous conditions. Suggest a
reason to explain why it is so.

AlCl3 + 6H2O  [Al(H2O)6]3+(aq) + 3Cl‾‾

[Al(H2O)6]3+ + H2O [Al(H2O)5(OH)]2+ + H3O+

In the presence of water, AlCl3 undergoes hydrolysis to form an acidic solution.

Hence AlCl3 cannot act as Lewis acid (electron pair acceptor) as there is no more
energetically accessible and vacant orbital in Al to accept a lone pair of electrons
from Cl. Thus the condition need to be anhydrous.
10(a) Draw the structural formulae of the organic product(s) formed when the following
compound reacts with the stated reagents:
CH2

(i) Br2 in CCl4 (iii) Br2 with FeBr3

Br

Br
Br
Br
Br

or

Br

Br
Br

(ii) cold, alkaline KMnO4 (iv) alkaline KMnO4, heat under reflux

_
COO
OH

OH

(b) Name the type of reaction occurring in each reaction.

(i) electrophilic addition (iii) electrophilic substitution +
electrophilic addition

(ii) mild oxidation (iv) oxidation of side chain

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11 Devise two-step syntheses, starting with methylbenzene, of

(i) 4-nitrobenzoic acid
(ii) 3-nitrobenzoic acid
Identify the reagents at each step, and draw the structural formulae of the
intermediates.
(i)
CH3 COOH
CH3
Step 1 Step 2

NO2 NO2

Reagents and conditions

Step 1 Concentrated nitric acid, concentrated sulfuric acid, 30°C

Step 2 KMnO4 (aq), H2SO4(aq), heat under reflux

(ii)
CH3 COOH COOH
Step 1 Step 2

NO2

Reagents and conditions

Step 1 KMnO4 (aq), H2SO4(aq), heat under reflux

Step 2 Concentrated nitric acid, concentrated sulfuric acid, > 55°C

Problem Solving Skill Set (PS3) for Q11

1. In order to achieve the desired product, think about how the presence of a first substituent (2,4
directing or 3-directing) will affect the position of substitution of the second substituent?

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12 For each of the following pair of compounds, describe one simple chemical test
that would enable you to distinguish between them. State clearly the observations
each compound will produce.

Note: Distinguishing tests are carried out in the laboratory by placing small
quantities of the unknown samples in test tubes. For reactions that require
heating, the reflux setup is not required, i.e. do not heat under reflux. Where
possible, free radical substitution of alkyl groups and electrophilic substitution of
benzene are not used in distinguishing tests.

(a)
Reagents and Conditions:
A. Aqueous Br2
B. Br2 in CCl4
C. KMnO4(aq), H2SO4(aq), heat (Do not heat under reflux)

A. Orange Br2 decolourised A. Orange Br2 remains

B. Orange red Br2 decolourised B. Orange red Br2 remains
C. Purple KMnO4 decolourised C. Purple KMnO4 remains

(b)
Reagents and Conditions:
KMnO4(aq), H2SO4(aq), heat (Do not heat under reflux)
CH3

Purple KMnO4 decolourised Purple KMnO4 remains

White precipitate of benzoic acid is
formed.

(c)
Reagents and Conditions:
KMnO4(aq), H2SO4(aq), heat (Do not heat under reflux)
CH3 CH2CH3

Purple KMnO4 decolourised. Purple KMnO4 decolourised

White precipitate of benzoic acid is White precipitate of benzoic acid is
formed. formed.
No effervescence. Effervescence of CO2 seen
Gas evolved gives a white ppt with
limewater.
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13(a) State the reagents and conditions to prepare methylbenzene from benzene.

CH3Cl, anhydrous FeCl3 catalyst, room temperature

(b) Describe the mechanism for the above reaction.

