Chemistry: Electrophilic Aromatic Substitution–1

Solved Problems
Objective

Problem 1: Which among the following molecules/species is/are aromatic

(a) cyclobutadienyl dianion (b) cyclooctadienyl dianion
(c) cycloheptatrienyl cation (d) all are aromatic

Solution: Cyclobutadienyl dianion has six, cyclooctadienyl dianion has ten and
cycloheptatrienyl cation has six delocalized  electrons. Therefore, all are
aromatic.
(d)

Problem 2: In which of the following molecules, the substituent does not exert its
resonance effect

(a) C6H5NH2 (b) C6 H 5 N H 3
(c) C6H5OH (d) C6H5Cl

Solution: In C6 H 5 N H 3 there is no lone pair electrons on the N- atom and hence it
cannot exert its resonance effect.
(b)

Problem 3: Which of the following species would be expected to exhibit aromatic

character?

(I) (II) (III) (IV)

(a) I and IV (b) II and IV

(c) I and III (d) II and III

Solution: II and III have delocalized six  electrons and hence are aromatic.
(d)

Problem 4: In aniline, the –NH2 group

(a) activates the benzene ring vai both inductive and resonance effects
(b) deactivates the benzene ring via both inductive and resonance effects
(c) activates the benzene ring via resonance effect and deactivates it via
inductive effect.
(d) activates the benzene ring via inductive effect and deactivates it via
resonance effect.

Solution: Due to lone pair on N atom, it activates the ring. On the other hand N
electronegativity is more than ‘C’ so it deactivates the benzene ring via
inductive effect.
Chemistry: Electrophilic Aromatic Substitution–2

(c)

Problem 5: The compound

X

Y
(where X is an O – P, directing group and Y is m-directing group)
is subjected to electrophilic substitution reaction for introduction of Z. The
compound formed would be
X
X

(a) (b)
Y
Z Y
Z
X
Z
(c) (d) Both (b) and (c)
Y

Solution: The orientation is decided by the activating group i.e. o, p- directing

(b) and (c)

Problem 6: When Nitrobenzene is treated with Br2 in presence of FeBr3, the major product
formed is m-bromonitro benzene. Statements which are related to obtain m-
isomer are:
(a) The electron density on meta carbon is more than that on ortho and para
positions.
(b) The intermediate carbonium ion formed after initial attack of Br+ at the
meta position is least destabilized.
(c) Loss of aromaticity when Br+ attacks at the ortho and para positions not at
meta position
(d) Easier loss of H+ to regain aromaticity from the meta position than from
ortho and para positions.

Solution: The intermediate carbonium ion formed after initial attack of Br+ at the meta
position is least destabilized.
(b)

Problem 7: Terepthalic acid is obtained by oxidation of which of following compounds?

CH3 CH3
CH3
(a) (b)
 Chemistry: Electrophilic Aromatic Substitution–3

CH3
CH3

(c) (d)
CH3
CH3

Solution: Terepthalic acid is a para dicarboxylic acid

(c

Problem 8: The most basic compound among the following is:

(a) Benzylamine (b) Aniline
(c) Acetaniline (d) p-nitroaniline

Solution: Rest all show less tendency to donate electron pair due to resonance.
(a)

Problem 9: Which of the following is the major organic product of the following reaction?
H3C

 
AlCl3
?
H3C Cl
H3C
CH3 CH3

(a) (b) CH3

CH3

CH3
CH3

(c) (d)
CH3

Solution: The product obtained by the more stable carbocation

(b)

Problem 10: Which of the following is correct for the mononitration of phenyl benzoate?

COO

O
O
O
O
(a) (b) NO2

NO2

COO

(c) (d) COO

NO2
Chemistry: Electrophilic Aromatic Substitution–4

Solution:  (a)

Problem 11: What are A and B in the following reaction sequence?

Br

AlCl3  Br2
 ? 
HNO3
H 2SO 4
A  B

Br Br
Br Br
NO2
NO2
(a)  (b) 
NO2
NO2
Br Br Br Br

 
(c) (d)
NO2 NO2
CH3 NO2 NO2

Solution: Since Br is on o- and p- directing group.

 (a)
Problem 12: Which of the following is correct for the following reaction?
H3C

 
conc. H 2SO4

H3C OH
H3C
CH3 CH3

(a) (b) CH3

CH3

CH3 CH3

(c) (d)
CH3

Solution: The isobutylium ion rearranges to give most stable t-butyl carbonium ion.
 (b)
Problem 13: Arrange the following compounds in order of increasing dipole moment
Toluene m-dichlorobenzene
(I) (II)

o-dicholrobenzene p-dichlorobenzene
(III) (IV)

(a) I  IV  II  III (b) IV  I  II  III

(c) IV  I  III  II (d) IV  II  I  III
Solution:  (b)
H3C

Problem 14: The reaction of OH with HBr gives:

 Chemistry: Electrophilic Aromatic Substitution–5

CH3 CH3
Br
(a) OH
(b) OH
Br
CH3 CH3
Br
(c) Br
(d) Br
Br
Solution: The benzylic carbocation is more stable.
 (b)

Problem 15: The products A and B in the following reaction sequence are:
H5 C6

Br2
 A 
i) NaNH 2 (3 equiv.)
ii) CH3I
B
CH2
Br

H5 C6 , H3C CH3
(a)

Br
NH2

(b) H3C C6 H4 H3C H4 C6

,
CH2 CH2
(c) Both of the above
(d) None of the above

Solution: (a)

Problem 16: When cinnamic acid is nitrated, the incoming electrophile ( NO 2 ) goes at
(a) ortho position only (b) para position only
(c) meta position only (d) both ortho and para positions

Solution: H E

 H
O  E
at para position
 O E 
O
E at ortho
position

H
H H

H E
H
O
E
O
H
H
H
O
E

H
The delocalization of positive charge in arenium ion is extensive (occurs even
in the side chain) when the electrophile attacks at ortho and para position in
Chemistry: Electrophilic Aromatic Substitution–6

comparison to when it attacks at meta position (where the delocalization all

occur only in the ring).
 (d)

