ANSWERS

Temasek Junior College

JC1 H2 Chemistry
Arenes Tutorial Answers
1 (a) Formula of the alkylbenzene is C6H5 – CnH2n+1
Total no. of C is 13  6 + n = 13 Hence n = 7
No. of H present = 2(7) + 1 + 5 = 20 Hence x = 20
The formula is C13H20.

1 (b) (i) Carbon atoms only are planar: P & Q

1 (b) (ii) All atoms are planar: P

Optional: Additional Question (Constitutional isomer covered in Qn 5)

Write the full structural formulae of two constitutional isomers of S (C9H12) for which all the carbon
atoms in the molecule are planar.

H H H H H H H H
C C C C
H H H HH H H H

H C C H C H
H C
H H H H
H C
H H

1,2,3-trimethylbenzene 1,2,4-trimethylbenzene 1,3,5-trimethylbenzene

1 (c) No. Due to the steric hindrance of Ha and Hb (i.e. the H atoms are too close together
in the same plane)
Ha Hb

Ha Hb
Hence the 2 benzene rings will be at 90o to each other (i.e. they are perpendicular
to each other)

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1 (d) To each sample separately, add KMnO4 and dilute H2SO4, and heat in a water bath.
For P, purple solution of KMnO4 will not be decolourised.

+ [O] no reaction

For Q, purple solution of KMnO4 will be decolourised to form a colourless solution.

CH3 + 3[O] CO2H + H2O

2 As the oxidation products show 2 carboxylic groups at position 1 and 2, L and M each
has two side chains at positions 1 and 2.

As L undergoes electrophilic addition with aqueous Br2, L contains an alkene in one of

its side chains.

L is

M does not undergo electrophilic addition with aqueous Br2. Thus, M does not contain
any alkene in its side chains. All 3 carbon atoms in its side chains are saturated and form
a cyclic structure (so that its molecular formula is C9H10 instead of C9H12).

M is

CH3 CH3
3 (a) (i)

3 (a) (ii) CH3 COOH

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4 (a) Step 1: Generating the electrophile, Cl+
AlCl3 + Cl - Cl ⇌ AlCl4 ‒ + Cl+
Step 2: Electron-rich benzene attacks the Cl+ electrophile

Step 3: Abstraction of proton followed by regeneration of the catalyst

4 (b) Bromobenzene. Br+ electrophile is preferably generated as the Cl in Cl−Br is more

electronegative, resulting in the Br carrying a partial positive charge.
BrCl + AlCl3 ⇌ AlCl4- + Br+

4 (c)

A is B is

5 (a) (i) Type :  Constitutional isomerism ( accept: Positional isomerism)

Definition:  Isomers with similar molecular formula, but differ in the position of
their functional groups

Comments: Definitions tended to be vague and non-specific with many answers making
no reference to isomers sharing the same molecular formula.

5 (a) (ii) C9H6N2O2

5 (b) (i) The methyl group is 2,4 directing so the incoming electrophile or +SO3H is more
likely to approach the 2- and 4- position relative to -CH3.

5 (b) (ii) The 2- position is closer to the -CH3 group and hence is more sterically hindered
so the incoming electrophile is less likely to approach the 2- position.

Comment: Weaker responses suggested that repulsion occurred between the 2 groups

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 5 (c) (i) Type of reaction: Electrophilic Substitution
Electrophile : SO3H+

[1] for curly arrows in both steps [1] for displayed formula of correct electrophile
[1] for correct intermediate.

5 (c) (ii) Reference Arenes notes p.10

 Benzene is resonance stabilised from the delocalisation of the π electron cloud

 Addition reaction will simply destroy the stable aromatic structure of the ring,
destabilising the compound.

Comments: Infrequently, answers were given in terms of the loss of resonance stability
in the product, as compared to the addition reactions, which retain resonance stability.
Many descriptions, in terms of the presence of the pi electron cloud were seen.

5 (c) (iii)  Order of reactivity towards electrophilic substitution: Methylbenzene > benzene > K
 Reason: for both explanations
Methylbenzene is the most reactive as the –CH3 substituent is electron releasing,
activating the benzene ring or making the ring very electron rich and more
susceptible towards attack with electrophiles.
K is the least reactive as the -COCH3 substituent is electron withdrawing,
deactivating the benzene ring or making the ring less electron rich than benzene
and less susceptible towards attack with electrophiles.

Comments: Correct order of reactivity was often given; explanations frequently were
incomplete. Confusion was evident in some responses that described K a more reactive
than benzene or reversed the order of reaction or in explanations: for example, “the
CH3CO group on K activating the ring” or “ electron withdrawing nature of the methyl
group”

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6 (a) (i)

6 (a) (ii)  I: alcoholic KOH, heat

 II: limited Cl2(g), UV light
 III: Br2(l), anhydrous FeBr3, room temperature

6 (b) (i)

6 (b) (ii)  meta-substituted product is less likely to be formed along with E since alkyl
substituent is 2,4- directing (i.e. ortho-, para-directing).

