Aromatic Compounds

IIT - 2022 : Chemistry
Ch. 17 : Aromatic Compounds

Syllabus : Aromatic hydrocarbonsBenzene and its homologues, Isomerism, Chemical reactions
of benzene. Structure of benzene resonance. Directive influence of substituents.
Preface :The term aromatic has been derived from the greek word “aroma” means pleasant odour.
The compounds such as resins, essential oils etc. were called aromatic compounds. The term
aromatic is misnomer, as now it is known that all aromatic compounds do not necessarily possess
pleasant smell, and many of aliphatic compounds also possess fine fragrance. The aromatic
hydrocarbons have been given a new name “Arenes.”
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MODULE 1
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Aromatic Hydrocarbon
The word ‘aromatic’ came from Greek word ‘Aroma’ which means pleasant odour. Earlier
all the compound had pleasant odour and differed from aliphatic and alicyclic compounds
called aromatic compound. But all aromatic compounds do not possess pleasant odour
and even some aliphatic compounds also possess pleasant smell.
Aromatic compounds have high percentage of carbon compared to aliphatic compounds
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and they are highly stable.
The term aromatic is now reserved for benzene and for all carbocyclic derivatives which
resembles with benzene in chemical behavior. These are called benzenoid compounds.
However, there are some compounds which resemble benzene in their chemical
behavior but do not contain benzene ring. Such compounds are termed as
non-benzenoid compounds.
i.e., Furan, thiophene, pyrrole, pyridine, pyrimidine
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N 
  
O S N
 
H N N
 
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Furan Thiophene Pyrrole Pyridine Pyrimidine
All aromatic hydrocarbons have been given a new name ‘Arenes’. Thus, the term
aromatic compounds stand for arenes and their derivatives.
Benzene is the simplest aromatic hydrocarbon.
(a) Benzene can adds six hydrogen atoms or six chlorine atoms.
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 It contains 3 bonds which accounts for 3 degree of unsaturation and 4th degree
of unsaturation must be for a ring.
Cat / D
C6H6  3H2   C6H12
Cyclohexane
D /P
C6H6  3Cl2 
 C6H6 Cl6 [BHC]
Benzenehexachloride
(b) Benzene forms a triozonide.

C6H6  3O3  C6H6 (O3 )3
Benzene triozonide
IIT/Booklets/Chem/C_6/Ch.17/Pg.191
(192) Vidyalankar : JEE (Advanced) Chemistry
Alkaline KMnO4 does not react with benzene in cold. Similarly, benzene does not
decolourise bromine solution. These are typical test of all unsaturated alkenes and
alkynes.
The above points thus confirm that benzene is a unsaturated compound but different
than aliphatic unsaturated hydrocarbons. The properties (a) and (b) suggest that the
molecule of benzene possesses three double bonds or two triple bonds.
Ring Structure :
The following are some more points which are in favour of different structure of benzene
and probably the ring structure.
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Benzene gives substitution reactions like halogenation, nitration, sulphonation, etc.
FeCl
(i) C6H6  Cl2  
 C6H5 Cl
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3
(Halogenation)
Chlorobenzene
H2SO4 (conc.)
(ii) C6H6  HNO 3   C6H5NO 2 (Nitration)
(conc.) Nitrobenzene
Heat
(iii) C6H6  H2 SO4   C6H5 SO3H (Sulphonation)
Benzene sulphonic acid
Benzene gives only one mono-substituted product. It shows that all the hydrogen atoms
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are equally and symmetrically distributed among the six carbon atoms.
Thus benzene molecule is flat with each carbon atom in sp 2 hybridized state, each
C C H bond angle of 120. Each C C bond length is 1.27 Å C H is 1.08 Å.
According to M.O.T. since all the six carbon atoms of benzene are completely equivalent,
hydrogen atom attacked to these will also be equivalent. Hence benzene should form only
one monosubstituted and three disubstituted products.
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Since benzene ring is surrounded by the  electrons cloud above and below the plane of
atoms, it is readily attached by electrophiles. Substitution reactions lead to resonance
stabilized substituted benzene derivatives, electrophilic substitutions are the main reactions
of benzene.
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Stability of Benzene
Resonance energy is the extra energy gained as a result of having delocalized electrons.
The resonance energy of benzene is 36 kcal/mole.
Pt
 H2  Hobserved = 28.6 k cal/mole
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Hobserved = 55.6 k cal/mole

Pt
 2H2  Hcalculated = 2  (28.6) = 57.2 k cal/mole
Hobserved = 49.8 k cal/mole

Pt
 3H2  Hcalculated = 3  (28.6)
= 85.8 k cal/mole
Difference (Resonance energy) = Hcalculated  Hobserved

= 85.8  (49.8) = 36 k cal/mole
Notes on Aromatic Compounds (193)
Aromaticity
An aromatic compound must fulfill the following theoretical requirements:
(a) It must have cyclic, conjugated and planar ring which satisfy the molecule.
(b) Huckel’s (4n + 2)  electrons (where n is an integer).
Benzene is aromatic since ring is planar, there is complete delocalization of  electrons

and (4n + 2) = 6  electrons used in delocalization. Examples
1. (4n + 2) = 2 (n = 0) Aromatic
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

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
 
1
2. 4n + 2 = 4, n  non-aromatic
2
3.  (4n + 2) = 6 Aromatic
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n=1
Delocalization taking place.



4. (4n + 2) = 6 Aromatic
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N n=1
5. (4n + 2) = 10 n = 2 Aromatic
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Anti Aromaticity
Planar, cyclic conjugated species, satisfying 4n   electron are antiaromatic species.
e.g.,
 
(n = 1)
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Cyclopropenyl anion Cyclopentadienyl cation

(4 electrons) (4 electrons)

(n = 2)
Cycloheptatrienyl anion Cyclooctatetraene

(8 e s) (8 e s)
• Aromaticity is shown by 1, 3  cyclopentadienyl anion but not by 1, 3  cyclopentadiene.
4 e 
[Non  aromatic] or 6 e  , Aromatic
cyclopentadienyl anion
The four electrons from double bonds plus two unshared electrons i.e., totalling six
electrons makes the anion aromatic.
• Aromaticity shown by cylopentatrienyl cation but not by cycloheptatriene.
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H H
sp3 
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or 
6e, Non planar Cyclopentatrienyl cation

[Non-aromatic] 6 e, planar [aromatic]
Cycloheptatriene inspite of having 6 electrons does not show aromaticity because of
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the presence of one sp3-hybridised carbon atom which prevents cyclic overlap of
p-orbitals.
Note :
 Benzene has a cyclic, planar hexagonal structure.
 All the hydrogen atoms in benzene are equivalent. Only one monosubstituted product
is formed.
 All carbon atoms in benzene are sp2-hybridized. All carbon-carbon bond lengths are
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identical (1.39 or 1.40 Å). The bond angles are 120.
 Due to delocalization of -electrons, electron density on benzene ring is very high. So
benzene undergoes electrophilic substitution reactions more easily under normal
conditions.
Preparation
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1. Decarboxylation of Sodium benzoate

