Chemistry : Electrophilic Aromatic Substitution

SECTION - I
SUBJECTIVE TYPE PROBLEMS

Problem 1: The pK a for cyclopentadiene is 16 and that of cycloheptatriene is 36.

Solution: Cyclopentadiene is more acidic because its conjugate base, cyclopentadienyl anion is unusually
stable due to aromatic character,

This is delocalized and give rise to a ring with six delocalized  electrons.
Problem 2: Treatment of biphenyl with a mixture of nitric acid and sulfuric acid gave two principal
products both having the molecular formula C12 H 9 NO2 . What are these two products?

Solution: Electrophilic aromatic substitution in biphenyl is best understood by considering one ring as
the functional group and the other as a substituent. An aryl substitent is ortho, para-directing.
Nitration of biphenyl gives a mixture of o-nitrobiphenyl and p-nitrobiphenyl.

HNO3

H 2SO 4
  NO2

O 2N
Biphenyl o-Nitrobiphenyl p-Nitrobiphenyl
(37%) (63%)

Problem 3: Nitrobenzene does not undergo Friedel – Craft’s alkylation.

Solution: The nitro group in nitrobenzene strongly deactivates the benzene ring. This decreases the
reactivity of benzene towards Friedel – Craft’s alkylation.
Problem 4: Aniline undergoes bromination in ortho and para position but in presence of strong
acid it gives m-bromo aniline. Explain?

Solution: – NH 2 group is o– and p-directing. However, in presence of strong acid aniline combines
 
with proton to form C5 H 5 N H 3 and – H N 3 group is m-directing. thus, -bromo product is

formed in presence of strong acid.

Problem 5: Reaction of chlorobenzene with p-chlorobenzyl chloride and aluminum chloride gave
a mixture of two products in good yield (76%). What were these two products?
Solution: The reaction is a Friedel-Crafts alkylation in which 4-chlorobenzyl chloride serves as the
carbocation source and chlorobenzene is the aromatic substrate. Alkylationoccurs at the
positions orhto and para to the chlorine substitutent of chlorobenzene.
 Chemistry : Electrophilic Aromatic Substitution

Cl
CH2 Cl
Cl  H2CCl Cl 
AlCl3

Chlorobenzene 4-Chlorobenzyl chloride 1-Chloro-2-(4'-chloroben

zyl-benzene
 Cl CH2 Cl
1-Chloro-4-(4'chloroben
zyl)-benzene

Problem 6: Fridel Crafts acylation requires an excess of the catalyst but Friedel Craft’s alkylation
requires only a catalytic amount. Eexplain.
Solution: The product of acylation co-ordinates with the catalyst and removes the latter from the
reactant side. For this reason Fridel crafts acylation requires an excess of catalyst. The
product of alkylation does not coordinate with the catalyst. So, the catalyst can form complex
with the alkylation agent and the catalyst propagates the reaction.
Problem 7: Although benzene is highly unsaturated, it does not undergo addition reactions.
Explain.
Solution:  -electrons of benzene ring are delocalized throughout the molecule. This makes the
molecule very table. The addition reactions would result in the breaking of this
delocalization, i.e., the stability of the molecule which is resisted.

Problem 8: Show by an arrow the preferred product of reaction with E  of each of the three
isomeric
(a) Nitrotoluenes
(b) Methoxy acetanilid’s. Explain your choices in each case.

NO 2
Solution: (a)
NO2
NO 2
Ortho Meta Para
(A) (B) (C)

In (A) CH3 directs E  to ortho and para positions which are also meta to NO2, i.e.
substituents reinforce each other. In (B) orientation is in opposition. The o–, p– director
controls the orientation, i.e. E  enters para to CH3  ortho position to NO2. In (C) both
groups are reinforcing i.e. ortho to CH3 and meta to NO2.
Chemistry : Electrophilic Aromatic Substitution

CH3 CH3 CH3

CO CO CO
NH NH NH
O
(b) CH3

Ortho Meta OCH 3 O Para

(A) (B) H3CO (C)