MCQ

1 2 3 4 5 6

D A D A C B

1 H H H H H
H H H
C C H H C H
H C C H H C C
H C C H H C C
C C H
H H H
H H H H

cyclohexane cyclohexene methylbenzene

A Both cyclohexene and methylbenzene also decolourise bromine in the presence

of light.
B Cyclohexene also contains sp2 hybridised carbon atoms at the >C=C<.
C Cyclohexane is not oxidised by hot acidified KMnO4 solution.
D All three compounds can undergo free radical substitution with chlorine gas in
the presence of uv light to form HCl.
Answer: D

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 2 sp2 NO2
H NO2 sp2
hybridised
sp3 hybridised
carbon
hybridised carbon
carbon

starting intermediate
reagent product

Answer: A

3 The intermediate complex is not planar, since the carbon atom carrying the −NO2 group
is sp3 hybridised and its bonds are arranged in a tetrahedral geometry.

NO2

There no chiral carbons.

Cis-trans isomerism is NOT possible without destroying the aromaticity of the benzene
ring.
Answer: D

4 A Compound to be made: 3-chloromethylbenzene

CH3

Cl
−CH3 is electron donating and 2,4-directing, the major products formed from
electrophilic substitution at the benzene ring (using Cl2 in the presence of
AlCl3) are
CH3
CH3
Cl

Cl
2-chloromethylbenzene 4-chloromethylbenzene
Even if 3-chloromethylbenzene is formed during the reaction, the yield is
going to be very low. Thus, 3-chloromethylbenzene is not made directly from
methylbenzene.
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 B Compound to be made: (chloromethyl)benzene
CH2Cl

(Chloromethyl)benzene can be formed by free radical substitution of the

–CH3 side-chain on the benzene ring.
Reagent: Limited Cl2(g)
Condition: uv light

C Compound to be made: 2-bromobenzene

CH3
Br

−CH3 is electron donating and 2,4-directing. Thus, one of the major products
of electrophilic substitution of methylbenzene by bromine is 2-
bromomethylbenzene. (The other major product is
4-bromomethylbenzene.)
Reagents: Br2(l), anhydrous AlBr3
Condition: Room temperature

D Compound to be made: benzoic acid

CO2H

Benzoic acid can be formed from oxidation of the −CH3 side-chain in

methylbenzene.
Reagents: KMnO4(aq), dilute H2SO4
Condition: Heat

Answer: A

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 5 Each position on the benzene ring has equal probability of being substituted by −NO2
group.
C−D bond is broken in the deuteriobenzene is broken as easily as the C−H bond.
 Rate of substitution of D atom by −NO2 = Rate of substitution of H atom by −NO2
There is NO difference in the substitution of D atoms and the substitution of
H atoms.
D
H H

H H
H

 The following 6 mono-nitrated structures are formed in equal proportion.

NO2
D

○
1

nitrobenzene

D
D
NO2
H
○
2

2-nitrodeuteriobenzene
identical
D
D
O 2N
H
○
3

2-nitrodeuteriobenzene

D
D

○
4
NO2
H
3-nitrodeuteriobenzene
identical
D
D

○
5
O 2N
H
3-nitrodeuteriobenzene

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 D
D

○
6

NO2
H
4-nitrodeuteriobenzene

To form 3-nitrodeuteriobenzene, there are 2 possible positions (out of 6) for

substitution.
2
 % 3-nitrodeuteriobenzene in product mixture =  100 = 33 %
6

Answer: C

2 1
C1 joins C6
3
6
CH3
CH3 CH2 CH2 CH2 CH2 CH2 CH3
1 2 3 4 5 6 4 5 Methyl group is on C6
after C1 joins C6.

C1 joins C6
2 1

CH3 CH2
 1 1 2 CH3
3 6
CH3
CH CH2 CH2 CH2 CH3
3 4 5 6 4 5
CH3
Methyl groups are on C3
and C6 after C1 joins C6.

CH3
CH3 CH3 1
1 2 Methyl groups
CH CH2 CH2 CH are on C2 and
 2 CH3
2 3 4 5
CH3
3 6
C5 after C1
6 joins C6.
4 5
CH3
C1 joins C6

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 CH3 CH3

C1 joins C6 CH3
1
CH3 2
 3 1
CH CH2 CH2 CH2 CH2 CH3 3 CH3
6
2 3 4 5 6
CH3 4 5

Methyl groups are on C2

and C6 after C1 joins C6.
(Compound formed is
1,3-dimethylbenzene.)

Answer: Isomers 1 and 2 only

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