Electrophilic substitution

FeCl3 + CH3Cl ⇌ FeCl4‾‾ + CH3+

H
CH3
slow
+
+
CH3 +
H
fast CH3
.. - CH3
FeCl4 - + + + HCl + FeCl3

14 Iodine monochloride, ICl, can be prepared by passing chlorine gas over iodine
crystals and it is collected as a dark brown liquid. Draw the structure of the likely
organic product of the reaction of ICl with methylbenzene, in the presence of
anhydrous AlCl3.
CH3 CH3

or

Problem Solving Skill Set (PS3) for Q14

1. What type of reaction is taking place? Hint: There is the presence of anhydrous AlCl 3.
Electrophilic substitution
2. Consider the mechanism of the reaction, what is the purpose of adding AlCl 3 in the reaction of ICl
with methylbenzene?
To generate I+ electrophile (I in ICl carries a partial positive charge as it is less electrongetive
than Cl)
3. Can we use AlI3 as the catalyst to get the same product?
Yes, as long as the catalyst used possesses energetically accessible and vacant orbital in Al to
accept a lone pair of electrons from Cl and function as a Lewis acid.

However, there could be Cl+ electrophile generated due to halogen exchange, leading to side
products.

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OC04 Arenes H2 Chemistry 9729

15 This question is about the structure and bonding of unsaturated hydrocarbons.

(a) The structure of ethene, C2H4, may be described in terms of the hybridisation of
orbitals.

(i) What type of hybridisation is present in the ethene molecule?

sp2

(ii) Sketch the shapes of the hybrid orbitals around one carbon atom in the
ethene molecule.

(b) The bonding in ethene may be described as a mixture of  and  bonding.

Each carbon atom forms three  bonds as shown in figure 14. 1 below.

H H

C C

H H

Fig. 15.1

Each of these  bonds is formed by hybridisation.

(i) On figure 15.1, sketch the  bond that is also present in ethene.

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(ii) Explain why the  bond in ethene is described as a localised  bond.

Two p-orbitals overlaps sideways to form a  bond whose electron cloud is

spread over the two C atoms.
(c) The molecule of benzene, C6H6, is a regular hexagon in which the  electrons are
described as being delocalised.

(i) By describing benzene as an example, with the aid of a diagram, what is

meant by the term delocalised  bond.

Six p-orbitals overlaps sideways to form  bonds whose electron cloud is

no longer spread over just two C atoms, but are spread over the whole ring
of six C atoms.

(ii) Give one physical and one chemical property that supports this structure.

physical

All six carbon-carbon bonds are of the same length.

FYI: Possess higher boiling point than other hydrocarbons of similar

molecular size (hexane, for example).
Reason: Instantaneous dipoles can be more easily formed due to the
presence of delocalised electrons, giving rise to stronger id-id forces.

chemical

Benzene undergoes electrophilic substitution and not electrophilic addition.

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(d) When ethene is reacted with HCl(g), C2H5Cl is the only product.
Benzene has no reaction with HCl(g).

(i) What type of reaction occurs between ethene and HCl(g)?

Electrophilic addition

(ii) Why is there no further reaction between C2H5Cl and HCl(g)?

There is no more  electron cloud present in C2H5Cl. Hence it is not

electron rich enough to attract the weak electrophile, HCl.

The ethyl group does not react with polar reagents.

(iii) Suggest why ethene reacts readily with HCl(g) but benzene does not.

Benzene is less nucleophilic due to delocalization of  electron cloud (less

electron rich) than ethene to weak electrophile like polarised HCl
(FYI: compared to Cl+, generated in the presence of halogen carrier).

(iv) Explain why benzene prefers to undergo substitution rather than addition
reactions.

Benzene does not undergo addition reactions as these would break the
ring of delocalised  electrons and result in the loss of aromatic stability.
Instead, benzene tends to undergo substitution reactions so that its 
electron ring remains intact.

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16 An organic compound, C8H7Cl, burns with a smoky flame and is a mixture of two
isomers, A and B. The two isomers react with Br2 in a 1:1 mole ratio to form the
same compound, C. Both A and B are oxidised by hot acidified KMnO4 to produce
the same compound D. D reacts with a mixture of concentrated nitric and sulfuric
acids to give E.