Problem 17: Which of the following structures correspond to the product expected, when
excess of C6H6 reacts with CH2Cl in presence of anhydrous AlCl3.
(a) (Ph)2CHCl (b) PhCHCl2
(c) Ph2CCl2 (d) Ph2CH2
Solution:
Cl  
Cl Cl 
Anhydrous
AlCl3
 Anhydrous AlCl
3

 (d)

Problem 18:
 (CH 3CO) 2 O 
BF3
P, P is
O
O
O
(a) CH3 (b)
O CH3
O
O
CH3
O
(c) O O (d) CH3
O
O

Solution: (b)

Problem 19: Benzene on reaction with ICl in presence of anhydrous AlCl3 gives?
(a) Cl (b) I
I
Cl
(c) (d) I Cl

Solution: When ICl is heated with AlCl3 I  Al Cl4 complex formation is more

farourable than Cl  Al Cl3 I complex. So iodiobenzene is formed.
 (b)

Problem 20: When the following compound is dissolved which of the following option is
Cl
formed.
 Chemistry: Electrophilic Aromatic Substitution–7

Cl Cl
(a) (b)

Cl Cl
(c) (d)

Solution: When the compound ionizes it will be exist as C because the cation
is highly stable.

 (c)

Subjective

Problem 1: Devise sequences for preparing the following compounds from benzene:
i) NH2 ii) OMe
Br

NO2

Solution: i) The process can be started if we can do the nitration to benzene ring two
times and then can reduce one of the group selectively. Ammonium
sulphide allows selective reduction of one nitro group in the presence of
another. The mechanism of this reaction is complex. It is the
transformation itself which you need to know.
NH2 NO2 NH2


H 2SO4
HNO3 / 
 
(NH 4 )2 S

NO2 NO2 NO2
Target

ii) The target can be achieved if we can form phenol from benzene.
Formation of phenol from benzene is not straight forward. The route
shown below involves the nitration, reduction to the aniline and
diazotization. “Hydrolysis” of the diazonium ion gives phenol.
OMe NO2 NH2 OH

Br


H 2SO 4
 
Sn / HCl
  HNO2
H 2 O(warm)

HNO3

Target

The next steps involve temporary introduction of a – SO3 group as a

protecting group of the para-position. This allows selective bromination of
the ortho-position. (note: which products would you get without the –SO3
group?)
Chemistry: Electrophilic Aromatic Substitution–8

OMe OMe OMe

Br


Me 2SO4 / NaOH
 H 2SO4


i) Br2 ,FeBr3
ii) H3O , 

SO3 H

Problem 2: Show the exact structure of the product (or products) of each EAS reaction
below. State whether each reaction is expected to be faster or slower than the
corresponding reaction of benzene
i) ii) O
HNO
 3
H 2SO 4


HNO3
H 2SO 4


iii) O iv) CH3

O

Br2



CH 2 Cl
AlCl3

CN

Solution: i) O2 N

 NO2

each phenyl group acts as an activating ortho/para director to the other

(equivalent) ring. This reaction would be faster than the nitration of
benzene.
ii) O

NO2
The carbonyl group acts as a deactivating meta director to both
(equivalent) rings. This reaction will be slower than the nitration of
benzene.
ii) Br
O O

Br
The oxygen – containing ring can be viewed as an OR group and an R
group attached to the benzene ring. Although both groups are activating,
the OR group is more strongly activating, so the position ortho and para to
it will be brominated. This reaction will be faster than the bromination of
benzene, which requires a catalyst.
 Chemistry: Electrophilic Aromatic Substitution–9

iv) CH3
O

CN
CH3
The reaction will be faster than that of benzene because of the activating
nature of OCH3 group which will be dominating over the deactivating
group CN.

Problem 3: The  N(CH 3 )3 and –CN substituents are both meta directors. Still nitration of
the corresponding benzene derivative does give a minor amount of the ortho
and para isomers of the product. Which of the two substituents should lead to
a greater ortho/para ratio? Why
Solution: The –CN group, being a linear two atom group, is much less sterically

demanding than the t-butyl like  N(CH 3 )3 group. So, the CN group should
give greater ortho/para ratio. In fact, here are the actual data:
Group % Meta % Ortho % Para Ortho/para ratio
 87 2 11 0.18
 N(CH 3 )3
– CN 81 17 2 8.5

Problem 4: Suggest a multi step synthesis for each of these compounds, starting with
benzene and any other reagents you need. Indicate with an asterisk each step
where a separation of positional isomers might be necessary.
CO2 H Br
i) ii)

(three steps)
(six steps)

NO2 Br

Solution: i) Since we start with benzene and ultimately generating the para isomer of
the product, we must at some point perform an EAS reaction with an
ortho/ para director already in place. Unfortunately, both -CO2H and - NO2
are meta directors. So, one or the other must have arisen from ortho / para
director during the synthesis. The only way we have seen so far to make a
-CO2H group involves KMnO4 oxidation of an alkyl group, which is an
ortho / para director! Therefore, a logical synthetic sequence would be
CH3 CH3 CO2 H


CH3Cl
 
HNO3
*
 
KMnO 4

AlCl3 H 2SO 4 H2O

NO2 NO2
* Separate para isomer from ortho (and some meta)
Chemistry: Electrophilic Aromatic Substitution–10

If we had nitrated first, then alkylated and oxidized, the meta isomer would
have been the predominant product.
ii) Since we generate the meta isomer in this case, we need to perform an
EAS at some point with a meta director already in place. But both groups
on the ring are ortho / para directors. Let's see if we can devise a logical
sequence using "retro" (backward) synthetic analysis, one that involves a
meta director ultimately transformed into an ortho / para director. The
logical last step in the synthesis would be benzylic bromination.
CH3 Br CH3


NBS

In

Br Br
The meta bromine could arise via diazotization of the corresponding amine
which, in turn, could result from reduction of a nitro group (a meta
director)


CuBr
 
HNO2

 
H2

H cat.

Br N2 NH2 NO2

Now, all we have to do is alkylate nitrobenzene. Unfortunately, Friedel

alkylations of deactivated ring usually fail because the catalyst coordinates
to the electron - withdrawing substituted rather than the alkyl halide. To
avoid this problem, the alkylation can be performed as follows:


CH3CH 2 OH

HNO3

H 2SO4 H 2SO4

NO2 NO2

In the case, the H2SO4 catalyst protonates the OH group ethanol, resulting
in the transfer of "CH3CH2+" to the meta position of the ring.

