Chapter 7

Aromatic hydrocarbon (Arenes)

Introduction
Aromatic hydrocarbons are also called arenes
General formula of arenes is CnH2n–6y where y is the number of benzene ring in
molecule
Following reactions are important in the determination of the structure of benzene
H2/D
(i) C6H6
Pt
O O
1. O3
(ii) C6H6 H–C–C–H
2. H2O/Zn
KMnO4
(iii) C6H6 No reaction (no decolourisation)
Cold & dil.
Br2CCl4
(iv) C6H6 No reaction
HCl
(v) C6H6 No reaction
On the basis of (i) and (ii) reactions Kekule in 1865 suggested that benzene is
equilibrium mixture of cyclohexatrienes [(I) and (II)] as follows

(I) (II)
But reaction (iii), (iv) and (v) cannot be explained by Kekule’s structure.

THE RESONANCE HYBRID STRUCTURE

According to the resonance theory, benzene is a resonance hybrid of the following canonical forms.
≈
≈ ≈

Q Q
Q
KEKULE structure

DEWAR'S structures

Contribution: Total 80% Total 20%

20
40% each i.e., ___
​   ​ % contribution by each
3
It should be noted that the concept of resonance is imaginary and the canonical forms mentioned above actually do not
exist. It is the hybrid structure which is a reality.
Physical Properties of Benzene
• Benzene is a colourless volatile liquid; it has characteristic smell
• Its boiling point is 80°C and freezing point is 5.5°C
• It is highly inflammable and burns with sooty flame
• It is lighter than water; its specific gravity at 20°C is 0.8788
• It is immiscible with water but miscible with organic solvents such as alcohol and ether
• It is a non-polar compound and its dipole moment is zero
• It is extremely poisonous substance. Inhalation of vapours or absorption though skin has a toxic effect.

Methods of Preparation of Benzene

NaOH + CaO/D
COOH
Sodalime

H2O/D
SO3H

H 2O
Mg – Br

Raney Ni
Cl
Ni-Al/NaOH

NaNO2/HCl/0°C
NH2 Benzene
H3PO2/D or C2H5OH/D

Zn
OH
reduction

Cr2O3 + Al2O3
500°C

Red hot Fe tube

HC CH
Polymerisation
CH2
HC (i) CH2 = CH2
HC (ii) Pt/D
CH2

Chemical Properties of Benzene

Aromatic Electrophilic Substitution Reactions

The most characteristic reactions of benzenoid arenes are the substitution reactions that occur when they react with elec-
trophilic reagents.
 The reactions in which one or more hydrogen atoms of the benzene ring are replaced by an electrophile are called
electrophilic aromatic substitution reactions.
These reactions are of the general type shown below:
H E

Lewis acid ≈ –
A
+E–A +H A–H

benzenoid arenes undergoes electrophilic substitution reactions because it has an electron rich system due to delocalized
-electron.

General Mechanism

Energy profile for a typical aromatic electrophilic substitution reaction: A more detailed picture of the arenium ion
mechanism may be represented by its energy profile.

Important Points
• Benzene is a poor nucleophile because it losses its aromaticity
• First step is RDS where Wheeland intermediate or s complex is formed
• s complex has 4 e– non-aromatic resonance stabilized carbocation
• Breaking of C–H bond takes place in fast step it means no isotopic effect thus rate of reaction is
C6H6 ª C6D6 ª C6T6
Note: In sulphonation and iodination isotopic effect considered because difference between TS1 and TS2 is very less.
Thus rate of reaction is C6H6 > C6D6 > C6T6

Halogenation of Benzene
Cl
FeCl3
+ Cl2 + HCl
25°C
Chlorobenzene (90%)

Br
FeCl3
+ Br2 + HBr
heat
Bromobenzene (75%)

The mechanism for aromatic chlorination is as follows.

≈ Q ≈ Q
Step-1 Cl–Cl+ FeCl3 Cl– Cl – FeCl3 Cl + FeCl4
H Cl
Step-2 ≈ slow
+ Cl +

Cl
H Cl
Step-3 – fast
+ + FeCl4 + HCl + FeCl3

Some facts
≈
(i) The function of Lewis acid is to convert weaker electophile (Cl2) into stronger electrophile (Cl)
(ii) The Lewis acids most commonly used to effect chlorination and bromination reactions are FeCl3, FeBr3, and AlCl3
all in the anhydrous form.
(iii) Ferric chloride and ferric bromide are usually generated in the reaction mixture by adding iron to it. The iron then
reacts with halogen to produce the ferric halide.
2Fe + 3X2 Æ 2FeX3
(iv) The Lewis acids behave as a halogen carrier.

Nitration of Benzene
A mixture of nitric acid and sulphuric acid is the nitrating reagent.
NO2
50–55°C + –
+ HNO3 + H2SO4 + H3O + HSO4

(85%)

The steps involved in the mechanisms are as follows.

Step-1 Formation of nitronium ion
+
HONO2 + 2H2SO4 + 2HSO4– + +NO2
Nitronium ion
Step-2 Electrophilic attack by nitronium ion

H NO2
+
+
+ NO2
Arenium ion
Step-3 Removal of proton

NO2
H NO2
≈ O–H
fast ≈
+ + H3O
H

Some facts
(i) In nitration HNO3 behave as bronsted base and H2SO4 as a bronsted acid.
(ii) For formation of 1 mol NO2+ 2 : 1 ratio for H2SO4 and HNO3 is used.
(iii) The rate determining step is the formation of carbocation (s complex).
(iv) Breaking of C–H bond takes place in fast stape so that there is no isotopic effect.
(v) NO2 is a deactivating group it means for further nitration, rate of reaction decreases.