Both the substituents are o–, p-directing and equally moderate strong activations. In
(B) both the groups are reinforcing and a mixture of two isomer is obtained. In (A) and
(C) two groups are in opposition. In (A) substantial amounts of all isomers are obtained
while in (C) substitution occurs ortho to both the groups.
Problem 9: The rates of bromination with ( FeBr3 ) catalyst of C 6 H 6 and C 6 D6 are the same.
Discuss.
Solution: All the evidence favous a bimolecular mechanism for bromination; this may be written as
follows
Mechanism
–
fast
Step (i) Br — Br  FeBr
3 Br — Br  — Fe Br3

H Br

slow
Step (ii)  Br — Br — FeBr3  FeBr4

Br
H Br

Step (iii)  FeBr4

Fast  HBr  FeBr3

Since step (ii) and (iii) both are bimolecular in which step-ii is rate determining step, but step-
iii is a fast step reaction. Since H is replaced by D in step-iii thereby C—H or C—D, bond
fission cannot be involved in rate determining step. Hence no kinetic isotopic effect is observed
when H is replaced by D. So, rate of bromination of C6 H 6 and C6 D 6 is same
Problem 10: Predict the major monosubstituted product in the following cases.

C(CH3)3 CF3
NH2
HNO3 Br2
(a) 
acetic acid
 (b) 
acetic acid


CH(CH3)2 O2N
 Chemistry : Electrophilic Aromatic Substitution

Br2
(c) OH 
CHCl3


OCH3

H 2SO 4
(d)  (CH 3 )2 C  CH 2 

CH3

C(CH3)3 CF3
NH2

Solution: (a) (b)

CH(CH3)2 O2N Br
NO2

OCH3
C(CH3)3

(c) OH (d)

CH3
Br
Chemistry : Electrophilic Aromatic Substitution

SECTION - II
SINGLE CHOICE PROBLEMS
Problem 1: Among the following where ortho/para ratio is highest (for electrophilic substitutions nitration).
(a) chlorobenzene (b) flurobenzene
(c) bromobenzene (d) Iodobenzene
Solution: Due to strong –I effect flurobenzene gives lowest ortho/para ratio (which is contradictory if
one only thinks about the size of the substitutent).
(d)
Problem 2: Which of the following pair are not a meta directing substituent when present on a benzene
ring
(a) —C6H5 and —NO2 (b) —Cl and –CO2H
(c) and —Cl (d) —Cl and —CN
Solution: When phenyl is attached with benzene ring it activates benzene in electrophilic aromatic
substitution reactions and it is ortho/para directing where as chlorine when attached with
benzene ring it slightly deactivate benzene ring but still it is ortho/para directing.
(c)
O
Problem 3:  H3C C O2 O BF3
 P, P is
O
O

O
CH3
(a) (b)
O O CH3
O

O
CH3 CH3
(c) (d)
O O O
Solution: (b) O
Problem 4: Which is the correct order of the following compound in decreasing reactivity towards
electrophilic substitution:
Dichloromethylbenzene, Difluorobenzene, Toluene, Chloromethyl benzene
(I) (II) (III) (IV)
(a) II > IV > III > I (b) III > IV > II > I
(c) III > IV > I > II (d) III > I > II > IV
Solution: Electron pushing group activates the electrophilic aromatic substitution reactions whereas
electron withdrawing group deactivates it.
(c)
 Chemistry : Electrophilic Aromatic Substitution