Problem 5: H3C

CH2

HF or BF3
A

Identify A and also the electrophile involved in the reaction.

Solution: H3C 
H3C

H

CH2 CH3
H3C CH3

H3C

CH3
(A)
A is iso propyl benzene (cumene) and electrophile involved is
CH3 – CH – CH3 (Isopropyl carbocation). Rearrangements are also possible
 Chemistry: Electrophilic Aromatic Substitution–11

in Friedel Crafts, reactions when benzene is treated with n-butyl chloride and
Lewis acid the product obtained is isobutyl benzene.

Problem 6: What happens when benzene is treated with methyl chloride in presence of
anhydrous AlCl3 and the product is treated with excess of chlorine in presence
of UV light?
Solution: anhy.
C6 H 6  CH 3Cl  Cl2
 C6 H 5CH 3  Cl2
 C6 H 5CH 2 Cl   C6 H 5CHCl2
Benzene AlCl3 UV light
Cl2
  C6 H 5CCl3
Benzotrichloride

Problem 7: Complete the following

H3C
a)
 CH2 
BF3
?
H3C
Cl
b)
 H3C 
AlCl3
?

H3C

c) OH


C2 H5 OH
Na
?

d)

Br2
?

Solution: a) H3C
H3C
CH3

 CH2 
BF3 CH3

H3C
H3C
b) Cl CH3
 H3C 
AlCl3
 H

H3C
OH O
c)

C2 H 5OH
Na


H Br
d)

Br2


H Br

Problem 8: Compounds (A), (B) and (C) are three methyl isomeric derivatives of benzene.
Identify which is o-, m- or p- from the products of nitration?
A 
conc. HNO3
H 2SO 4
two mononitro product
B 
conc. HNO3
H 2SO 4
 three mononitro products
Chemistry: Electrophilic Aromatic Substitution–12

C 
conc. HNO3
H 2SO 4
one mononitro product

Solution: CH3 CH3 CH3

CH3 CH3 CH3

HNO3
H 2SO 4

NO2
o-xylene
(A) NO2
CH3 CH3 CH3 CH3

NO2


HNO3
H 2SO 4
  
CH3 CH3 CH3 O2N CH3
m-xylene NO2
(B)
CH3 CH3
NO2

HNO3
H 2SO 4

CH3 CH3
p-xylene
(C)

Problem 9: O

Starting with benzene and succinic O

anhydride synthesise

 -tetralone .

Solution: O
O

C
CH2
 O 
AlCl3
FCR
 Zn  Hg  conc. HCl

4[H ], –H 2 O

CH2
C
O
HO CH2
CH2
CH2  

SOCl2 AlCl3 / CS2
–SO2 , – HCl FCR

CH2
C O
HO CH2   Tetralone

Problem 10: How the following conversions are achieved?

a) C6H5C2H5  C6H6 b) C2 H5

C2 H5
 Chemistry: Electrophilic Aromatic Substitution–13
CH3 O
c) d)
OH

C3 H7

e) Li

Solution: a) CH3 O OH


KMnO4

Soda lime



b) C2 H5

 2C2 H 5OH 

BF3

C2 H5
CH3 CH3 CH3 CH3
c)
Br

CH3I
AlCl3
 
Br2
Fe
  
Separate

Br Br
CH3


C3H7 Br
Na (C2 H5 )2 O


C3 H7
O

Cl CN
CH3 OH
d)


CH3 I
AlCl3
 
Cl 2
Sunlight 
KCN
 
H2O / H


e)

Br2
Fe
 
2Li
 LiBr

Br Li

Problem 11: Predict the structures of the intermediates in the following reaction sequence.
CH3
O O CH3 O
O

 O 
(A) (B) 
i) AlCl3
ii) H3O
Zn / Hg
HCl
H3 PO4

O
Chemistry: Electrophilic Aromatic Substitution–14

Solution: O
CH3
O
O CH3 O CH3
O
 O  
i) AlCl
3
ii) H O

Zn / Hg
HCl

3

O
O
O
HO
O (B)
HO CH3 O
(A)
O


H3 PO4
or HF


Problem 12: Predict the major monosubstituted product in the following cases.
C(CH3)3
a)

conc. HNO3
conc. H SO

2 4

CH(CH3) 2
b) CF3
NH2
Br2  AlBr3 (anhy.)
 

O2N
c)
OH  
Br2
CHCl3

OCH3
d)
 (CH 3 ) 2 C  CH 2 
H 2SO4

CH3

Solution:
C(CH3)3
a) c)
OH

CH(CH3) 2
NO2
Br
CF3 OCH3
b) d)
NH2 C(CH3)3

O2N Br
CH3

Problem 13: Write the structure of the major product (only monosubstitution is involved in
each case)
i) F ii) O
CH2 H3C C NH
Cl
 
AlCl3
?
 CH3COCl 
AlCl3
CS2
?
 Chemistry: Electrophilic Aromatic Substitution–15

iii) OH

CH2 
Br2
CHCl3
?

Solution: i) F ii) O

HN C CH3

CH3

C6H5 CH2
O CH3
iii) OH

CH2

Br

Problem 14: Hydrocarbon (A) with molecular formula C8 H 8 gave the following reactions:
1. On shaking with bromine, a bromo derivative (B) C8 H 8 Br2 was formed.
2. Vigorous oxidation of the hydrocarbon with alkaline KMnO 4 gave a
monobasic acid (C).
3. Acid (C) on distillation with sodalime gave C6 H 6 . Deduce structures of A,
B and C and name compound (A).