NO2 NO2 NO2

≈ ≈ ≈
NO2 NO2 NO2
50°C 100°C 5 day
NO2 O2N NO2
1, 3, 5-tri nitro benzene (T.N.B)
(explosive)

Sulfonation of Benzene
Benzene reacts with fuming sulphuric acid at room temperature to produce benzene-sulfonic acid. Fuming sulphuric acid
is sulphuric acid that contains added sulphur trioxide (SO3). Sulfonation also takes place in concentrated sulphuric acid
alone, but more slowly.
SO2H
25°C
Conc. H2SO4
+ H2O

Benzenesulfonic acid
(56%)

The steps involved in the mechanisms are as follows :

+
Step-1 2H2SO 3O + HSO4– + SO3
O H SO
–
3
Step-2 + S slow
+
O O
–
–
SO 3
H SO 3
Step-3 – fast + H2SO4
+ + HSO 4

–
SO SO3H
3

Step-4 +
+ H3O + H2O
Some facts
(i)
C6H6 + H2SO 6H5SO3H + H2O
For sulphonation, we require excess of H2SO4 along with SO3 and for desulphonation we use excess of H2O along
with heating (100–175°C).
(ii) Sulphonation is a reversible reaction because different between T.S1 and T.S2 is very less.
(iii) Order of reactivity in isotopic benzene is C6H6 > C6D6 > C6T6.

Friedel–Crafts Alkylation
A general equation for a Friedel–Crafts alkylation reaction is the following:
R
AlCl3
+ R– X + HX

The steps involved in the mechanisms are as follows:

– +
Step-1 RCl + AlCl 4 + R
H R
Step-2 +R
+ slow
+

R
H R
Step-3 + AlCl4
–
fast
+ + HCl + AlCl3

Here AlCl3 acts as a Lewis acid.

Friedel–Crafts Acylaction
O
C–R

AlCl3
+ R–C–Cl + HCl
O

O
C–R

AlCl3
+ R–C–O–C–R + R–C–OH
O O O

The steps involved in the mechanisms are as follows:

In most Friedel –Crafts acylation the electrophile appears to be an acylium ion formed from an acyl halide in the
following ways:
O
≈ ≈ Q
Step-1 R–C–Cl + AlCl3 R–C=O R–C O + AlCl4
An acylium ion
(a resonance hybrid)
 R H
+C C–R
Step-2 +
+
O O
Arenium ion
O
H O
Step-3 C–R Q C–R
+ + AlCl4 + HCl + AlCl3

Limitation of Friedel-Crafts Reactions:

(i) When the carbocation formed from an alkyl halide, alkene, or alcohol can rearrange to a more stable carboca-
tion, it usually does so and the major product obtained from the reaction is usually the one from the more stable
carbocation.
(ii) Vinyl halides and aryl halides do not react in Friedel-Crafts alkylation because carbocation derived from vinyl halide
and aryl halide are highly unstable.
(iii) Friedel-Crafts reaction usually give poor (almost no yields) yields when powerful electron withdrawing groups are
present on the aromatic ring due instability of s complex.
(iv) When the ring bears an – NH2, –NHR, or –NR2 group, these groups are changed into powerful electron– withdraw-
ing groups by the Lewis acids used to catalyze Friedel-Crafts reaction so that –NH2, –NHR, and –NR2 groups are
not give Friedel-Crafts reaction.
(v) Another limitation of Friedel-Crafts alkylation arises because of polyalkylation as an alkyl substituted benzene is
more reactive than benzene. However no Polyacylation takes place.

Effect of Substituents on Reactivity and Orientation

When substituted benzene undergo electrophilic attack, groups already on the ring affect both the rate of the reaction and
the site of attack therefore substituent groups affect both reactivity and orientation in electrophilic aromatic substitutions.
We can divide substituent groups into two classes according to their influence on the reactivity of the ring. Those that
cause the ring to be more reactive than benzene itself we call activating groups. Those that cause the ring to be less reac-
tive than benzene we call deactivating groups.

Theory of Orientation
A group attached to benzene has a directing influence on the electrophilic substitution reaction. Two types of groups have
been classified based on their orientation effects.

Activating Group
A group that releases electrons to benzene ring is an activating group. It directs the incoming electrophile to ortho or para
position. Examples include
Strongly activating: –NH2, –NHR, –NR2, –OH, –OCH3
Moderately activating: –NHCOCH3, –OCOCH3
Weakly activating: –CH3, –CH=CH2, –C6H5

Deactivating Group
A group that withdraws electrons from benzene is a deactivating group. It directs the incoming electrophile to meta posi-
tion. Examples include
+
Strongly deactivating: –N(CH3)3,–NO2, –CN, –SO3H
Moderately deactivating –CHO, –COR, –COOR, –COOH, –COCl
*Weakly deactivating: F, –Cl, –Br, –I (o/p director)
Orientation Based on Sigma Complex Stability
Case-I: Activating Groups : Ortho para Directors
(a) When group is +H/+I group only, i.e., Alkyl group: Structures of the carbocation intermediates formed from the
reaction of an electrophile with toluene at the otrtho, at the ortho, meta and para position

CH3 CH3 CH3

E E E
ortho ≈

≈ ≈
3° 2° 2°
(Most stable)
(I) (II) (III)

CH3 CH3 CH3 CH3

≈ Meta ≈ ≈
+E
≈ E E E
2° 2°
2°
(IV) (V) (VI)

CH3 CH3 CH3

Para ≈

≈ ≈

E E E
2° 2° 2°
(VII) (VIII) (IX)
(Most stable)

(b) When group +M/–I group: The structures of the carbocation intermediates formed from the reaction of an elec-
trophile with anisole at the ortho, meta and para positions.
OCH3 OCH3 OCH3
E E E
ortho ≈

≈ ≈
(I) (II) (III)

≈
O— CH3
E

Specially stable
(IV)
OCH3 OCH3 OCH3 OCH3
≈ Meta ≈ ≈
+E
≈ E E E
(IV) (V) (VI)

OCH3 OCH3 OCH3

Para ≈
 (IV) (V) (VI)

OCH3 OCH3 OCH3

Para ≈

≈ ≈

E E E
(VII) (VIII) (IX)

≈
O— CH3
E

E
Specially stable
(X)