Problem 5: Which of the following statements is correct

(a) Polyalkylation and polycacylation both are very common in Fridel Crafts reaction
(b) Polyalkylation is common but polycacylation is rare in Friedel Crafts reaction
(c) Both Polyalkylation and polycacylation is rare in Fridel Crafts reaction
(d) Polycacylation is common but Polyalkylation is rare in Fridel Crafts reaction
Solution: Alkyl groups are electron releasing groups, and once one is introduced into the benzene ring
it activates the ring towards further substitution.
Polyacylations are not a problem in Friedel-Crafts acylations however. The acyl group
(RCO–) by itself is an electron-withdrawing group, and when it forms a complex with in the
last step of the reaction, it is made even more electron withdrawing. This strongly inhibits
further substitution and makes monoacylation easy.
(b)
Problem 6: Among the following statements on the nitration of aromatic compounds, the false one is
(a) the rate of nitration of benzene is almost the same as that of hexadeuterobenzene
(b) the rate of nitration of tolnene is greater than that of benzene
(c) the rate of nitration of benzene is greater than that of hexadeuterobenzene
(d) nitration is an electrophilic substitution reaction.
Solution: Sigma complex formation is the rds in nitration. It doesn’t show kinetic isotope effect. Due
to this the rate of nitration of benzene and that of hexadeuterobenzene occurs at same rate.
(c)
Problem 7: Among the following which is maximum soluble in water
(a) 3 Bromo cyclopropenyl bromide
(b) Cyclopentadienyl bromide
(c) Bromocyclopropane
(d) 3-Bromocyclobutenyl bromide.
Solution: Water is a polar solvent so the compound which has maximum ionic character should have
maximum solubility in water. 3 Bromo cyclopropenyl bromide has the maximum ionic character
as gets aromatic stability. (a)
Problem 8: Among the following which statement is correct
(a) Pyridine is weaker base than pyrrole and its dipole moment is away from the ring.
(b) Pyridine is stronger base than pyrrole and its dipolemoment is towards the ring.
(c) Pyridine is weaker base than pyrrole and its dipolemoment is towards the ring.
(d) Pyridine is weaker base than pyrrole and its dipole moment is towards the ring.
Solution: (a)
Chemistry : Electrophilic Aromatic Substitution

Problem 9: Benzene on reaction with ICl in presence of anhydrous gives ?

Cl I

(a) (b)

I
I
Cl
(c) (d)

Cl
Solution: When ICl heated with I+Al–Cl4
complex formation is more farourable than Cl+Al–Cl3I
complex. So iodiobenzene is formed.
(b)
Problem 10: When the following compound is dissolved which of the following option is

Cl

formed.

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)
 Chemistry : Electrophilic Aromatic Substitution

SECTION - III
MULTIPLE CHOICE PROBLEMS
Problem 1: Which of the following are electrophiles?
(a) Water (b) Ammonia
(c) Triphenylsulphide (d) Iodides
Solution : (a, c)
Problem 2: Which of the following are examples of electrophilic addition?

OH
|
(a) CH3CH  CH3  H 2 O 
 CH 3 —CH — CH 3

Peroxides
(b) CH3 CH  CH3  HBr   CH 3 CH CH 3
|
Br

(c) CH3CH  CHCH 3  Br2 

 CH3 CH— CH— CH 3
| |
Br Br
(d) none of these
Solution : (a, c)
Problem 3: The conversion
CH2 CH2CH3 CH2 CH2CH3

Br

can be effected using

(a) Br2/CCl4 (b) Br2/H2O
(c) Br2/Fe (d) Br2/benzoyl peroxide
Solution : (c)
Problem 4: Isopropylbenzene can be prepared by
(a) Benzene + CH3 CH  CH 2 
H SO2 4

(b) Benzene + CH3 —CH — CH 3 

H 2SO 4
|
Cl
AlCl3
(c) Benzene + CH3 CH— CH3  
|
Cl
AlCl3
(d) Benzene + CH3 CH 2CH 2Cl  
Solution : (a, b, c, d)
Chemistry : Electrophilic Aromatic Substitution

Problem 5: Which of the following do not undergo a Friedel–Crafts reaction with benzene?
(a) Aniline (b) Chlorobenzene