Solution: 1. The molecular formula of (A) and step (3) suggest (A) to be an aromatic
organic compound.
2. Step (2) suggests that (A) has a double bond in side chain. Thus, (A) may
be
CH CH2

(A) Phenylethene or Vinylbenzene or Styrene

Reaction:
1. CHBr
CH CH2 CH2Br

Br2

(B)

2. COOH
CH CH2 
Oxidation

alkaline KMnO 4

(C)Benzoic acid

3. COOH

Soda lim e

benzene
Problem 15: Describe how mescaline could be synthesized from toluene
Chemistry: Electrophilic Aromatic Substitution–16
NH2

H3C
O O
O CH3
H3C
mescaline

Solution CH3 CH3 CH3 CH3

OH
SO3 H OH
conc. H 2SO4  HNO3

fu min g H 2SO 4


i) NaOH, 
ii) H+
  
O2 N

SO3 H OH OH

conc. H 2SO4 , 

CH3 CH3 CH3

O OH OH
CH3
NaOH, 
3(CH ) sO  NaOH, 

3 2 4
 
H

O2 N O O2 N OH O2 N SO3 H
O CH3 OH OH
H3C
1. Sn/HCl
2. NaNO 2  HCl
3. H3 PO 2

CH3
O O H3C O
CH3 CH3 CH3
CH3Cl  AlCl3 (Excess)
alk. KMnO4 , 
   Heat

O O O
O CH3 O CH3 O CH3
H3C H3C H3C
H2N
Cl2 / h
CN Cl
O
CH3 O O
CH3 CH3

LiAlH 4
 
KCN

O
O O
O CH3
H3C O CH3 O CH3
H3C H3C

Assignments (New Pattern)

SECTION – I Single Choice Questions

1. Write the major product of the following reaction:

H5 C6
 
1. Br2 , heat, light
2. NaCN
?
CH3
CH3
H3C
(a) H5 C6 (b)
CN
CN
(o)NC C6 H4 m-NC C6 H4
(c) (d)
CH3 CH3

2. Among the following compounds (I – III), the correct order in reaction with
electrophile is
CH3 NO2

I II III

(a) II  III  I (b) III  I  II

 Chemistry: Electrophilic Aromatic Substitution–17

(c) I  II  III (d) I = II  III

3. Identify the correct order of reactivity in electrophilic substitution reactions of the

following compounds:
CH3 Cl NO2

1 2 3 4
(a) 1 > 2 > 3 > 4 (b 4 > 3 > 2 > 1
(c) 2 > 1 >3 > 4 (d) 2 > 3 > 1 > 4
4. Which one of the following is a free radical substitution reaction?
CH3

(a)  H3C Cl 

Anh. AlCl3


Cl NO2
(b)  AgNO2 


OH

(c) H3C  HCN 

 H3C
O CN
CH3
Cl
(d)  Cl2 
Boiling


5. The ortho/para directing group among the following is

(a) –COOH (b) –CN
(c) –COCH3 (d) –NHCOCH3
6. The treatment of benzene with isobutene in the presence of sulphuric acid gives
(a) isobutyl benzene (b) tert-butyl benzene
(b) n-Butyl benzene (d) No reaction

7. Benzoic acid, when heated with soda lime yields

(a) benzaldehyde (b) benzene
(c) toluene (d) benzylalcohol
(e) cyclohenxane

8. In the Friedel-Crafts synthesis of toluene, reactants in addition to anhydrous AlCl3 are

(a) C6H6 + CH4 (b) C6H6 + CH3Cl
(c) C6H5Cl + CH3Cl (d) C6H5Cl + CH4
9. Which of the following compounds will be most easily attacked by an electrophile?
NO2 Cl

(a) (b)
NH2 CH3

(c) (d)

10. In Friedel Craft’s alkylation, besides AlCl3, the other reactants are
Chemistry: Electrophilic Aromatic Substitution–18

(a) C6H6 + NH2 (b) C6H6 + CH4

(c) C6H6 + CH3Cl (d) C6H6 + CH3COCl

11. The reaction,

Benzene + Methy halide  
anhyd. AlCl3
 toluene, is known as
(a) Kolbe reaction (b) Wurtz reaction
(c) Perkin reaction (d) Friedel-Crafts reaction

12. Benzene does not undergo addition reactions easily because

(a) It has a cyclic structure
(b) Double bonds in it are very strong
(c) Resonance stabilized system is to be preserved
(d) It has six hydrogen atoms

13. The melting points of isomeric xylenes are in the order:

(a) p-xylene  o-xylene  m-xylene (b) p-xylene  m-xylene  o-xylene
(c) o-xylene  m-xylene  p-xylene (d) p-xylene  p-xylene  m-xylene

14. The correct order of C – C bond lengths in benzene (I), ethane (II), ethylene (III) and
acetylene (IV) is
(a) II  III  IV  I (b) IV  III  II  I
(c) II  I  III  IV (d) IV  III  I  II

15. Which of the following groups is ortho and para directing?

Cl

(a) (b) –– CHO

O
CH3

(c) –– OH (d)
O

16. The reaction of

H3C
OH with HBr gives

Br
H3C
H3C
(a) (b) OH
OH
Br
Br
H3C
H3C
(c) Br
(d) Br
Br

17. The correct order of reactivity towards the electrophilic substitution of the compounds,
aniline (I), benzene (II) and nitrobenzene (III), is
(a) II > III > I (b) I > II > III
(c) I > II > III (d) III > II > I
 Chemistry: Electrophilic Aromatic Substitution–19

18. Among the following compounds, the decreasing order of reactivity towards electrophilic
substitution is

CH3 O CF3
H3C
I II III IV

(a) III > I > II > IV (b) IV > I > II > III
(c) I > II > III > IV (d) II > I > III > IV

19. A group which deactivates the benzene ring towards electrophilic substitution but directs
the incoming group towards o- and p- positions is
(a) –NH2 (b) –Cl
(c) –NO2 (d) –C2H6
20. Which species represents the electrophile in aromatic nitration?
(a) NO 2 (b) NO 2
(c) NO2 (d) NO 3

21. The most reactive compound for electrophilic nitration is

(a) Benzene (b) Nitrobenzene
(c) Benzoic acid (d) Toluene

22. The function of AlCl3 in Friedel Crafts reaction is

(a) to absorb water (b) to absorb HCl
(c) to produce electrophile (d) to produce nucleophile
23. Which one of the following compounds will be most easily attacked by an electrophile?
Cl

(a) (b)
OH CH3

(c) (d)

24. Benzene reacts with CH3COCl gives

(a) Chlorobenzene (b) Toluene
(c) Benzyl chloride (d) Acetophenone

25. Which of the following will have fastest rate of reaction with Br2/FeBr3
NO2

(a) (b)
CH3 O
CH3
(c) (d)