COONa
CaO
+ NaOH + Na2CO3
Heat
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Sodium benzoate Benzene

2. From phenol : Benzene is obtained by distillation of phenol with zinc dust.
OH
+ Zn Distill.
+ ZnO
Phenol Benzene
[ OH group of the benzene nucleus is replaced by  H in this reaction]
3. From chlorobenzene : Chlorine of the benzene nucleus can be substituted by

hydrogen in two ways :
By doing reduction with Ni  Al alloy and NaOH.
Cl
Ni  Al alloy
+ 2H + HCl
NaOH
Chlorobenzene Benzene
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4. Hydrolysis of Grignard reagent.
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OH
Mg H2O
C6H5Cl C6H5MgCl C6H6 + Mg
Dry ether
Chlorobenzene Phenyl Benzene Cl
magnesium
chloride
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5. Benzene is obtained by boiling benzene sulphonic acid with dilute hydrochloric acid
under pressure at 150  200 C or hydrolyzing it with super heated steam.
SO3H
150200 C
+ HOH + H2SO4
HCl, Pressure
Steam
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Benzene Benzene
sulphonic acid
6. Aniline is first diazotized with sodium nitrite and hydrochloric acid at 0  10C when
benzene diazonium chloride is formed which is then reduced to benzene by SnCl2
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and NaOH or absolute ethyl alcohol or hypophosphorus acid (H3PO2 ) .

NaNO2  HCl  NaCl  HNO2
NH2 N2Cl
010 C
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+ HNO2 + HCl + 2H2O
Aniline Benzene diazonium

chloride
N2Cl
SnCl2
+ 2H + N2 + HCl
NaOH
Benzene
N2Cl
+ C2H5OH + N2 + HCl + CH3CHO
N2Cl
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+ H3PO2 + H2O + N2 + HCl + H3PO3
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7. When acetylene is passed through a red hot Copper tube, cyclic polymerization takes
place and benzene is formed.
HC
+
HC CH
Red hot Cu
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+
HC
CH
Three molecules of
acetylene

CH3
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Red hot Cu
3CH3 C CH
Propyne 
H3C CH3
Mesitylene
CH3
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Red hot Cu
2CH CH + CH3 C CH

Toluene
CH3
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Red hot Cu
2CH3 C CH + CH CH

8. Aromatisation of nhexane CH3
m xylene
Cr O
nC6H14 
2 3
600C
4H2 
Solved Examples
1. Write down the directing nature of the following groups in so far as electrophilic
substitution on benzene is concerned.

(i) CN (ii)  NHCOCH3 (iii) COOR (iv) OCOR
Solution :
(i) C ≡ N group attaches itself to a benzene ring through the ‘C’ atom. This in its
bonded to a strongly electronegative element, ‘N’, by a multiple bond. Owing to
the greater electronegativity of ‘N’ than that of ‘C’, the N atom will withdraw
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electron from the C ≡ N bond. As a consequence the -electrons of the benzene
ring will be withdrawn by the C ≡ N group and thus C ≡ N will act as a
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deactivating group through  I and  R effects. Deactivation will occur mostly at
o and p positions. So it will direct an incoming electrophile to the m-position will
be more electrondense than the o and ppositions.

(ii) The lone pair of electron on the ‘N’ atom of  NHCOCH3 can undergo p
conjugation since they are in p Atomic orbital which is parallel 6 p atomic orbitals
of benzene. Therefore the group will exhibit +M  effect. Since +M  effect
an activates o/ppositions, NHCOCH3 group is an o/pdirecting group. This is
further supported by the fact that the complexes (intermediate) for the oattack
and pattack are more stable than the complex for the mattack.
(iii) It is a mdirecting group.
(iv) OCOR is an o/p directing group. The explanation for the directing nature is as
given for the NHCOCH3 group.
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2. Arrange the following compounds in increasing order of o/p product. PhCH2Cl,
PhCHCl2, PhCCl3, PhCH3.
Solution :
PhCCl3 < PhCCl2 < PhCH2Cl < PhCH3
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The increasing steric congestion and decreasing +I effect (increasing I effect from
CH3 to CCl3) are the causes for the decreasing o/p ratio.
3. Write IUPAC names of the following compounds :

CH3
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(a) CH2 CH2 CHCH2 (b) OH
Solution :
2 CH3
(a) (b) OH
1
2 - Methylphenol
4. Explain why the following systems are not aromatic ?
(i) CH2 (ii) (iii)
Solution :
(i) Due to the presence of a sp3-hybridized carbon, the system is
not planar. It does contain six -electrons but the system is not fully conjugated
since all the six -electrons do not form a single cyclic electron cloud which
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surrounds all the atoms of the ring. Therefore, it is not an aromatic compound.
Due to presence of a sp3-carbon, the system is not planar. Further it
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(ii)
contains only four  electrons, therefore, the system is not aromatic
because it does not contain planar cyclic cloud having (4n + 2)
-electrons. This system, however, behaves as a diene.
(iii) Cyclooctatetraene is not planar but is tub-shaped.

Further, it has only 8-electrons. Therefore, the
an system is not aromatic since it does not contain a
planar cyclic cloud having (4n + 2)  electrons. The
planar cyclooctatetraene is, however, antiaromatic.
5. How would you convert the following compound into benzene ?

(i) Ethyne (ii) Ethene (iii) Hexane
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Solution :
(i)
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(ii)
Ethene 1, 2, Dibromoethene Vinyl bromide Ethyne Benzene

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(iii)
Hexane Cyclohexane Benzene
Classwork Problems
Subjectives
1. How can you convert Ethylbromide to benzene.
2. Convert cyclohexanol into cyclohexa1, 3, 5triene.
Objectives
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Single Correct Answer Type
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1. Which of the following is heterocyclic aromatic species ?
(A) (B) (C) (D)
O O N
H
2. Which of the following species is aromatic?
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(A) (B)
Multiple Correct Answer Type

(C) (D)
1. Benzene can be obtained by

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(A) Dehydrogenation of cyclohexane (B) Dimerisation of propyne
(C) Trimerisation of ethyne (D) Hydrogenation of cyclohexene
2. Benzene can be prepared by

(A) decarboxylation of sodium benzoate
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(B) reduction of benzyl chloride with Ni-Al alloy and NaOH

(C) distillation of phenol with zinc dust
(D) Fitting reaction
Paragraph Type
Using the following Paragraph, solve Q. 1 & 2

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In order for a compound or species to be aromatic it must have a cyclic, planar and
conjugated ring which can satisfy Huckel's rule of aromaticity.
1. Which of the following is aromatic?