Case-II: Deactivating Groups : Meta Directors

(a) When group is –I group: Structure of the carbocatoin intermediates formed from the reaction of an electrophile
with protonated aniline (–I group) at the ortho, meta and para positions

≈ ≈ ≈
NH3 NH3 NH3
E E E
ortho ≈

≈ ≈
Least stable

≈ ≈ ≈ ≈
NH3 NH3 NH3 NH3
≈ Meta ≈ ≈
+E
≈ E E E

≈ ≈ ≈
NH3 NH3 NH3
Para ≈

≈ ≈

E E E
Least stable

(b) When group is –M/–I group: Structures of the carbocation intermediates formed from the reaction of an electro-
phile with a substrate, having an –M group, at the ortho, meta and para position
 O d+
R O R O R
C C C
E E E
ortho ≈

≈ ≈
Least stable

O R O R O R O R
C C C C
≈ Meta ≈ ≈
+E
≈ E E E
d–
O R O d+
R O R
C C C
Para ≈

≈ ≈

E E E
Least stable
Case-III: Halo Substituents : Deactivating Ortho-Para Directors
Structures of the carbocation intermediates formed from the reaction of an electrophile with a halogenated benzene at the
ortho, meta and para position
Cl Cl Cl
≈
E E E
ortho
≈ ≈

≈
Cl
E

Relatively stable
Cl Cl Cl Cl
≈ Meta ≈ ≈
+E
≈ E E E
Cl Cl Cl
Para ≈

≈ ≈

E E E
≈
Cl
E

E
Relatively stable
EFFECT OF SUBSTITUTENTS ON REACTIVITY:
In presence of different substituents on benzene ring, rate of reaction increased or decreased is known as substitution
effect.

1
Reactivity of ArsE µ Activating power µ
Deactivating power

Classification of Substituents
ORTHO-PARA DIRECTIORS META DIRECTORS
Strongly activating Moderately Deativating
–NR2, –NHR, –NH2, –OH, –O– –C∫N, –SO3H, –CO2H, –CO2R, –CHO, –COR

Moderately activating Strongly deactivating

–NHCOR,–OCOR,–OR –NO2, – NR3+ , –CF3, –CCl3

Weakly activiating
–CH3, –C2H5, –C6H5
Weakly deactivating
–F, –Cl, –Br, –I

Summary of Substituent Effects on orientation

We can summarize the effect that groups have on orientation and reacvtivity in the following way.
Full or partial (+) charge on directly attached atoms At least one nonbonding pair on directly attached atom Alkyl or aryl
Halogen –NH2,–OH, etc.
¨ meta directing ortho-para directing
deactivating activating

Aromatic Electrophilic Substitution Reactions of Polysubstituted Benzene

What happens when two or more substituent groups are attached to the benzene ring ? Where is the electrophile likely to
attack? Some qualitative rules have been formulated to answer this question.
(i) The most activating group will control orientation.
(ii) No substitution occurs between two meta substituents because of crowding.
(iii) When both groups are meta directors, it is difficult to introduce third group.

Summary of main electrophilic substitutions on benzene

Reaction Reagents Electrophile Products
Bromination Br2 and Lewis acid, e.g., ≈ Q C6H5—Br
Br Br AlCl3
AlCl3, FeBr3, Fe Powder, I2 ≈
Br Br Fe
Nitration HNO3 + H2SO4 ≈ O C6H5—NO2
N
O
Q

Sulphonation Concentrated H2SO4 or H2SO4 + SO3(oleum) ≈ C6H5—SO3H

SO3H or SO3

Friedel–Crafts alkylation R—X + Lewis acid usually AlCl3 R≈ C6H5—R

Friedel–Crafts acylation RCOCl + AlCl3 ≈ O

R C O
C6H5 C R
Gatterman–Koch CO, HCl, AlCl3, Cu2Cl2 ≈ C6H5—CHO
H C O

H C=O
≈
+ ≈
Gatterman aldehyde HCN, HCl/AlCl3, H C6H5—CHO
H C NH

H C=NH
≈

Chloromethylation CH2O, HCl ZnCl2 ≈ C6H5—CH2OH

CH2OH

Mercuration Hg(OAc)2/D ≈ C6H5—HgOAc

Hg(OAc)

Thallunation Tl(OCOCF3)3/D ≈ C6H5—Tl(OCOCF3)2

Tl(OCOCF3)2

Some other reactions of benzene

H2/Ph or Pt or Ni
H.T.P.
Na/liq.NH3
Birch reduction

Cl Cl
Cl2/sunlight
Cl Cl

Cl Cl
Benzene hexa chloride (B.H.C)
(Gammaxene)

O3/H2O/Zn CHO
(Glyoxal)
Ozonolysis CHO

Benzene
(i) CrCl3 + AlCl3 Sandwitch
Cr
(ii) Na2S2O4 (reduction) Compound

Combustion C
6 CO2 + 3 H2O + DH (exothermic)

V2O5/300°C
OH (Phenol)
Oxidation
O
V2O5/400°–300°C
Oxidation O (maleic anhydride)
O
Methods of preparation AND CHEMICAL PROPERIES OF TOLUENE:
CH3
O CH3

CH3 CH3–C–Cl/AlCl3 C Cl +
COONa F.C.R
NaOH + CaO O
C–Cl
D
O
CH3 CH3
CH3
OH C2H5Cl/AlCl3 C2H5
Zn
F.C.R +
D
C2H5
CH3 CH3 CH3
SO3H H2O/H
≈
HNO3 + H2SO4 NO2 +
H.T.P. Nitration

NO2
CH=O CH3
HNO3 + H2SO4
O2N NO2 T.N.T.
Zn–Hg/HCl CH3 Fuming (explosive)
Clemmensen's redution
NO2
CH=O Toluene CH3 CH3
H2SO4
–
N2H4/OH Sulphonation SO3H +
Wolff-kishner reduction
SO3H
CH3 CH3 CH3
NaNO2/HCl/0°C CH3Cl/AlCl3 CH3
+
H3PO2 or C2H5OH/D
–o/p-xylene
–
NH2 CH3
CH3
CH3Cl/AlCl3
CH3–Cl/AlCl3
80°C
F.C.R. CH3
meta-xylene

Cl CH2–Cl

CH3–Cl/2Na/ether Cl2/hv
(Free radical
Wurtz-Fitting substitution)
reaction
CCl3
MgCl
Cl2/hv
CH3–Cl excess
CHO
CrO2Cl2
Cr2O3 + Al2O3 ETARD oxidation
500°C COOH
≈ –
KMnO4/HorOH
Fe/D Strong oxidation
CH3–C CH+CH CH
CH3
H2/Pd
Hydrogenation
 Solved Example
1. In the reaction

The major product (X) is

(1) (2)

(3) (4)

Sol. [2]
3. What is the product of the following reaction?