Draw the structural formulae of A, B, C, D and E.

Observation Type of reaction Deduction

C:H ratio is about 1:1
Combustion which indicates that a
benzene ring is present.
An organic compound,
C8H7Cl, burns with a smoky
A pair of cis-trans
flame and is a mixture of
isomers exists in A and B
two isomers, A and B.
and both carbon atoms in
the alkene are attached
to two different atoms.

The two isomers react with Electrophilic addition Presence of one alkene
Br2 in a 1:1 mole ratio to
in A and B
form the same compound,
C.

Presence of alkene in A
Oxidative cleavage and B
Both A and B are oxidised
(or side chain oxidation) (or the carbon atom
by hot acidified KMnO4 to
bonded to benzene has
produce the same
at least one hydrogen
compound D.
atom)

Substituent on benzene
Electrophilic substitution ring in D is 3-directing
and results in only 1
D reacts with a mixture of nitrated product.
concentrated nitric and
sulfuric acids to give E. FYI: 2, 4-directing
substituents would give
rise to two nitrated
products.

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Structures of A, B, C, D and E:
H
H H H Cl

Cl H
Br
Br
H Cl

A BH3 CH4

COOH COOH

NO2
DH E

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17 The position of substitution in the electrophilic substitution of mono-substituted

arenes depends on the nature of the group, A, already attached to the ring. This
selectivity can be explained based on the stability of the intermediate formed in
the first step. Fig. 16.1 shows three possible first steps in the nitration of a mono-
substituted arene and the products obtained.

A A
NO2
NO2
+ H

2-position
isomer 2-position

A A A

3-position
+
NO2
NO2
H isomer 3-position
4-position
A A
+

H NO2
NO2
isomer 4-position
Fig. 16.1

Use this information to predict which substituted isomers in Fig. 16.1 will be
formed the least and the most when A is a (CH3)3C— group. Explain your
reasoning.

Isomer which formed the least Isomer 3-position

Reason Electron donating (CH3)3C– group is directly bonded to the carbocation

centre hence it disperses the positive charge on the carbocation centre in the
intermediates for isomer 2-position and isomer 4-position more effectively than for
isomer 3-position, forming a more stable tertiary carbocation. Hence, isomer 3-
position will be formed the least as it is formed from the less stable secondary
carbocation.

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Isomer which formed the most Isomer 4-position

Reason Due to the close proximity, the incoming –NO2 group/electrophile will
experience steric hinderance from the bulky (CH3)3C– group as it approaches the
2-position. This destabilises the carbocation intermediate for isomer 2-position.
Hence, isomer 4-position will be formed the most.

Problem Solving Skill Set (PS3) for Q17

Consider the two properties of the existing substituent attached to the ring.

(CH3)3C— is an electron donating alkyl group and a bulky substituent.

Based on the structures of the three intermediates, what factor affects the

1. stability of the carbocation

number of electron donating alkyl groups which determines the type of carbocation (primary,
secondary or tertiary)

2. amount of steric hindrance experienced by the incoming NO2+ electrophile

proximity to bulky substituent (e.g. highly branched alkyl group and large phenyl ring)

Comments
Some strong and clear answers were seen. Most candidates were able to predict which
isomer will be formed the most and the least and to give some relevant reasoning.
However, a clear explanation in terms of the stability of the carbocations was normally
absent.

Do not accept
 electron withdrawing NO2 group is closest to positive charge in the intermediate for
isomer 2-position as the positive charge can be delocalised to be further away (as
shown in following resonance diagrams.)

P P P

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Acceptable
 In the 4-posiiton intermediate, p orbital of carbocation is between π orbital of two
C=C hence they can overlap, resulting in the positive charge of carbocation being
dispersed over the 2 C=C, stabilising it to a greater extent than the 2-positon
intermediate. This is also applicable to intermediates of other isomers due to
resonance structures (see above 2nd resonance diagram for 3-posiiton):

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