+  _
+
(A) (B) (C) (D)
2. Which of the following is nonaromatic?

 
(A) (B) (C) (D)
Numerical Type
1. The molecular formula of diphenyl methane is C13H12. How many structural isomeric
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are possible when one of the hydrogen displace by chlorine atom ?
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2. How many benzylic hydrogens are present in the hydrocarbon shown ?
Matrix Match Type

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1. Match the following
(A)
Column I
(p)
Column II
Huckel number of e
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(B) (q) Aromatic
(C) (r) Nonaromatic

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(D) (s) Dipolar

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Homework Problems
Subjectives
1. 7  Bromo  1, 3, 5  cycloheptatriene exists as ionic compound while 5  bromo  1,

3  cyclopentadiene does not ionize even is the presence of Ag+ ion . Explain.
2. How can you prepare benzene from lime ?
Objectives
1. Oil of vanilla bean is :
(A) (B) (C) (D)
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2. Oil of bitter almonds is :
(A) (B) (C) (D)
3. The bond order of individual carbon-carbon bonds in benzene is

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(A) one
(C) between one and two
(B) two
(D) one and two, alternately
4. Molecule in which the distance between the two adjacent carbon atoms is largest is
(A) ethane (B) ethene (C) ethyne (D) benzene
CrO /Al O
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5. 
3 2 3 (x)majorproduct. ‘x’ is
600C
(A) (B)
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(C) (D)
6. Hybridization of nitrogen atom in pyridine is:

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(A) sp3 (B) sp2 (C) sp (D) sp3d
1. An aromatic molecule will

(A) have 4n -electrons (B) have (4n + 2)-electrons
(C) be planar (D) be cyclic
2. Which of the following is/are aromatic?

(A) (B) (C)  (D)
3. Choose the compounds below that are aromatic :
(A) (B) (C) (D)
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4. Choose the compounds below that are antiaromatic :
(A) (B) (C) (D)
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5. Which of the following are deactivating group ?
(A) (B)
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(C) CF3 (D)
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6. Dipole moment of which compound is not zero ?
(A) (B) (C) (D)

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7. Which of the following molecules, in pure form, is (are) unstable at room temperature ?
(A) (B) (C) (D)
Paragraph Type
Using the following Paragraph, solve Q. 1 to 3
According to Huckel Rule or (4n + 2) Rule a system possessing the following

characteristics would behave as an aromatic compound.
i) It should be planar.
ii) It should have complete delocalization of  electrons in the ring.
iii) It should have (4n + 2)  electrons in the ring.
Thus, benzene molecule having six   electrons (aromatic sextet) behaves as an
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aromatic compound.
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1. Which of the following is nonbenzenoid aromatic compound?
(A) Naphthalene (B) Anthracene (C) Biphenyl (D) Pyridine
2. Choose the correct option

(A) When acetylene is passed through red hot iron or quartz tube at 873 K,
it trimerises to give benzene.
(B) When anhydrous sodium benzoate is heated with sodalime it gives benzene.
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(C) When vapours of phenol are passed over heated zinc dust, it gives benzene.
(D) All of these.
3. Which of the following is aromatic ?

(+)
(+)
(A) (B) (C) (D)

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Numerical Type
1. From the given species, how many are anti aromatic ?

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+ +
+
, , , , , ,
I II III IV V VI VII
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2.
A is :
(1) (2) (3) (4)
3. Count the total number of correct conversion method

(i) Benzene to cyclohexane : Benzene on heating with hydrogen at 458 K to 473 K
in the presence of Ni catalyst forms cyclohexane.
(ii) Benzene to glyoxal : Benzene on reaction with ozone forms benzene triozonide
which on hydrolysis with water in the presence of Zn forms three molecules of
glyoxal.
(iii) Benzene to chlorobenzene  Chlorination of benzene in the presence of anhydrous
AlCl3 forms Chlorobenzene.
(iv) Benzene to hexachlorobenzene  When benzene reacts with excess of
chlorine in presence of anhydrous AlCl3, hexachlorobenzene is obtained. All the
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six hydrogen atoms of benzene ring are replaced the electrophile Cl.
(v) Benzene to benzene hexachloride  Benzene (C6H6) with chlorine in the
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presence of U.V. or bright sunlight gives addition reaction forming C6H6Cl6.
(vi) Benzene to bromobenzene  Bromine reacts with benzene in dark in presence
of Ferric bromide, FeBr3 and forms bromobenzene.
(vii)Benzene to nitrobenzene  When benzene is heated with a mixture of
concentrated nitric acid and concentrated sulphuric acid in proportion 1 : 2, called
nitrating mixture, at about 313 K  333 K, nitrobenzene is formed.
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(viii) Benzene to ethyl benzene  Benzene on reaction with ethyl chloride in the
presence of anhydrous aluminium chloride forms ethyl benzene.
(ix) Benzene to toluene  Benzene on treatment with methyl chloride in the
presence of anhydrous AlCl3, forms toluene.
(x) Benzene to benzene sulphonic acid  When benzene is heated with fuming
sulphuric acid (a mixture of H2SO4 and SO3) at 373 K ; it forms benzene
sulphonic acid by an electrophile SO3.
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Matrix Match Type
1. Column I Column II (Product)

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(A) (p) Aromatic
+
Obey’s Huckel (4n +
(B) (q)
2) Rule
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Planar on almost
(C) (r)
planar
(D) (s) Anti aromatic
(t) Non-Aromatic
Classwork Problems
Subjectives
Br Br
1. CH3  CH2  Br  alcKOH Br2 CCl4
 CH2  CH2  CH2  CH2
alc KOH
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NaNH 2 /
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reduced Cu
CH CH
3 CH  C  
300 C

2.
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Objectives
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1. (C) 2. (C)

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1. (A), (C) 2. (A), (C)
Paragraph Type
1. (C) 2. (C)
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Numerical Type
1. [4] 2. [5]
Matrix Match Type
1. (A)  (p), (r) ; (B)  (p), (q) ; (C)  (p), (q), (s) ; (D)  (p),(q),(s)
Homework Problems
Subjectives
Br
+
+
Ag
1. + AgBr
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The cation obtained is tropylinium ion which is aromatic in nature and is most stable.
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But ,
Br
+
+
Ag
+ AgBr
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Where the cyclopentadienyl cation is antiaromatic and is less stable, thus formation
of the same is renote. Therefore it doesn’t go under ionisation.
Objectives
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1. (A) 2. (C) 3. (C) 4. (A) 5. (D) 6. (B)

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1. (B), (C), (D) 2. (A), (C) 3. (A), (C), (D)