Friedel–Craft Reaction
2. is nitrated and the resulting product is reduced with
tin and hydrochloric acid. The product so obtained
is diazotized and then heated with potassium iodide. (1) (2)
The reaction mixture so formed contains:
(1) Mixture of o– and p–iodotoluenes
(2) Mixture of o– and p–diiodobenzenes
(3) Mixture of o– and p–iodoanilintes
(4) Mixture of o– and m–iodotoluenes
Sol. [1] (3) (4)

Sol. [4]

4. The intermediate product ‘X’ of following synthesis

is identified as:

 Sol. [2]

COOH
NO2 KMnO /D NO2
(i) HNO3 4
(ii) H2SO4

NO2 NO2
(A) (B)
(1) (2)
sodalime

NO2

(3) (4) NO2

(C)

6. Each of the following compounds gives a Friedel–

Crafts alkylation, except:
Sol. [2]
OH OCH3
Cl Cl Cl
NO2 NO2 (1) (2)
Cl2/FeCl3 Conc. H2SO4 Fuming HNO3
D

SO3H SO3H O
Cl
–
NH3/Cu2O/D 120°C O
(3) (4)
NH2 NH2
NO2 1 NO2 NO2 NO2
2
6 dil. H2SO4.D
5 3 100°C Sol. [4]
de-Sulpnonation
4 Due to presence of de-activating group Friedel–Craft
SO3H reaction does not take place because s complex is
2, 6-dinotro anilene
unstable

C2H5
5. ;
Etard
7. Reaction ?
Product (C) of this reaction is:
CHO CH2COOH
NO2 NO2
(1) (2) (1) (2)
NO2
NO2
CH2CHO COOH

NO2 NO2 (3) (4)

(3) (4)
NO2 Sol. [3]
NO2
 CH2–CH3 CH2–CH = O 10. The major product formed in the reaction

Etard
Reaction Conc. H2SO4
+ HNO3
8. Benzene undergoes methylation in presence of AlCl3
followed by oxidation with CrO3 in the presence of
(CH3CO)2O. It gives a product ‘A’ which on treat-
ment with Zn-Hg/HCl produces:
(1) C6H5COOH (2) C6H6 NO2
(3) C6H5–CH3 (4) C6H5–CH=O (1) (2)
Sol. [3] NO2
CH3 CH = O

Methylation CrO3/Ac2O NO2

AlCl3 Etard reaction

(A) (3) (4)

Zn–Hg/HCl
NO2
CH3
Sol. [2]
1a–H
+HØ
9. Provide the appropriate sequence of reagents that can
bring about the following: Conc. H2SO4
COOH
NO2

2a–H
+H≠
NO2
11. The reactivites of C6H5CH3 (I), C6H5CH2Cl (II),
(1) CH3Cl/AlCl3 then conc. HNO3/conc. H2SO4 then C6H5CHCl2 (III), C6H5CCl3 (IV) toward nitration are
KMnO4/NaOH in the order
(2) Conc. HNO3/Conc. H2SO4 then CH3Cl/AlCl3 (1) I > II > III > IV (2) II > I > III > IV
then KMnO4/NaOH (3) IV > III > II > I (4) III > I > II > IV
(3) CH3Cl/AlCl3 then KMnO4/NaOH then conc. Sol. [1]
HNO3/Conc. H2SO4 Nitration ∫ Ar–SE µ activating power
(4) Conc. H2SO4/conc. HNO3 then CH3COCl/AlCl3 1
then KMnO4/NaOH µ _________________
​        ​
De-activating power
Sol. [1] + H (CH3 > –CH2–Cl > –CHCl2 > –CCl3)
CH3 CH3
12. The final product obtained in the reaction
CH3–Cl/AlCl3 Conc HNO3
CH3CH2COCl CH3NH2
Conc H2SO3
AlCl3 X H2,Ni
is

NO3 O
KMnO4/NaOH
(1) H3C–NH CH2CH2CCl
COOH

(2) CHCH2CH3
NHCH3
NO2
 O
(3) CH2–CH2–C–NHCH3
14. ; Product B is

O
(4) C–CH2CH2NHCH3

Sol. [2]
(1) (2)
O N–CH3

O C–CH2–CH3 C–CH2–CH3

CH3–CH2–C–Cl CH3–NH2
AlCl3

(X) (3) (4)

Reduction H2/Ni

NH–CH3
CH–CH2–CH3 Sol. [2]

13. m-Nitrobenzoic acid can be obtained by

(1)

(2)
1° halide predominantly gives SN2 reaction
(3) 15. Which of the following structures correspond to the
product expected, when excess of C6H6 reacts with
(4) All these methods CH2Cl2 in presence of anhydrous AlCl3?
Sol. [1]

(1)

(1)
(2)

(3)
(2)

(4)

Sol. [4]
(3) The reaction takes place as follows:
AlCl3
+ ClCH2Cl + CH2

Diphenyhmethane
 Exercise 1

1.
(3) (4)
The structure of compound:

4. The major product formed in the reaction

(1) (2)

(3) (4)

2. , Product

(1) (2)
(B) is:

(1) (2)

(3) (4)

(3) (4) 5. Benzene is allowed to react with succinic anhydride

in the presence of anhydrous AlCl3 and subsequently
treated with dilute HCl. The product formed is:
3. In a set of reactions, p–nitrotoluene yielded a product E

(1)

The product E would be: (2)

(1) (2)
(3)
 (4)

6. (I) (1) Free Radical, Friedel–Craft alkyaltion

(2) Carbocation, Friedel–Craft alkyaltion
(3) Carbocation, Friedel–Craft acylation
(4) Carbanion, Friedel–Craft alkylation
(II)
9. In the reaction for dinitration,

(III) ,

The major dinitrated product (X) is:

(IV)

Friedel–Craft acylation reaction can be used to obtain (1) (2)

the compounds
(1) II, III, and IV (2) I, III and IV
(3) I and II (4) II and III
7. Consider the following reaction sequence:

(3) (4)

10. Which represents an intermediate formed in the reac-

tion of toluene and chlorine at elevated temperature
in sunlight?