SECTION – II May be more than one choice

1. Which of the following are true?

Chemistry: Electrophilic Aromatic Substitution–20

(a) Benzene tends to undergo substitution rather than addition reactions

(b) All hydrogen atoms of benzene are equivalent
(c) The carbon-carbon bonds of benzene are alternatively short and long around the ring.
(d) There can be two o-disubstituted derivatives

2. The major products of the following bromination reaction

Br2 ,h

400  600 C

CH3
Br

(a) Br (b)
CH3
CH3
CH3
(c) (d)
Br Br

3. Isopropylbenzene can be prepared by

CH3
Benzene + H3C  
(a) H 2SO4
(b) Benzene + H3C 
H 2SO4

CH2
Cl
CH3
Benzene + H3C 
AlCl3

(c) Benzene + H3C 
AlCl3
 (d)
Cl
Cl

4. Which of the following characteristics does an aromatic compound exhibit?

(a) It should have (4n + 2) -electrons (b) It should be planar and conjugated
(c) It should have 4n -electrons (d) It should process high resonance energy
5. Which of the following do not undergo a Friedel-Crafts reaction with benzene?
(a) Aniline (b) Chlorobenzene
H3C CH3

(c) (d) Acetyl chloride

H3C Cl

6. The reaction of biphenyl with HOCl in the presence of a strong acid gives
Cl Cl

(a) (b)

Cl

(c) Cl (d) Cl

7. Which of the following statements are true for benzene?

(a) It is a flat, regular, hexagonal molecule
(b) Each C – C – C angle is 109°28
(c) The C – C bond length is 1.39Å
(d) All carbon atoms are sp3 hybridised
 Chemistry: Electrophilic Aromatic Substitution–21

8. Which of the following are electrophilic substitution reactions?

(a)  Cl2 

FeCl3
 (b) + fuming H 2SO4 


(c)  Cl2  

UV light
 (d) All of these

9. Toluene reacts with ethyl bromide in the presence of anhydrous AlCl3 to produce
(a) o-ethyltoluene (b) p-ethyltoluene
(c) m-ethyltoluene (d) a mixture of all of these

10. Isopropylbenzene can be obtained by

(a)  H3C 

AlCl3
 (b)  H3C 
AlCl3

CH2 Cl
H3C
(c)  Cl 
AlCl3
 (d)  H3C 

H3C O CH3

11. The sulphonation of toluene with oleum at 35°C produces

(a) p-toluene sulphonic acid
(b) o-toluene sulphonic acid
(c) m-toluene sulphonic acid
(d) a mixture of (a), (b) and (c) in approximately equal proportions

12. Which of the following groups are ortho and para-directing?

(a) – OH (b) – CHO
(c) – CN (d) – NHCOCH3

13. m-Nitrobenzoic acid can be obtained by

(a) toluene 
[O]
KMnO 4
A 
HNO3
H 2SO 4

(b) toluene [O]
CrOCl2
 A 
HNO3
H 2SO4
 B 
[O]
KMnO 4

(c) toluene 

nitration
HNO3  H 2SO 4
 A 
[O]
KMnO 4

(d) all these methods

14. Which of the following statements are correct?

(a) An activating group is an electron-releasing group
(b) An activating group activates all positions of the benzene ring.
(c) The effect of any group –– whether activating or deactivating –– is the strongest at the
ortho- and para-positions in the benzene ring.
(d) An activating group activates only the ortho- and para-positions in the benzene ring.

15. The necessary conditions for halogenation are

(a) low temperature (b) darkness
Chemistry: Electrophilic Aromatic Substitution–22

(c) the presence of a halogen carrier (d) none of these

16. Benzene can undergo

(a) substitution (b) addition
(c) elimination (d) oxidation
17. Which of the following statements about the nitration of aromatic compounds are correct?
(a) The rate of nitration of toluene is greater than that of benzene
(b) The rate of nitration of benzene is almost the same as that of hexadeutrobenzene
(c) The rate of nitration of benzene is greater than that of heaxadeutrobenzene
(d) Nitration is an electrophilic substitution reaction
18. Which of the following intermediate stages are possible in the conversion of
benzaldehyde into benzoin by reaction with HCN?
CN CN
(a) H3C H (b) H3C
OH OH
CN H

(c) H3C C6H5 (d) None of these

OH OH

19. Which of the following can be represented by a resonance hybrid?

(a) Sulphur trioxide (b) Benzene
(c) Toluene (d) Benzene sulphonic acid

20. Iodobenzene can be obtained by

(a) C6 H 6  I 2 
 (b) C6 H 6  I 2 
HNO3

(c) C6 H5 N 2 Cl  KI  (d) C6 H 6  HI  
21. Toluene, when treated with Br2/Fe, gives p-bromotoluene as the major product because
the –CH3 group
(a) is ortho - para directing (b) is meta directing
(c) activates of the ring by hyperconjugation (d) deactivates the ring

22. What is the end product obtained by nitration of toluene?

(a) o-Nitrotoluene (b) p-Nitrotoluene
(c) 2,4-Dinitrotoluene (d) 2,4,6-Trinitrotoluene

23. Ozonolysis of p-xylene gives

(a) Glyoxal (b) Methyl glyoxal
(c) Both of these (d) None of these

24. In the reaction,

+ Cl2 
FeCl3
 Cl  HCl

the attacking species is

(a) Cl2 (b) Cl+
(c) Cl– (d) FeCl4
 Chemistry: Electrophilic Aromatic Substitution–23

25. During electrophile substitution in benzene, the intermediate species involved is

(a) Carbocation (b) Carbanion
(c) Free radical (d) None of these

SECTION – III Comprehension Type Questions

 Write-up I
A third group is least likely to enter between two groups in the meta relationship. This is
the result of steric hindrance and increases in importance with the size of the groups on
the ring and with the size of the attacking species.
When a Meta-directing group is meta to an ortho-para directing group, the incoming
group primarily goes ortho to the meta directing group rather than para.