4. (B), (D) 5. (A), (B), (C) 6. (A), (B)
7. (B), (C)
Paragraph Type
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1. (D) 2. (D) 3. (D)
Numerical Type
1. [4] 2. [2] 3. [10]
Matrix Match Type
1. (A) (p), (q), (r); (B)  (p), (q), (r); (C)  (r), (s); (D)  (t)
MODULE 2
Physical Properties
i) Benzene is a colourless and volatile liquid. It's boiling point is 80C and freezing point
is 5.5C. It has characteristic odour.
ii) It is highly inflammable and burns with sooty flame.
iii) It is lighter than water. It's specific gravity at 20C is 0.8788.
iv) It is immiscible with water but miscible with organic solvents such as alcohol and
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ether.
v) Benzene itself is a good solvent. Fats, resins, rubber, etc., dissolve in it.
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vi) It is a nonpolar compound and its dipole moment is zero.
vii) It is an extremely poisonous substance. Inhalation of vapours or absorption through
skin has a toxic effect.
Chemical Properties
The principal reactions of benzene can be studied under four categories.
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(1) Addition reactions.
(2) Electrophilic substitution reactions.
(3) Oxidation reactions
(4) Reduction reactions
(1) Addition Reaction :

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i) Addition of Hydrogen :
Ni
+ 3H2 or C6H12
150 C, pressure
Benzene
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Birch reduction takes place in presence of Na and liquid NH3 .

H H
Na / liq. NH3
+ [H]
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Benzene 1,4 dihydrobenzene
ii) Addition of halogens :

Benzene reacts with chlorine or bromine but not with iodine in presence of sunlight or
ultraviolet light to produce crystalline hexachlorides and hexabromides, respectively.
Sunlight
C6H6  3Cl2   C6H6 Cl6
BHC
-isomer of benzene hexachloride is most important and used as a powerful
insecticide under the name of ‘gammaxene’ or ‘666’ or ‘lindane’.
iii) Addition of Ozone : When treated with ozone, benzene triozonide is produced
which on hydrolysis yields glyoxal.
O O
CH O CH
HC CH HC CH O CHO
3H2
+ 3O3 O 3 + 3H2O + 3ZnO
HC CH HC CH 3Zn CHO
O
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(Glyoxal)
CH O CH
Benzene
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O O
Benzene triozonide
(2) Electrophilic Substitution Reactions

Benzene undergoes electrophilic substitution reactions because it is an electron rich
system due to delocalized electrons. The reactions can be represented as :
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+ E Nu
Catalyst
E
+ HNu
E Nu E + + Nu
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Fig. : The freeenergy diagram for an electrophilic aromatic

substitution reaction. The arenium ion is a true intermediate lying
between transition states 1 and 2. In transition state 1the bond
between the electrophile and one carbon atom of the benzene ring is
only partially formed. In transition state 2 the bond between the same
benzene carbon atom and its hydrogen atoms is partially broken.
Aromatic Electrophillic Substitution (ArSE)

H E E
X = + Mgr (activating gr.)
E+
+
= O , NR2 , NHR , NH2 , H
+
OH , OR,  NHCOR,
 OCOR , CH3 , (CH3)2CH,
X (+Mgr.) X X
(CH3)3C
E
E+
Y =  Mgr (deactivating gr.) +
 
r
=  NH3 ,  NR3 ,  NO2 , CN, SO3H, Y (-Mgr.) Y
E
ka
+
CHO,
CO, COOH, COOR, CONH2,
E
F, Cl, Br, (Weak deactivating gr.) E
 ArSE  Activating power of the + M group

1

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Mechanism
deactivatingpoweroftheMgroup
In all electrophilic aromatic substitution reactions, the first step is the attack by an
electrophile, E+.
al
Step 1 : (slow step)
 H
E
E  
(Slow )
 
dy
Carbonium ion
(s-complex)
H H
 H
E E E

Vi
Resonance forms of carbonium ion (arenium ion)
Step 2 :
 H
E (Fast) E
 Nu:     H  Nu
Carbonium ion Substitution product
The removal of an proton, occurs rapidly relative to step 1 and has no effect on the
overall rate of reaction.
(A) Halogenation :
Cl Cl Cl
Cl
AlCl3 Cl2
+ Cl2 +
or FeCl3 FeCl3
r
o dichloro benzene
Cl
ka
pdichlorobenzene
Benzene does not react with bromine or chlorine unless a Lewis acid is present in the
mixture. Hence benzene does not decolorize a solution of bromine in carbon
tetrachloride.
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Mechanism
Step 1 :
Formation of the electrophile (Cl+)
Cl  Cl + FeCl3  Cl+ + FeCl4

al
Step 2 :
 H H H
Cl Cl Cl
Cl 
(Slow)
 
 

 
dy
Benzen
Arenium ion
Step 3 :
H Cl
Cl
Vi
Cl  FeCl3 
  FeCl3  HCl
Chlorobenzene
A proton is removed from the arenium ion to become chlorobenzene.
Iodination of benzene is reversible and slow (Cl2 > Br2 > I2). Therefore iodination
takes place in presence of an oxidizing agent, i.e. HIO3 or HgO to remove HI
formation, (which is a strong reducing agent).
(B) Nitration :
NO2
H2SO4 (conc.)
+ HNO3 + H2O
Conc. 60 C
NO2 NO2
80 C
 HNO 3    H2 O
r
H SO (conc.)2 4
(conc.)
NO2
ka
Nitrobenzene m-Dinitrobenzene
NO2
H2SO4 (conc.)
+ 3HNO3 + 3H2O
 100C
an
Mechanism
Step 1 :
(Fuming) O2N
H
NO2
O O
 |+ 
HO3 SO  H  H  O N  H  O N  HSO4
al


O O
In this step nitric acid accepts a proton from the stronger acid, sulfuric acid.
Step 2 :
H
dy
|
O

   H2O + O  N  O Nitronium ion
H  O N

O
Step 3 :
O H 
H H
|| NO2
NO2 NO2
Vi
slow
 N  
|| 
O 
Step 4 : Arenium ion


H

O H NO2 H O H
NO2 + +
H H
The arenium ion then loses a proton to a Lewis base and becomes nitrobenzene.
(C) FriedelCrafts Alkylation :

This reaction used for introducing an alkyl or acyl group in benzene nucleus by an
alkylating or acylating agent in presence of a suitable catalyst.
The alkylating agent is usually an alkyl halide, an alcohol or an alkene, while the
acylating agent may be an acid chloride or acid anhydride. The catalyst may be AlCl3,
FeCl3, SnCl4, BF3, BCl3 or ZnCl2.
i) Alkylation :
AlCl
C6H6  CH3 Cl 
3
C6H5 CH3  HCl
r
AlCl
ii) C6H6  C2H5 OH 
3
C6H5 C2H5  H2 O
ka
AlCl
iii) C6H5H  C2H4 
3
C6H5 C2H5
Ethylene
AlCl
iv) 2C6H5H  CH2 Cl2 
3
(C6H5 )2 CH2  2HCl
AlCl
v) 3 C6H5H  CHCl3 
3
(C6H5 )3 CH  3HCl
an
Mechanism
Step 1 :
CH3Cl + AlCl3  CH3
Electrophile
 AlCl4
[Lewis acid  base reaction]
Step 2 :
 H
al
CH3
 CH3 
Electrophile
Benzene Carbonium ion
dy
Step 3 :
 H Cl CH3
CH3 
 Cl Al Cl   AlCl3  HCl
Cl Toluene Regeneration of AlCl3

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Propyl chloride react with AlCl3 and give npropyl carbocation which rearrange and give
2 carbocation which react with benzene and give cumene instead of propyl benzene.