The final product of this reaction sequence is: (1) (2)

(3) (4)
(1) (2)
11. Deduce structure of (A) is:

(One-product only)

(3) (4)
(1) (2)

8. In the given reaction, the intermediate formed and

name of the reaction is: (3) (4)
 12. (1) (2)

Product (B) of this reaction is:

(1) (2) (3) (4)

16. In the alkylation of benzene, unstable s-complex can

(3) (4) No-reaction be:

(1) (2)

13.
(3) (4)

Major product (B) of this reaction is:

17. The Birch reduction of toluene gives

(1) (2)
(1) (2)

(3) (4)

(3) (4)
18. Product:

14. Which of the following produces isophthalic acid

upon oxidation?

(1) (2)
(1) (2)

(3) (4)
(3) (4)

15. Consider the following sequence of reaction:

19. ‘Z’is:

The end product (E) is:

(1) (2)
 20. When an aromatic compound undergoes ozonoly-
sis followed by treatment with H2O/Zn, it produces
(3) (4) glyoxal, monomethylglyoxal and dimethylglyoxal.
It could be
(1) benzene (2) toluene
(3) o-xylene (4) m-xylene

Exercise 2
1 Which of the following is the most stable arenium The final product is:
or benzenium ion?

(1)
(1) (2)

(2)
(3) (4)

(3)

2.

(4)

4. The end product of following sequence of reactions

is:

Which of the following statements is wrong about
the reaction? (1)
(1) At lower temperature, the reaction is kinetically
controlled and o/p directive effects of the (Me)
group operate.
(2) At a higher temperature, the reaction is thermo- (2)
dynamically controlled, and longer reaction times
are employed for equilibrium to be reached. The
most stable form of m-toluene sulphonic acid is
obtained.
(3) (Me–) group is activated by +I effect, and o–,
p– directing. (3)
(4) (Me–) group is deactivating by hyperconjugation
and is m directing

(4)
3.
 5. Major product obtained in given reaction is:

(1) I > II > III > IV (2) IV > III > II > I
(3) I > III > IV > II (4) II > III > I > IV
(1) (2) 8. Which of the following statements is correct?
(1) Monobromination of p-toluenesulphonic acid
followed by treatment with acid and superheated
steam gives m-bromotoluene.

(2) The mononitration of

(3) (4)

gives the product

(3) The reactivity towards ring nitration of

2, 4-dinitrotoluene is greater than that of
m-dinitrobenzene.
6. ?, The most appropriate product is: (4) The reactivity towards ring nitration of 2,
4-dinitrophenol is smaller than that of 2,
4-dinitrochlorobenzene.
9. Which of the following statements is not correct?
(1) In electrophilic aromatic substitution reaction,
the formation of intermediate arenium cation is
the rate-determining step.
(1) (2) (2) The C–H bond in benzene is slightly stron-
ger than the C–D bond in deuterated benzene
(C6D6).
(3) The overall rate of an electrophilic substitution
reaction, except sulphonation in benzene and
deuterated benzene, are identical.
(4) The sulphonation reaction involving benzene is
(3) (4) a reversible reaction.
10. Which of the following statements is correct?
(1) The oxidation of naphthalene with KMnO4 in
acid gives phthalic acid.
(2) The oxidation of naphthalene with O2/V2O5
7. Arrange the following in order of decreasing boiling gives 1, 4-naphthaquinone.
point. (3) Treatment of p-chlorotoluene with NaOH (aq.)
at 340°C exclusively gives p-hydroxyoluene.
 (4) Chlorine in p-chlorotoluene is replaced by
OH when taken in NaOH (aq.) at 340°C.
No such replacement occurs for 2,6- (1)
dimethylchlorobenzene.
11. Which of the following carbocation is expected to be
most stable?
(2)
(1) (2)

(3) (4)
(3)

12.

(4)

The end product (C) is:

14. Arrange the following in decreasing order of reactivity
towards EAS (electrophilic aromatic substitution)

(1) (2)

(1) a > b > c (2) c > b > a
(3) a > c > b (4) c > a > b
(3) (4)

15.

13. In the above reaction o/p ratio will be highest

when:
(1) R = – CH3 (2) R = –CH2 – CH3
Product (B) in the above reactions is: (3) R = – CHMe2 (4) R = – CMe3

Exercise 3
One and More Than One Option Correct Type (3) Compound ‘A’ can also be synthesised by reaction
Question of benzene diazonium chloride with H3PO2
(4) Compound ‘B’ gives grey colour with aq. HgCl2
1. solution
2. Consider the following reaction,
Select the correct statement among following:
(1) Compound ‘B’ form silver mirror on reaction
with [Ag(NH3)2]OH
(2) Compound ‘B’ can also be obtained by the reac-
tion of toluene with chromyl chloride
 The correct statement(s) is/are
(1) Major bromination occur at C–2
(2) Major bromination occur at C–3 (1)
(3) Bromination at C–3 and C–4 are equally
probable
(4) Bromination occur at a rate slower than that at
benzene
3. What makes the following compound aromatic?
(2)

(1) Add one electron to p-bond to give C9H–10
(2) Add two electrons to p-bond to give C9H2–10
(3) Remove an ion, H+, from sp3 carbon
(4) Remove an ion, H+ from sp2 carbon (3)
4. What is/are regarding sulphathiazole?