1. Chlorination of m-chloro nitro benzene gives

NO2 NO2

(a) (b)
Cl
Cl Cl Cl
NO2 NO2
Cl
(c) (d)
Cl Cl

2. CH3
OH


E

CH3 CH3
OH OH
(a) (b)
E E
CH3
OH
(c) (d) (a), (b)

3. O

HN CH3


Cl2 / CH3COOH

Chemistry: Electrophilic Aromatic Substitution–24

O O

HN CH3 HN CH3
Cl
(a) (b)
Cl
CH3 CH3
O O
HN CH3 HN
Cl Cl
(c) (d)

Cl CH3

4. CH3


HNO3
H 2SO 4

NO2
CH3
CH3
NO2
(a) (b)
NO2
NO2
NO2
CH3
CH3
O2 N
(c) (d)
NO2
NO2

 Write-up II
The leaving group is the functional group that is eliminated with electrons of the -bond
in a reaction. The nature of the leaving group is important to both SN1 and SN2 reactions.
Better the leaving group faster is the reaction. The relative leaving ability of leaving
group Y in R – Y is enhanced by.
i) the strength of the R – Y bond
ii) the polarizability of R – Y bond
iii) the stability of Y– and
iv) the degree of stabilization through solvation of Y.

5. Which one of the following is good leaving group?

(a) Triflate (b) Mesylate
(c) Tosylate (d) all are equal

6. Which one of the following statement is correct?

(a) The nature of leaving group important to SN1 only
(b) The nature of leaving group important to SN2 only
(c) The nature of leaving group important to SN1 and SN2
(d) All

7. Which one of the following is correct statement?

 Chemistry: Electrophilic Aromatic Substitution–25

(a) HO–, RO– and NH 2 are strong bases and therefore are good leaving groups
(b) I– is good leaving group than F–
(c) charged species are bad leaving groups than neutral leaving groups
(d) The conjugate bases of strong oxygen acids such as Tosylate are bad leaving group

8. Which one of the following is correct?

(a) Protonation of alcohols with strong acids converts the poor leaving group hydroxyl
group into much better leaving group.
(b) The hydroxyl group converted into a good leaving group by reaction of alcohols with
p-toluensulfonxyl chloride
(c) the amine group converted into a good leaving group by treated with HNO2 5°C in
primary amines
(d) RO– is strong base therefore good leaving group.

9. Which is/are not readily under goes nucleophilic substitution?

H2C
(a) Cl
(b) Ph Cl

Cl

(c) (d) All of these

 Write-up III
In benzene all carbon atoms are sp2 hybridized. Each carbon atom carries one
unhybridised ‘p’ orbital. Because benzene is planar molecule, all the six unhybridised p-
orbitals overalp to form a single  molecular orbital which is in a state of constant
delocalization, and this delocalization gives the molecule stability. So benzene serves as a
source of electrons. So the electrophile which is electron deficient will be attracted by 
cloud of benzene, while nucleophiles with completed shell structure will be repelled by
the  cloud of benzene. So the characteristic reactions of benzene are electrophilic
substitution reactions.

10. Hybridisation of nitrogen in nitronium ion is

(a) sp (b) sp2
3
(c) sp (d) dsp2
11. Benzene reacts with n-propyl chloride in presenceof anhydrous AlCl3 to form
(a) n-propyl benzene (b) acetophenone
(c) cumene (d) propiophenone

12. Benzene reacts with phosgene in presence of anhydrous AlCl3 to form

(a) Benzyl chloride (b) Phenyl chloroform
(c) Benzoyl chloride (d) benzylidene chloride

13. Which under goes nitration faster

(a) nitrobenzene (b) Benzene
(c) Tolulene (d) All three will have same reactivity

 Write-up IV
 
C6H6 + CH3Cl 
Anhy
AlCl3
 A 
SeO2
 B CN

alcoholic
 C 
Dil. HNO3
 D 
Dil. OH
E
Chemistry: Electrophilic Aromatic Substitution–26

14. In the above reaction ‘E’ is

HO O O O
(a) C C (b) C C

OH

(c) CHO (d) Ph COO

Ph

15. The order of reaction from ‘B’ to C

(a) I (b) II
(c) III (d) zero

16. Para nitro benzaldehyde undergo

(a) benzoin condensation (b) Aldol condensation
(c) Cannizaro reaction (d) None of these

17. Benzaldehyde in presence of conc. NaOH produces

(a) PhCOO–, PhCH2OH (b) Ph–CO–CO–Ph, Ph–CHOH–CO–Ph
OH

(c) Ph COO , PhCH 2 OH (d) PhCOO–, Ph–CO–CO–Ph

Ph

SECTION – IV Subjective Questions

LEVEL – I

1. Predict the major product in each of the following reactions.

O

CH3 1. Br2 (1 equivalent)


2. NaBH 4
3. Base
?

2. What would be the major product in following reaction?

O

N 
1 eq.Br2 / Fe
?

3. When benzene is treated with DCl at low temperatures a compound C6H6DCl©, is

formed. On warming the reactants, C6H6 and DCl are re-formed. However, in the
presence of AlCl3 an isomer of C6H6DCl(D) is produced, which on warming, gives
mainly C6H5D and HCl. Explain
4. Give structure of the principal organic products expected from mononitration of
a) o-nitrotoluene b) m-dinitrobenzene
c) m-cresol d) m-nitrotoluene
5. Account of the following
 Chemistry: Electrophilic Aromatic Substitution–27

Br
Ph Ph
h
CH3  1 eq. Br2  CH3
H3C H3C
with little or no PhCH2C(Br)(CH3)2 formed.
6. C7H7Cl has four isomers A1, A2, A3 and A4
A4   Benzene, Identify A1, A2, A3 and A4.
I ) KMnO 4
II ) Soda lim e, 

7. H5C6

CH3   A 

B
alc. KOH HBr
heat

Br

8. Oxidation of toluene by acidic KMnO4 gives poor yield of benzoic acid while oxidation
of p-nitrotoluene gives good yield of p-nitrobenzoic acid. Why?
9. What happens when p-xylene is treated with concentrated sulphuric acid and the resultant
product is fused with KOH?

10. CH3


conc. HNO3 – conc. H 2SO4

NO2
In the above reaction which product is most likely to be formed?