CH3CH2CH2Cl + AlCl3  CH3 CH2 CH2  AlCl4
 
CH3 CH2 CH2  CH3 CHCH3
less stable carbocation More stable carbocation
Alkyl groups are electron releasing groups, and once one is introduced into the benzene
ring it activates the ring toward further substitution.
H3C CH3
CH
CH3
  CH 

CH3 (Cumene)
r
Limitation of Friedel-Craft’s Alkylation :
ka
1. At the end of reaction, mixture contains more than one product due to
polysubstitution. R R R R
CH CH
R
AlCl +
+ CH Cl 
3
an R
2. The possibility of the rearrangement of alkyl group.

3. Aryl halides cannot be used in place of alkyl halides.
R
CH
R
Cl
al
No Friedelcrafts reaction.
AlCl3
No Friedelcrafts reaction.
dy
C=C , AlCl3
4. An aromatic rings containing the NH2, NHR or NR2 group do not undergo Friedel-
Craft’s alkylation.
Friedel crafts alkylation are not restricted to the use of alkyl halides and aluminum
Vi
chlorides.
CH(CH 3) 2
0 C
 CH3 CH  CH2 
HF

propene
Isopropylbenzene (cumene)
0 c
+ 
HF

Cyclohexene Cyclohexyl benzene
OH
60c
+ 
BF
 + H2O
3
Cyclohexanol Cyclohexyl benzene
r

Where y = (NO2 , CN, NR3 , SO3H , CHO,
AlCl3
RX Noreaction COCH , COOMe , NH , NHR , NR )
ka
FC.Re action 3 2 2
Strong + mgr
CH3 CH3
H3 CCCH3 H3 CCCH3
an
(leq.)
tBuc/(leq.)
AlCl 3

(minor)
+
C(CH3)3 (major)
al
C(CH3)3
tBuCl


(excess) (major)
dy
(D) Friedel Crafts Acylation (Formation Of Ketones)

H

NH2 H N AlCl3
Vi
+ AlCl3
Does not undergo a Friedelcrafts reaction.
Substitution of hydrogen by acyl group in aromatic compound is known as

FriedelCrafts Acylation. The most commonly used catalyst is anhydrous AlCl3,
although other Lewis acids can also be used. The acylating reagents are either acid
halides or acid anhydrides.
Mechanism
Step 1:
O
   
R  C  Cl  AlCl3  R  C  O  R  C  O  AlCl4 OR RCO  AlCl4
Step 2:
H
r
 R  C   O 
Slow
 COR
RDS
ka
Step 3:
H COR
COR AlCl 4

Fast  HCl  AlCl3
an
Long chain alkyl benzene can be prepared by Friedel Crafts acylation with appropriate
reagent followed by Clemmensen reduction (conc. HCl/Zn amalgam).
+ CH3 CH2  C||  Cl AlCl


3
O
C CH2CH3
+ HCl
O Zn(Hg)
HCl,reflux
al
CH 2CH 2CH3
O O O
dy
CH 2 C C CH 2CH 2 C OH Zn(Hg),HCl
+ O  
3
AlCl   
reflux
CH 2 C
O
Benzene
(excess) Succinic
anhydride
Vi
CH2CH2CH2COOH
80c
CH2 CH2 AlCl ,CS
  
3 2

SOCl 2
CH2
ClC O
4phenylbutanoic acid   tetralone
O
4phenyl butanoyl chloride
Note :
1. Aryl and vinylic halides cannot be used in Friedel crafts reactions as they do not
form carbocations easily.
AlCl3
+ H2C CHCl No reaction
2. In substituted benzenes, Friedel craft reactions gives poor yield when electron
withdrawing groups are present on the ring.
3. In Friedel craft alkylation, most stable carbocation (from alkyl halide or alkene)
r
determines the final substitution product.
4. Intramolecular Friedel craft reactions of  and  aryl alkanoic acid or alkanoyl
ka
chlorides give cyclic products.
CH2CH2CH2COOH
HF
0 C
O
tetralone
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(E) Sulphonation :
CH2CH2CCl
O
AlCl3
O
+ HCl
Benzene forms benzene sulphonic acid with hot concentrated sulphuric acid while
with fuming sulphuric acid or oleum (conc. H2SO4 + SO3) at high temperature,
al
m-benzene disulphonic acid is formed.
So for sulphonation, the attacking electrophile is SO3.
Mechanism
dy
Step 1:  Formation of the electrophile (SO3).
2H2 SO 4  H3 O   HSO 4  SO3
Step 2:   H
SO3  C6H6  C6 H5 _
slow
SO3
Vi
 H _
Step 3:  C 6H 5 + HSO 4  C6H5 SO 3  H2 SO 4 fast

SO 3
 
C6H5 SO
3  H3 O  C6H5 SO 3H  H2 O
Step 4: 
(equilibirum far to the left)
(F) Formylation : O
It is a direct method for introducing an aldehydic group ( C H) in benzene. It is
called GattermannKoch synthesis when a mixture of dry HCl gas and carbon
monoxide is used in presence of anhydrous aluminium chloride.
AlCl
C6H6  CO  HCl 
3
C6H5 CHO  HCl
(G) Gattermann  Aldehyde Reaction (Reaction with HCN)
r
AlCl3
C6H5H + HC N + HCl C6H5CH NH . HCl
HOH
ka
C6H5CHO + NH4Cl
(H) Chloromethylation :
AlCl
C6H6  HCHO  HCl 
3
C6H5 CH2 Cl  H2 O
Solved Examples
an
1. p-Chloronitrobenzene has less dipole moment (2.4D) than p-nitrotoluene (4.4D).
Explain.
Solution :
al
Cl NO2 H3C NO2
In p-chloronitrobenzene individual moments are in the opposite direction and cancel

dy
each other partially whereas in p-nitrotoluene, both the moments are in the same
direction hence are added. So, the dipole moment of p-nitrotoluene is more than p-
chloronitrobenzene.
2. How does benzene reduced to 1, 4-cyclohexadiene using sodium in liquid ammonia

in presence of ethanol ?
Vi
Solution :
H C2H5OH H H H H C2H5OH H H
Na  Na 

e 

e
  
H H H H H
3. Complete the following reactions with appropriate reagents?
(a) 1. 2. 3.