(1) It is an aromatic
(2) It has six delocalised pi-electrons
(3) Extent of delocalisation is equivalent to (4)
benzene
(4) It absorb Br2 when reacted with Br2-CCl4
5. Predict major product of the reaction below.

+
CH3COCl CH3MgBr H
CH3 O 7. What is/are the principal products of the following
AlCl3 reaction?

(1)
(1) (2)

(2)
(3) (4)

(3) Assertion and Reason Type Question

(1) If both (A) and (R) are cor-
rect and (R) is the correct explanation
for (A)
(4)
(2) If both (A) and (R) are correct and (R) is not
the correct explanation
6. Select the reaction in which the correct orientations (3) If (A) is correct and (R) is incorrect
have been mentioned in the major products. (4) If (A) is incorrect and (R) is correct
 8. Assertion: Sulphonation of benzene is reversible in 12. The most likely structure of P is
nature.
Reason: Deuterated benzene reacts slower than ben-
zene in sulphonation with hot conc. H2SO4.
(1) (2)
9. Assertion: Pyrene, although aromatic, decolourise
brown colour of bromine water.

(3) (4)

13. What is Q?
Reason: It has one pi-bond extra which is not the
part of aromatic system.
10. Assertion: Both toluene and iso-propyl benzene give (1) (2)
the same product on oxidation with KMnO4.
Reason: KMnO4 oxidises side aliphatic chain of
arenes to –COOH group.
11. Assertion: Furan is an aromatic system, has reso-
nance energy comparable to that of benzene. (3) (4)
Reason: Furan decolourises the brown colour of bro-
mine water solution.
Sol. [2]
14. What is R?

Comprehension type question (1) (2)

Comprehension (Q. 12-14)

Consider the following road-map reaction,
(3) (4)

Column Matching Type Question

15. Consider the compounds on left column and match with reactions form right column by

Column-I Column-II

(A) (P) C6H6 + (CH3)3CCl

(B) (Q) C6H6+(CH3)2 C=CH2

 (C) (R) C6H6 + (CH3)3 CCOCl

COH
(D) (S) CH6H6 + (CH3)3

(T) CH6H6+{(CH3)3CCO}2O
Code
A B C D
(1) P, Q Q R, T R, S
(2) S R, S Q P, Q
(3) S R P, T Q
(4) R, T P, Q, R, S, T R, T R, T
16. Match the reactions from Column-I with expected product(s) from Column-I

Column-I Column-II

(A) CH6H6 + CH3Cl (P)

(B) CH6H6 + CH3CH2 Cl (Q)

(C) (R)

(D) C6H6 + CH3COCl (S)

Code
A B C D
(1) P, R, S Q Q, R, S Q
(2) S R, S Q P, Q
(3) S R, S P, Q Q, S
(4) R, S S Q, R P

Single digit integer type question

19. How many monobromo derivatives exist for
17. If the following compound is treated with Br2–Fe, anthracene?
how many mono bromination products are formed
in principle?

18. How many isomers of C8H10 when reacts with hot

alkaline KMnO4 give only aromatic dicarboxylic 20. How many isomers of C7H8O exists that has a phenyl
acid. ring?
 Exercise 4
1. Phenyl magnesium bromide reacts with methanol to
give [JEE Main-2006] (3) (4)
(1) a mixture of benzene and Mg(OMe)Br
(2) a mixture of toluene and Mg(OH)Br 7. The product of the reaction between ethyl benzene
and N-bromo succinamide is:
(3) a mixture of phenol and Mg(Me)Br
[JEE Main Online-2012]
(4) a mixture of anisole and Mg(OH)Br
2. The reaction of toluene with Cl2 in presence of FeCl3
gives predominantly [JEE Main-2007]
(1) benzoyl chloride (2) benzyl chloride (1) (2)
(3) o-and p-chlorotoluene (4) m-chlorotoluene
3. Presence of a nitro group in a benzene ring
[JEE Main-2007]
(1) activates the ring towards electrophilic
substitution
(2) renders the ring basic
(3) (4)
(3) deactivates the ring towards nucleophilic
substitution
(4) deactivates the ritng towards electrophilic 8. Which of the following would not give 2-phenylbutane
substitution as the major product in a Friedel–Crafts alkylation
4. The electrophile E+ attacks the benzene ring to gen- reaction? [JEE Main Online-2013]
erate the intermediate s-complex. Of the following (1) 1-butene + HF
which s-complex is of lowest energy? (2) 2-butanol + H2SO4
[JEE Main-2008] (3) butanoylchloride + AlCl3 then Zn, HCl
(4) Butyl chloride + AlCl3
9. In a set of reactions p-nitrotoluene yielded a product
E [JEE Main Online-2014]
(1) (2)

(3) (4)
The product E would be:
5. Toluene is nitrated and the resulting product is
reduced with Sn and hydrochloric acid. The product
so obtained is diazotised and the heated with cuprous
(1) (2)
bromide. The reaction mixture so formed contains
[JEE Main-2008]
(1) mixture of o- and m-bromotoluenes
(2) mixture of o- and p-bromotoluenes
(3) mixture of o- and p-dibromobenzenes
(4) mixture of o- and p-bromoanilines (3) (4)
6. The nonaromatic compound along the following is
[JEE Main-2011]
10. In the following sequence of reaction
(1) (2)
Toluene
The product C is [JEE Main-2015]
 (1) C6H5COOH (2) C6H5CH3
(3) C6H5CH2OH (4) C6H5CHO (3) (4)
11. The compound below has four phenyl rings, but very
less stable due to an opposing factor of stability. 13. The major compound Y is [JEE Adv.-2015]
Therefore, this compound absorbs bromine in dark.
How many bromine molecules, when added to this
molecule, would make it stable and prevent further (1)
bromine addition? [IIT-JEE 2005]

(2)

(3)

Comprehension (12 and 13)

(4)

14. Among the following reactions(s) which gives (give)

tert-butyl benzene as the major product?
[JEE Adv.-2016]