LEVEL – II

1. Give the products of the following reactions

CH3
a) b)
N 1. NBS/

2. Mg/Et 2 O
3. ethylene oxide

4. H +
 Br2 


F
c)
F F

 Cl2 
anhy.FeCl3


2. An aromatic compound A (C7H7NO2) on reduction gives B (C7H9N). Diazotization of B

and subsequent treatment with CuCN/KCN gives C (C8H8O2). Hydrolysis of C followed
by oxidation forms D, which has equivalent mass of 83g eq–1. D forms only one mono
substitution product. Give structure for A, B, C and D.

3. A compound (C8H10O) upon treatment with alkaline solution iodine gives a yellow
precipitate. The filtrate on acidification gives a white solid E (C7H6O2). Write the
structures of D, E and explain the formation of E.
Chemistry: Electrophilic Aromatic Substitution–28

4. Give the product(s) obtained from the reaction each of the following compounds with
Br2/FeCl3.
NO2
a) b)
O

H3C O

5. Write the structures of the compounds from the following data.

a) Ph
CH3  Br2 (A) 
(B)  (C) 
hv alc. KOH cold dil hot
KMnO4 KMnO4
(D)
Ph H
b)
 Br2  FeBr3 (anhy.) 
(E) HBr

peroxide
(F)
H CH3

H3C
6. CH3
H3C
Br
CH3
 Br2 
 AlBr3
 CH2  HBr

H3C

7. Compounds (A) and (B) are isomers having the formula C8H10. On oxidation (A) gives
benzoic acid while (B) gives phthalic acid which forms an anhydride (C) on heating.
Identify (A), (B) and (C).

8. How will you synthesize

CH3

from benzene?
9. Identify A to C in the following:
CH3


alkaline KMnO4
 A 
LiAlH4
 B 
conc. HCl
ZnCl, 
C

10. Complete the following reactions:

a) 4-bromo-2-methylphenol treated with 2-methylpropene and sulphuric acid.
b) p-cresol treated with propanoyl chloride and aluminium chloride.
c) 2,5-dichlorophenol reacts with chlorine in acetic acid.
LEVEL – III (Judge yourself at JEE level)

1. Phenyl ring is known to exert negative inductive effect. But each phenyl ring in biphenyl
(C6 H5 — C6 H 5 ) is more reactive than benzene towards electrophilic substitution.
Explain.

2. Show synthesis of p-bromonitrobenzene from benzene in two steps.

3. Fill in the blanks with appropriate structure of reaction products in the following
transformations:
o — HOOC — C6 H 4 — CH 2 — C6 H 5  SOCl2
 A 
Anhydrous
AlCl3
 B 
Zn –Hg
HCl
C

4. Predict the structures of the intermediates/products in the following reaction sequence.

 Chemistry: Electrophilic Aromatic Substitution–29

OMe O O
OMe
 O  A  B 
1. AlCl3
2. H3O
Zn / Hg / HCl H3 PO4

5. Predict the product

Me CH3 CCl3

i) Br 
Anhydrous
? ii)
 H3C
AlCl3

Cl2
Fe
?
H

6. Convert
CO2H CO2H

F
7. Predict the product
O


Cl2 ,FeCl3
 A 
Na —Hg / HCl
 B 
HNO3 / H 2SO4
C
Cl

8. Predict the product

O

N 
Br2 / Fe
(1 eq)
?

9. 7-bromo-1, 3, 5-cycloheptatriene exists as a ionic substance whereas 5-bromo-1, 3-

cyclopentadiene does not ionize even in the presence of Ag+ ion. Explain?

SECTION – V Miscellaneous Questions

Match the following

1. X Y
a) Cyclic conjugated polyenes with i) Arenes and alkyl halides in presence of
(4n + 2)-electrons anhydrous AlCl3
b) o-dichlorobenzene does not exist ii) Aromatic compounds
as two isomers
c) Friedel crafts reaction iii) Delocalization of -electrons
d) Meta directing group iv) Activates the ring towards electrophilic
substitution
e) Ortho directing group v) Deactivates the ring towards electrophilic
Chemistry: Electrophilic Aromatic Substitution–30

substitution

The following questions (2 to 5) consists of two statements, one labelled as ASSERTION (A)
and REASON (R). Use the following key to chose the correct appropriate answer.
(a) (A) and (R) both are correct and (R) is the correct explanation of (A)
(b) (A) and (R) both are correct but (R) is not the correct explanation of (A)
(c) (A) is correct but (R) is incorrect.
(d) (A) is incorrect but (R) is correct

2. Assertion: Tropylium ion

is aromatic in character
Reason: The only property which decides the aromatic character is its planar
nature.

3. Assertion: Friedel crafts reaction between benzene and acetic anhydride in presence
of anhydrous AlCl3 yields acetophenone and not poly substituted products.
Reason: Acetophenone formed poisons the catalyst preventing further reaction.

4. Assertion: Cyclobutane is less stable than cyclopentane

Reason: Presence of bent bonds causes loss of orbital overlap.

5. Assertion: Alkyl benzene is not prepared Friedel Crafts alkylation of benzene

Reason: Alkyl halides are less reactive than acyl halides.

Answers to Assignments
SECTION - I

1. (a) 6. (b) 11. (d) 16. (b) 21. (d)

2. (c) 7. (b) 12. (c) 17. (c) 22. (c)
3. (c) 8. (c) 13. (a) 18. (a) 23. (c)
4. (d) 9. (c) 14. (c) 19. (b) 24. (d)
5. (d) 10. (c) 15. (c) 20. (b) 25. (d)

SECTION - II
 Chemistry: Electrophilic Aromatic Substitution–1

1. (a), (b) 10. (a), (b), (c) 19. (a), (b), (c), (d)
2. (a), (c),(d) 11. (a), (b) 20. (b), (c)
3. (a), (b), (c), (d) 12. (a), (d) 21. (a, c)
4. (a), (b), (d) 13. (a), (b) 22. (c)
5. (a) , (b), (c) 14. (a), (b), (c) 23. (c)
6. (a) , (b), (c) 15. (a), (b), (c) 24. (b)
7. (a), (c) 16. (a), (b),(d) 25. (a)
8. (a), (b) 17. (a),(c), (d)
9. (a), (b) 18. (a), (b), (c)

SECTION - III

1. (d) 6. (c) 11. (c) 16. (d)

2. (d) 7. (b) 12. (c) 17. (a)
3. (b) 8. (b) 13. (c)
4. (d) 9. (d) 14. (d)
5. (a) 10. (a) 15. (c)

SECTION - IV

LEVEL - I

O
1.