  

O I
(b) NH C CH3 7.
 
 
 
8. 9. 10.
NO2
r
Solution :
ka
(a) O /H O LiAlH conc. H2SO4
  O  
4
3 2
(1) [H] OH 
Heat

(2) (3)
Cyclopentanone Cyclopentanol Cyclopentene
O
(b)
an NH C H /H2O
CH3 
(7)


Aniline
NH2 
2

NaNO HCl


0 5 C
(8)
Benzene diazonium
chloride
(9)
N
NaNO2/Cu
NCl
I
al
I /HgO
NO 2 
2
(10)
 NO2
I Nitrobenzene
3,5Diiodo1nitrobenzene
dy
4. Write down the relative rate order of monobromination of the following compounds
and assign reasons for the order. PhNH2, PhCOOH, PhH, PhNO2, PhCH3.
Solution :
Among the given compounds PhNH2 and PhCH3 have activating groups, NH2 and
CH3 respectively. NH2 has a strong +M effect and CH3 has +I effect and
Vi
hyperconjugative effect; +M effect being stronger than the +I and hyperconjugative

effects, PhNH2 will undergo the reaction more readily than PhCH3. Again PhCOOH,
PhBr, PhNO2 have deactivating groups the order of increasing deactivating effects is:
Br < COOH < NO2
So among these three the rate order will be : PhBr > PhCOOH > PhNO2
PhH has neither a deactivating nor an activating group; so it will be more reactive than
the compounds with deactivating groups. Therefore, the decreasing rate order is :
PhNH2 > PhCH3 > PhH > PhBr > PhCOOH > PhNO2
5. What happen when

(i) PhH is heated with CH2Cl2 in the presence of anhydrous AlCl3.
(ii) Chlorobenzene and benzene is treated together in the presence of AlCl3.
Solution :
PhH PhH
(i) Ph  H  CH2 Cl2  PhCH2 Cl 
AlCl
PhCH2Ph
3
AlCl3
(ii) PhH  PhCl  No reaction; since chlorobenzene does not form phenyl cation.
r
6. How will you convert benzene into
(i) pNitrobromobenzene (ii) m  Nitrochlorobenzene
ka
(iii) pNitrotoluene (iv) Acetophenone ?
Solution :
(i)
an
al
(ii)
(iii)
dy
Vi
(iv)
7. Write down the products of ozonolysis of 1, 2dimethylbenzene (oxylene). How

does the result support Kekule’s structure of benzene?
Solution :
The products of ozonolysis are glyoxal, 2, 3butanedione and 2oxopropanal. The
r
products of ozonolysis suggest three double bonds in the ring. This also suggests
that the positions of double bonds as shown in I and as shown II. This supports
ka
Kekule’s structure of benzene.
The structure I on ozonolysis is

expected to yield glyoxal and
2oxopropananl while structure II is
expected to yield glyoxal and 2,
3butanedione.
an
8. Why does benzene undergo electrophilic substitution reactions easily and
nucleophilic substitutions with difficulty?
Solution :
Benzene molecule has two  cloud rings, one above and the other below the plane of
al
atoms. Therefore, it is likely to be attacked by electrophiles which subsequently
brings about substitution. The nucleophiles would be repelled by the electron rings
and hence benzene reacts with nucleophiles with difficulty.
9. Arrange the following set of compounds in order of their decreasing relative reactivity
dy
with an electrophile, E+.

(a) Chlorobenzene, 2, 4-dinitrochlorobenzene, p-nitrochlorobenzene
(b) Toluene, p-H3CC6H4NO2, pO2NC6H4NO2.
Solution :
(a) The typical reactions of benzene are electrophilic substitution reactions. Higher
the electron-density in the benzene ring, more reactive is the compound towards
Vi
these reactions. Since, NO2 is a more powerful electron-withdrawing group than

Cl, therefore, more the number of nitro groups, less reactive is the compound.
Thus, the overall reactivity decreases in the order :
Chlorobenzene > p-nitrochlorobenzene > 2, 4-dinitrochlorobenzene
(b) Here, CH3 group is electron donating but NO2 group is electron-withdrawing.
Therefore, the maximum electron-density will be in toluene, followed by
p-nitrotoluene followed by p-dinitrobenzene. Thus, the overall reactivity
decreases in the order : Toluene > p-H3CC6H4NO2 > p-O2NC6H4NO2.
10. Suggest the name of a Lewis acid other than anhydrous aluminium chloride which
can be used during ethylation of benzene.
Solution :
Ethylation means introduction of an ethyl group in the benzene ring. This is usually
carried out by Friedel-Crafts reaction of benzene with ethyl halide (chloride or
bromide), ethene or ethanol. The Lewis acid catalysts other than anhydrous AlCl3
used in this reaction are : anhydrous FeCl3, SnCl4, BF3, etc.
Classwork Problems
r
Subjectives
ka
1. Arrange the following sets of compounds in order of decreasing reactivity towards
electrophilic substitution. Dichloromethyl benzene, toluene, difluoromethyl benzene,
chloromethyl benzene.
2. Complete the following reaction with appropriate structure of products/ reagent.
an C6H5CH  CH2 
Objectives
2

Br
 [A] 2
(ii) CH I
i)NaNH (3 eqv)
[B]
3
1. Among the following compounds (I  III), the correct order in reaction with
al
electrophile is
OMe NO2
dy
I II III
(A) II > III > I (B) III < I < II (C) I > II > III (D) I = II > III
Vi
2. Sulphanilic acid has high melting point. This is due to :
(A) the molecule exists as zwitter ion

(B) intramolecular hydrogen bonding takes place
(C) the compound is purely ionic in character
(D) none of the above
1. Which of the following compound yield glyoxal as the product of ozonolysis ?

(A) Benzene (B) Mesistylene (C) Isoprene (D) Ethyne
2. Which of the following reactions will produce benzene ?
(A) (B)
r
ka
(C) (D)
Paragraph Type

an
In the electrophilic substitution of benzene ring, the second substituent is directed by the
group already present. Electron releasing groups (+l and +M) are orthopara directing
and activating , whereas the electron withdrawing groups (I and M) are meta-directing
and deactivating.
Halogens are placed under the category of +T(Tautomeric) groups because they have
– Inductive and + Mesomeric effect. These groups are deactivating but ortho-para-
al
directing.
In the introduction of third group to the benzene ring, the product of minimum steric
hindrance is formed.
dy
1. Ortho-xylene on mono nitration gives :
(A) two products (B) three products (C) one product (D) four products
2. In the reaction,
Vi
Which of the following products is not formed at all?
(A) (B) (C) (D)
3. Which of the following is not an ortho, para-directing group?