12. Compound X is [JEE Adv.-2015] (1) (2)

(1) (2) (3) (4)

Answer Key

Exercise # 1 Exercise # 3
1. (3) 2. (2) 3. (2) 4. (1) 5. (1) 1. (1,2,3,4) 2. (2,4) 3. (3) 4. (1,2,4) 5. (3)
6. (3) 7. (3) 8. (2) 9. (1) 10. (3) 6. (1,3,4) 7. (2,3) 8. (2) 9. (1) 10. (1)
11. (2) 12. (2) 13. (4) 14. (1) 15. (2) 11. (4) 12. (3) 13. (2) 14. (3) 15. (4)
16. (4) 17. (2) 18. (4) 19. (2) 20. (3) 16. (1) 17. (5) 18. (3) 19. (3) 20. (5)

Exercise # 2
Exercise # 4
1. (2) 2. (4) 3. (2) 4. (2) 5. (2)
1. (1) 2. (3) 3. (4) 4. (3) 5. (2)
6. (2) 7. (2) 8. (3) 9. (2) 10. (4)
6. (2) 7. (3) 8. (3) 9. (2) 10. (4)
11. (4) 12. (2) 13. (2) 14. (1) 15. (1)
11. (3) 12. (3) 13. (4) 14. (2,3,4)
Hint and Solution

Exercise # 1

1. [3]

C N COOH CO–Cl O=C

6. [3]
≈
H3O SOCl2 AlCl3 • De-activating group (–M) containing benzene
H ring do not give Friedel–Craft acylation due to
instability of s complex.
Friedel–Cracft acetylation • –NH2, its derivative containing benzene ring also
does not give Friedel–Craft acylation because
2. [2] they form salt by acid base reaction with Lewis
acid (AlCl3)
7. [3]

3. [2]

CH3 CH3 CH3

+M
Br Br
Br2/FeBr3 Sn/ HCl
Ar-SE

–M
NO2 NO2 NO2

CH3 CH3 NaNO2/HCl

Br Br
CuBr
HCl
8. [2]
Br N=N–Cl

4. [1]

Friedel–Craft alkylation

9. [1]
5. [1]
The most activating group will control orientation at
least stericly hindred ortho and para position.
10. [3]

15. [2]
Free radical substitution reaction
11. [2]

12. [2]

16. [4]
Resonance do not take place at mea position so that
+ve charge is not occurred at meta position thus s
complex unstable at meta position.

17. [2]

CH3 CH3 CH3 CH3

Na liq NH3 1. Na
– 2. liq.NH3


18. [4]
13. [4]

19. [2]
14. [1]
 4. [2]
CH3 CH–Cl
CH2
Cl2, D PhH, AlCl3
Chlorination Friedel
craft reaction
Bromination Br2/D

20. [3]
5. [2]

Exercise # 2
1. [2]
6. [2]

2. [4]

Due to hyperconjugation, Methyl group is activating
and o/p director. 7. [2]
3. [2] Boiling point a molecular weight
8. [3]
(1) The product is o-bromotoluene
CH3 CH3 CH3
Br Br
Br2 H2O, heart
Fe H3SO4
o. bromotoluene
SO3H SO3H

(2) Substitution is faster in the ring that is not deac-

tivated by –NO2. Thus, the compounds obtained
will be
 (4) , there is no Roth-H, thus ben-

zyne cannot form.

11. [4]
(3) In 2,4-dinitrotoluene, there are two deactivating –NO2 group is benzene deactivator, it is meta
(NO2) groups and one activating (CH3) group directing.
while in m-dinitrobenzene, there are only two 12. [2]
deactivating groups.
(4) 2,4-dinitrophenol contains a strongly activating
group (–OH) while 2, 4 dinitrochlorobenzene
contains weak deactivating group (–CL)
9. [2]
(1) The formation of intermediate arenium cation is
slow while the elimination of H+ from this cat-
ion is fast. The former involves the removal of
aromaticity while the latter restores aromaticity
(2) The C–D bonds are stronger than C–H bonds. In
fact, the bond with the heavier isotope is slightly
stronger than that with the lighter isotope
(3) In electrophilic substitution reaction, the rate-
determining step is the formation of arenium
cation

In this step, E+ bonds to the aromatic ring

without cleavage of a C–H bond. The latter
is broken in the second step, which is fast as
it restores the stable aromatic system. Since 13. [2]
C–H or C–D bond is not broken in the rate- Intramolecular electrophilic aromatic substitution
determining step, the overall rates of reaction then nitration with respect to phenyl ring.
are identical. 14. [1]
10. [4] –CH3 > –CD3 > –CT3
(1) The product is 1,4-naphthaquinone. Order of hyperconjugation on the basis of bond
(2) The product is phthalic acid. energy
(3) Two products namely p-hydroxytoluene and 15. [1]
m-hydroxytoluene are obtained. This reaction The steric demand of HQ is, however, extremely
proceeds through the formation of benzyne and small, and when attack on C6H5Y is by any other
is known as elimination-addition reaction electrophile, E≈, which will necessarily be larger,
there will be increasing interaction between E and Y
CH3 CH3 CH3 CH3 CH3 in the transition state for attack at the position o- to
Y (57 b, R = E) as attacking electrophile and sub-
–
OH OH
–
stituent increase in size; there can be no such inter-
+
– action in the transition state for p- attack (57 a,
H OH
Benzyne R = E). This will be reflected in an
Cl Cl OH for o-attack, a consequently slower reaction, and the
 relative proportion of o-product will thus fall as the 5. [3]
size of E and / or Y increase. This is illustrated by COCH3
the falling fo– /fp– ration which are observed for the CH3COCl
nitration of alkylbenzenes (Y – CH3 Æ CMe3) under O AlCl3
comparable condition; O
HO
+
CH3MgBr H
+
H
O O
6. [1, 3, 4]
When two group attach with benzene ring, then
major product at the o/p-position of strong activat-
Exercise # 3
ing group
1. [1, 2, 3, 4] (1) + H (–CH3) > +M (– Cl)
CH=O CH3 (2) + H (–CH3) < + M (–NH–CO–CH3)
(3) + M (–OH) > – M (–CH=O)
Al2O3 CO + HCl CrO2Cl2
Hydro formation AlCl3 Etardr reaction (4) Ring which is not de-active by –NO2 group, will
Gattermann gives major product.
(A) Koch synthesis (B) 7. [2,4]
(Ag(NH3))2 OH +
+
H3PO2 H