O
2.
N Br

3. Since D is not incorporated into the benzene ring in the absence of AlCl3, isomer C has
no C – D  bond. Instead, the D end of DCl is attracted to the  cloud of benzene to form
a loosely bound  complex, indicated by an arrow in the structural formula.  complexes
are also called charge – transfer complexes, because the electron – rich benzene ring, the
donor molecule, transfers some electron density to the electron-poor D of DCl, acceptor
molecule. With the catalyst AlCl3, exchange of D+ for H+ occurs on warming. This
exchange requires the formation of a C – D bond to give the  complex. with D+. The
benzene ring is reformed by losing an H rather than the D because the C – H bond is
weaker than the C – D bond. Notice the delocalization of the positive charge in the 
bond.

D  Cl   C6 H 6  DCl

 complex, C
Chemistry: Electrophilic Aromatic Substitution–54

CH3 NO2 OH CH3

4. a) b) c) d)
NO2 O2 N

O2 N NO2 CH3 NO2

NO2 NO2

Ph Ph Ph
5.
CH3  Br2 / h CH3 and CH3

H3C H3C H3C

2 benzylic 3 alkyl

Br Br

Br
CH3
Ph
Ph
CH3 Br
H3C
H3C
(major) (little yield)
This reaction proceeds via free radical mechanism forming 2 free radicals, of which 2°
benzylic free radical is stabilized more by resonance of phenyl ring and with
hyperconjugation of –CH3 group, thus resulting in the formation of PhCH(Br)CH(CH3)2
as the major product.
6. A1, A2, A3 are o, p, m-chlorotoluenes A4 - benzyl chloride
7. Br
H5 C 6
A= CH3
B= H5 C6

CH3

8. Oxidant is an electrophile, it can attack and destroy the ring in case of toluene. But in p-
nitrotoluene, the –NO2 group deactivates the electrophilic attack on benzene nucleus and
thus increases the yield of p-nitrobenzoic acid.

9. CH3 CH3 CH3

SO3H
conc. OH
  fusion
 
H 2SO4 with KOH

CH3 CH3
CH3
p-Xylene
2-5,Dimethylphenol
10. CH3
O2N

NO2
LEVEL - II
 Chemistry: Electrophilic Aromatic Substitution–55

1. a) b) CH3 OH

N N 1. NBS/
N

2. Mg/Et 2 O
3. ethylene oxide

Br Br 4. H +

 Br2 
 

(minor)
Br
(major)
F F
c)
F F F F

 Cl2 
FeCl3

Cl

2.
H3C NO2 H3C NH2
A= B=
1-methyl-4-nitrobenzene p-toluidine
O O O
H3C D
C= OH = HO OH
4-methylbenzoic acid terephthalic acid

3. The reaction of C8H10O with alkaline solution of iodine is an iodoform reaction. This
reaction is possible if the compound D has –CO2 – CH3 or – CH(OH) – CH3 group. The
high carbon content in D indicates that D is an aromatic compound containing a benzene
ring. To account for the given formula, the compound D may be C6H5CH(OH)CH3. The
given reactions are
CH3 CH3 O Na I

 [O]


I2 / NaOH
 I
OH O O I
1-phenylethanol

H
OH

O
benzoic acid

NO2
4. a) b)
O Br Br

H3C O

5. a) Br
H5 C6
H5 C6
A= B=
H3C
H3C
Chemistry: Electrophilic Aromatic Substitution–56

OH OH

H5 C 6 O
C= D= O
OH  H3C

H3C C6 H5 OH
b) p-Br
p-Br C6 H4 Br
H4 C 6 H
E= F=
CH3
H CH3

6. The Friedel-Crafts alkylation can be reversed especially when a 3° alkyl group such as
Me3C is present. Dealkylation is effected with Alr3 by transfer of Me3C+ to another arene
used as solvent, or at high temperature by protonation as H+ and loss of Me3C as
Me2C = CH2.
H3C H3C
CH3 CH3
H3C
CH3 
CH3  Br 

+

  CH2  HBr
H
Br Br H3C

7. CH3
CH3
CH3
(A) is (while (B) is

O
HO O
CH3 O O

CH3 O
OH 
 [O] 

 H 2O

O
(B)

CH3 OH

[O]


(C)

O
8.
H3C CH3
 O 
AlCl3
 
Zn (Hg) / HCl
(Clemmensen reduction)

CH3
Cl

O
9.
OH Cl
A= OH B= C=

OH CH3 OH
10. a) H3C
CH3 CH3 CH3

 H3C 
H 2SO 4 H3C

CH2
Br Br
 Chemistry: Electrophilic Aromatic Substitution–57

OH O
b) OH

 H3C 
AlCl3

O CH3
CH3 Cl CH3
Cl Cl
c)
OH OH
2Cl2

CH3COOH

Cl Cl
Cl Cl

LEVEL - III

1. Phenyl group also can exert +R effect; in biphenyl one of the phenyl groups acts as
electron donor and other electron acceptor. This makes biphenyl more reactive than
benzene towards electrophilic substitution.

Br
2. Br Br

NO2


Br2
Fe
 
HNO3
H 2SO4
 

NO2

ortho 38% para 62%

Fractional crystallisation

3. O O

Cl
(A) (B) (C)
CH2

4. OMe OCH3

(A) (B)
CO2H CO2H

5. CCl3
CH3

(i) H 3C C CH3 (ii)

CH3 Cl

6. CO2H CO2H CO2H


Conc.
H 2SO 4
 
KHF2
Fusion

SO3H F
Chemistry: Electrophilic Aromatic Substitution–58

7. O NO2

(A) (B) (C)

Cl Cl Cl
Cl Cl
8. O

N Br

9. is aromatic and hence exists as ion but the carbocation will be antiaromatic

and hence will not exists as ion even in presence of Ag+ ion.

SECTION - IV

1. (a – ii), (b –iii), (c – i), (d – v), (e – iv)

2. (a)
3. (c)
4. (a)
5. (b)