(A) F (B) NC (C) OCOCH3 (D) CCl3
4. Which of the following substituted benzene derivatives would furnish three isomers
when one more substituent is introduced ?
(A) (B) (C) (D)
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5. A deactivating group in electrophilic substitution reaction :
(A) deactivates only ortho- and para-positions
ka
(B) deactivates only meta-position
(C) deactivates meta-position more than ortho- and para-positions
(D) deactivates ortho- and para-positions more than meta-position
Numerical Type
1. Identify the most reactive compound towards aromatic electrophilic substitution
reaction.
an CH3 Cl NO2
1 2 3 4
al
O
1
2
2. N Br2 /Fe(1e.q.)
8  
 ______? Major Product.
dy
3
4 5 6 7
In the product, Br is present at C___ position.
Homework Problems
Vi
Subjectives
1. An electron donating substituent in benzene orients the incoming electrophilic group

to the meta position. State true or false.
2. Write tautomeric forms for phenol.
3. Phenyl group is known to exert negative inductive effect. But each phenyl ring in
biphenyl (C6H5-C6H5) is more reactive than benzene towards electrophilic substitution.
Give reason.
4. Write the structure of the major organic product expected from each of the following
reaction?
AlCl
+ (CH3)2 CHCH2Cl 
3
(i)
CH3
(ii) N + HNO2
CH3
r
boil
(iii) CH3 CH2 CHCl2 
alkali

ka
H SO
(iv) C6H6  (CH3 )2 CHCH2 OH 
2 4

5. Complete the following, giving the structures of the principal organic products :
Me
CH3
an + H3C – C – CH2Br + Anhyd. AlCl3  ...... D ..............
6. Give reason in one or two sentences.

Nitrobenzene does not undergo Friedel–Crafts alkylation.
al
7. Increase order of reactivity towards ArSE;
CH3 NHCOCH3 OH COCH3
dy
1. Which has maximum dipole moment?

Vi
(A) (B)
O
O
C
(C) (D) C
2. Which of the following is most reactive towards electrophilic substitution reaction?
(A) (B) (C) (D)
3. Which of the following will have lowest heat of hydrogenation per mole of compound?
(A) (B) (C) (D)
r
ka
4. The strongest orthopara and strongest metadirecting groups respectively are :
(A) NO2 and NH2 (B) CONH2 and NH2
(C) NH2 and NO2 (D) X and CONH2
5. Which is the most stable arenium carbocation

CH3 CH3 CH3 CH3
an
(A)

NO2
H
(B)
H

NO2
(C)
H

NO2
(D)

H
NO2
CH2CH2CHCH CH2
al
6. H+
A, A is :
CH3
CH3
(A) (B)
dy
H3C CH2CH3
CH2CH3
(C) (D)
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CH3
CH3
7. X deactivates the ring and directs ortho/para in ; X is

(A) OH (B) Br (C) NH4 (D) NO2
8. Which can lose a proton from methyl group most readily.
(A) CH3 (B) CH3 (C) CH3 (D) CH3
9. Benzene reacts with CCl4 in presence of anhydrous AlCl3 to give :

(A) tetraphenyl methane (B) chlorobenzene
(C) tetrachlorobenzene (D) triphenyl methyl chloride
r
CH3CHC CH2
ka
10. + HBr A. A is :
Br
CH3CHCH CH2
CH3CHCHCH3
an(A)
Br
CH3CCH2CH3
(B)
Br
CH3CHCH2CH2Br
(C) (D)
al
CH3CHC CH2
11.
dy
+ HBr A. A is :
Br
CH3CHCH CH2
CH3CHCHCH3
Vi
(A) (B)
Br
Br
CH3CHCH2CH2Br
CH3CCH2CH3
(C) (D)
12.
(A) (B)
(C) (D)
r
ka
13. In the reaction,
an(A) is :
(A) H3PO2 (B) Cu2 Cl2 (C) HgSO4/H2SO4 (D) H+/H2O
14. Aniline when diazotised in cold and then treated with dimethylaniline gives a coloured
product. Its structure would be :
al
(A)
(B)
dy
(C)
Vi
(D)
15. Toluene is nitrated and the resulting product is reduced with tin and hydrochloric acid.
The product so obtained is diazotised and then heated with cuprous bromide. The
reaction mixture so formed contains a :
(A) mixture of oand mbromotoluenes
(B) mixture of o and pbromotoluenes
(C) mixture of o and pdibromobenzenes
(D) mixture of o and pbromoanilines
16. Identify ‘B’ in the following reaction :
r
(A) (B) (C) (D) none of these
ka
17. Among the following, the compound that can be most readily sulphonated is
(A) benzene (B) nitrobenzene (C) toluene (D) chlorobenzene
18. an(A) (B)
(C) (D)
al
19. In the reaction,
dy
(A) is :
(A) H3PO2 (B) Cu2 Cl2 (C) HgSO4/H2SO4 (D) H+/H2O
Vi
20.
The compound ‘X’ is :
(A) (B) (C) (D) none of these
21. Aniline when diazotised in cold and then treated with dimethylaniline gives a coloured
product. Its structure would be :
(A)
(B)
r
(C)
ka
(D)
22. Among the following, the compound that can be most readily sulphonated is
(A) benzene (B) nitrobenzene (C) toluene (D) chlorobenzene
an
23. Choose the incorrect statement.
(A) The overall rate of an electrophilic substitution reaction, except sulphonation in
benzene and deuterated benzene, are identical.
(B) The sulphonation reaction involving benzene is a reversible reaction.
(C) The reaction of benzene with npropyl chloride in the presence of AlCl3 gives
al
1phenylpropane as the only product.
(D) The iodination of benzene can be carried out by using ICl.

dy
1. Choose the correct statement.

(A) Heats of hydrogenation & combustion of benzene are lower than the expected
values.
(B) Benzene undergoes nucleophilic substitution reactions.
(C) For a molecule to be aromatic, it must contain 4n + 2 delocalized  electronic
cyclic cloud above and below the plane of the molecule.
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(D) Cycloheptatrienyl cation has unusually low stability.

(A) In electrophilic aromatic substitution reaction, the formation of intermediate
arenium cation is the rate determining step.
(B) The monobromination of acetanilide proceeds slower than benzene.
(C) All electrophilic substitution reactions (except iodination, sulphonation etc.) involving
benzene are irreversible.
(D) The monobromination of acetophenone proceeds faster than benzene.