N=N–Cl (Ag(NH3))2 HgCl2

X
Ag Ø Hg
Silver mirror grey ppt +
+ve +ve +
Y Ph
2. [2,4]
+
+ H
H H H
+ Br2 Br2 Br2 Br2
N N + N N + X

No such stabilisation of intermediate carbocation

occurs by attack of Br+ at C–2 or C–4 carbon.
Electron withdrawing–I effect of nitrogen destabilises + Ph
Y Ph
carbocation to some extent. Hence, pyridine is less
reactive than benzene towards electrophilic substitu-
8. [2]
tion reaction.
Both are correct, however, the correct explanation
3. [3]
is small difference in the potential energies of two
transition states in sulphonation reaction.
9. [1]
One of the resonance structure shown below indicates
clearly that the central pi-bond is not involved in
aromaticity, show the general reactions of a typical
4. [1, 2, 4] alkene.
It is aromatic, has six delocalised pi electrons but not
as aromatic as benzene because 3p orbitals of S do
not overlaps effectively with 2p orbitals of carbon.
Hence, it does show reactions of alkenes to some
extent.
 10. [1]

(ii)

G Æ must have benzylic H (iii)
Both toluene and iso propyl have benzylic H
11. [4] CH3
(iv) C6H6
AlCl +
{(CH3)3CCO}2O CH3–C–C =O A
CH3
CH3
+ C6H6
Due to abve resonance, furan acquire 6p electrons CH3–C + CO A
and show aromaticity but to a very small extent due CH3
to development of positive charge on electronegative 16. [1]
oxygen atom. Hence, resonance stabilization of furan
(i) Friedel–Craft methylation and dimethylation
is much less than benzene. Due to this reason, furan
gives p, r and s,
show, to some extent, reactions of alkene.
(ii) Friedel–Craft alkylation, i.e. ethyl group is added
12. [3]
O
to benzene, thus, q is the product
O
(iii) Aromatisation of octane gives all p, r and s.
AlCl3 CH3Li
+ O + + (iv) Friedel–Craft acylation produces benzo-
H /H2O H /H2O
O
HOOC
Methylation of acid O
phenone which on reduction produces
(P) (Q) 1-phenylethane.
(excess) CH3MgBri (A) Æ P, R, S; (B) Æ Q; (C) Æ Q, R,S ;
+
H3O/H
(D) Æ (Q)
OH OH OH
H
+ 17. [5]
+ –OCH3 is ortho and para directing
(R) OH OH

13. [2]
14. [3]
15. [4]
18. [3]
CH3 O CH3 Ortho, meta and para xylene gives dicarboxylic acid
+ C6H6 on treatment with KMnO4.
CH3–C C–Cl + AlCl3 CH3–C–C = O A 19. [3]
CH3 CH3 Br Br
CH3 +
–CO + C6H6 (CH3)3C–C=O
CH3–C (3° carbocation) B D

CH3 (I) (II)

Br

(i)
(III)
 Br
20. [5]
OH CH2–CH3 CHCH3
OCH3 CH2OH CH3
N.B.S
F.R.S.R

OH OH
Substitution takes place at benzylic Carbon.
CH3 8. [3]
In (1), (2), (4) electrophile is alkyl carbocation
which are stabilised by re-arrangement, so that
CH3 2-phenylbutane would not obtain as the major
product.
Exercise # 4 (1)
1. [1] (2)
Me–OH
Ph–MgBr ææææ Æ Ph–H+ Mg(OMe)Br
2. [3] In (3) electrophile is acyl carbocation, which
Toluene undergoes electrophilic substitution reaction cannot be re-arranged.
in ortho and para positions, since the methyl group
attached to benzene, being ring activator, is ortho and (4)
para directing group.
3. [4]
Nitro group is an electron-withdrawing group, thereby
it deactivates the ring towards electrophilic substitu-
tion of benzene ring.
4. [3]
The nitro group is electron withdrawal group. This
decreases the tendency of electrophilic substitution
reaction. The intermediate s-complex of nitrobenzene
has larger energy as compared to that of benzene.
5. [2] (3)

9. [2]

CH3 CH3 CH3

Br Br
Br2 Sn/HCl
FeBr2
Ar-SE
NO2 NO2 NH2
p-nitrotouece

CH3 CH3
Br Br
NaNO2 CuBr/HBr
6. [1] HCl HCl
An aromatic compound has (4n + 2) p-electrons,
where n is an integer. Cyclopentadiene has only 4p N=N–Cl Br
electrons and thus will be nonaromatic.
7. [3]
10. [4] 14. [2,3,4]

(1)

C2H­O– (a strong nucleophile causes) El reaction

to form isobutene as the major product.
(2)
≈
AlCl3 1, 2-hydride
Cl
11. [3] shift
1° carbocation
It has three anti-aromatic (cyclobutadiene) rings
which makes it unstable, if 3 molecules of Br2 are
≈
added to central benzene, anti-aromaticity would be
removed completely.
12. [3] 1° carbocation Tertiary butyl
(Major) benzene (X)

C C–H CH=CH2
Pd/BaSO4
H2 (3)

(C8H6)

OH
(i) B2H6 (4)
(ii) H2O2, NaOH, H2O

(2-phenyl ethanol)

Hydroboration oxidation brings about anti-

Markownikoff’s hydration of alkene.
13. [4]
O
C CH
H2O, HgSO4 CH3
H2 C2H5MgBr, H2O

CH3 CH3
+
H /D CH3
OH CH3

De-hydration takes places by syatzeff rule