H3C CH3
(c) C C (d) Acetyl chloride

H3C Cl

Solution : (a, b, c)
Problem 6: Aniline, on acetylation followed by bromination (Br2/CH3COOH) and subsequent hydrolysis,
gives
(a) o–bromoaniline (b) p–bromoaniline
(c) m–bromoaniline (d) m–bromoacetanilide
Solution : (a, b)
Problem 7: Which of the following groups are electron–withdrawing?
(a) –COOH (b) –C 6H5
(c) –NH2 (d) –OH
Solution : (a, b)
Problem 8: 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.
Solution : (a, b, c)
Problem 9: 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 hexadeutrobenzene
(d) Nitration is an electrophilic substitution reaction
Solution : (a, c, d)
Problem 10: The reaction

C6 H6 
 C6 H 5CH3
is a
(a) Friedel–Crafts reaction (b) Wurtz reaction
(c) Perkin reaction (d) Grignard reaction
Solution : (a)
 Chemistry : Electrophilic Aromatic Substitution

MISCELLANEOUS PROBLEMS
SECTION - IV
COMPREHENSION TYPE PROBLEMS

Write up – I
When a monosubstituted benzene undergoes an electrophilic substitution, the position taken up by the
incoming group and the rate of the reaction are determined by the substituent already present on the
benzene ring. On this basis various substituents can be divided into three categories :
(1) o, p-directing and activating
(2) m-directing and deactivating
(3) o, p-directing and deactivating

Problem 1 : Which of these is o, p–directing and deactivating group?

(a) –F (b) –Cl

(c) –Br (d) all of these
Solution : (d)
Problem 2 : Which one of the following compounds is most reactive for ArSE reaction?
(a) C6H5–F (b) C6H5–Cl
(c) C6H5–I (d) C6H5–NO2
Solution : (a)
Problem 3 : Which compound is most reactive for ArSE reaction?
(a) C6H5–NO2 (b) C6H5–CN
(c) C6H5–OCH3 (d) C6H5–CH3
Solution : (c)

Write up – II
Electrophilic substitutions are characteristic reactions of aromatic compounds. In this reaction hydrogen
of the aromatic ring is replaced by an electrophilic because hydrogen in the form of H+ is very good
leaving group. –COOH and –SO3H are also good leaving groups when they are present either at
ortho or at para to the highly activating groups like –NH2 and –OH.

Problem 4 : In the given reaction

NH2

COOH Br2 (excess)

H O
[X]
2

[X] will be
Chemistry : Electrophilic Aromatic Substitution

NH2 NH2

COOH Br COOH

(a) (b)

Br Br
NH2
NHBr
Br Br
COOH
(c) (d)

Br
Solution : (c)
Problem 5 : Which one of the following compounds will not give electrophilic substitution reaction?
CN

(a) (b)

(c) C6Cl6 (d) C6H5–SO3 H

Solution : (c)
Problem 6 : . The product of the given reaction
CCl 3


(i) HOH /OH Br2 / Fe

(ii) H O 
  [X]
3

is
CHO CH2 OH

(a) (b)
Br Br
COCl COOH

(c) (d)
Br Br
Solution : (d)
 Chemistry : Electrophilic Aromatic Substitution

MATCHING TYPE PROBLEM

7. Column (I) Column (II)

(P) Sandmeyer (A) Acytation
(Q) Friedal Crafts (B) Carbene
(R) Reimer-Tieman (C) Carbocation
(S) Fries rearangement (D) Free radical
Sol. (a)
(P) (Q) (R) (S)
(a) D C B A
(b) D C A B
(c) C D B A
(d) C D B C

ASSERTION-REASON TYPE PROBLEMS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
8. Assertion : Alkylation of benzene by Friedel-Crafts reaction gives polyalkylated benzene
Reason : The ring gets activated for further substitution after the introduction of one alkyl group.
Solution : (a)
9. Assertion : Phenoxide ion is more reactive than phenol towards electrophiles.
Reason : Phenoxide ion is more stable than phenol.
Solution : (b)
10.Assertion : In toluene methyl group is ortho-para directing group for ArSE reactions.
Reason : Alkyl group decreases electron density at ortho and para-positions due to the hyper conjugation.
Solution : (c)