(A) The order of reactivity toward aqueous HBr in the following alcohols is
N C CH2OH > CH2OH > HO CH2OH
(B) The order of ease of dehydration in the following compound is

(C6H5)2CCH3 > (C6H5)CHCH3 > C6H5CH2OH
r
OH OH
ka
(C) The order of reactivity towards ring nitration is pxylene > toluene > ptoluic acid
> terephthalic acid
(D) The CH bond in benzene is slightly stronger than the CD bond is deuterated
benzene (C6D6).
an
4. Isopropyl benzene can be obtained by :
(A) +
(B)
(C) (D)
al
5. Styrene undergoes following reaction in acid medium :
dy
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The various intermediates formed are :
(A) (B) (C) (D)
6. Which of the following are more reactive than diphenyl in electrophilic aromatic
substitution reaction ?
(A) (B)
r
(C) (D)
ka
CH3
O /Me S
7. 
3 2 Products.
The possible products are
CHO
an
(A) CH3  CHO (B) CH3 CCHO (C)
O
CHO
(D) CH3 CCCHO
8. Which of the following compounds are expected to have zero dipole moment ?
O O
(A) p-dichlorobenzene (B) m-dichlorobenzene

(C) cis-1, 2-dichloroethene (D) trans-1, 2-dichloroethene
al
9. Which of the following groups when attached to benzene ring increase its reactivity
towards electrophilic substitution ?
(A)  SO3H (B)  COCH3 (C)  CH3 (D)  NH2
dy
(A) No organic molecule other than benzene has a molecular formula of C6H6.
(B) The electrophile in the sulphonation of aromatic molecule may be either SO3 or
HSO3 .
(C) In FriedelCrafts alkylation the electrophile is a carbocation.
(D) In FriedelCrafts alkylation, AlCl3 acts as a Lewis base.
Vi

(A) A substitutent which stabilizes the intermediate carbocation in the electrophilic
substitution in benzene activates the latter.
(B) +R group activates ortho and para positions in benzene ring towards aromatic
electrophilic substitution.
(C) A deactivating group deactivates ortho and para positions whereas the meta
position is activated.
(D) Benzene in the presence of AlCl3 reacts with isobutyl bromide to give
tertbutylbenzene.

(A) The rates of sulphonation reactions involving benzene & deuterated benzene are
slightly different.
(B) The reduction of CO group into CH2 group may be carried out via
Clemmensen reduction which involves the use of hydrazine and strong base.
(C) Iodine solution in benzene is brown due to the formation of chargetransfer
complex between iodine and benzene.
(D) The structure C C C is less stable than C C C
r
ka
(A) The order of reactivity towards ring nitration in Ph(CH2)NO2 and PhNO2 is
PhCH2NO2 > PhNO2
(B) The order of reactivity towards electrophilic substitution is
C6H5CH3 < C6H5CH2COOC2H5 < C6H5CH(COOC2H5)2
(C) Each ring of biphenyl, C6H5  C6H5, is more reactive than benzene towards
an electrophilic substitution, and the chief products are ortho and para isomers.
(D) In benzyl radical, the two side chain hydrogens are perpendicular to the benzene
ring.
14. Which of the following reactions give alkylation product ?

al
(A) (B)
(C) (D)
dy
15. Iodobenzene can be obtained by :
(A) (B)
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(C) (D)
16. When nitrobenzene is treated with Br2 in presence of FeBr3, the major product
formed is m–bromonitrobenzene. Statements which are related to obtain the
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 destabilised.
(C) Loss of aromaticity when Br+ attacks at the ortho and para positions.
(D) Easier loss of H+ to regain aromaticity from the meta position than from ortho &
para positions.
Paragraph Type
r
Using the following paragraph, solve Q. 1 & 2
If aromatic ring is substituted by more than one group then electrophilic aromatic
ka
substitution reaction takes place according to more activating group. Types of groups
which donate electron in aromatic ring are known as activating groups
1. Major product formation take place at which position in this reaction :
an
(A) 3 (B) 1 (C) 6 (D) 4
2. The correct order of reactivity towards aromatic electrophillic substitution ArSE for the
given compounds….
al
CH 3 Cl NH2 OH
I II III IV
dy
(A) I < II < III < IV (B) II < I < IV < III
(C) III < IV < I < II (D) IV < III < II < I
Using the following paragraph, solve Q. 3 & 4

If aromatic ring is substituted by more than one group then electrophilic aromatic
substitution reaction takes place according to more activating group. Types of groups
Vi
which donate electron in aromatic ring are known as activating groups.
3. Find out major product of following reaction :
(A) (B)
r
(C) (D)
ka
4. Identify the correct order of reactivity in electrophilic substitution reactions of the
following compounds :
CH3 Cl NO2
an 1 2 3 4
(A) 1 > 2 > 3 > 4 (B) 4 > 3 > 2 > 1 (C) 2 > 1 > 3 > 4 (D) 2 > 3 > 1 > 4
al
Benzene and its derivatives undergo substitution reactions

dy
5. Which of the following electrophilic substitution reactions does not involve positively
charged electrophile ?
(A) Nitration (B) Sulphonation (C) Alkylation (D) Halogenation
6. Which of the following electrophilic substitution reactions is a reversible reaction ?
(A) Nitration (B) Alkylation (C) Acylation (D) Sulphonation
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7. Which of the following compounds does not undergo electrophilic substitution

reactions in the presence of AlCl3 ?
(A) Chlorobenzene (B) Benzene (C) Nitrobenzene (D) Phenol

The electrophilic aromatic substitution of monosubstituted benzene is decided by the
substituent in benzene ring. Identify the characteristics of the indicated substituent in the
benzene ring.
8. Methyl group has

(A) Weak electrondonating inductive effect with none resonance effect.
(B) weak electrondonating inductive effect with strong electron donating resonance
effect.
(C) strong electronwithdrawing inductive effect with weak electrondonating
resonance effect.
(D) strong electronwithdrawing inductive effect with strong electrondonating
resonance effect.
9. Chlorine has
r
effect.
ka
resonance effect.
resonance effect.
10. CHO group has
an
effect.
resonance effect.
resonance effect.
al
Numerical Type
CH3
(CH CO) O
1. 
3
AlCl
2
Product. What is the degree of unsaturation of the product?
3
dy
2. From the given groups or substituents how many are meta directing ?
NHCOCH3, CONH2, OCOCH3, COOCH3, CHO, COCH3, NH2, CH3, CCl3, CN.
Vi
Classwork Problems
Subjectives
CH3
1. In toluene , Methyl group has (+I) effect, thereby increasing electron density
in the benzene ring and makes it susceptible for the electrophilic substitution.
CH2 Cl
In chleromethyl benzene , due to (I) effect of Cl atom slightly (+ve) charge
is developed on CH2 carbon atom.
+ 
CH2-Cl
r
Similarly in dichloromethyl benzene, due to presence of two-Cl atom
ka
Cl Cl
CH
CH carbon becomes more positively charged.

an
Now, I effect of F > > I effect of Cl
 Electron density decreases from chleromethyl benzene to difluoromethyl
benzene gradually.
Hence, the above order.
2. A  C6H5 CH CH2 , B  C6H5 C  CCH3

| |
al
Br Br
Objectives
dy
1. (C) 2. (A)
1. (A), (D) 2. (A), (B), (D)

Vi
Paragraph Type
1. (A) 2. (D) 3. (D) 4. (A), (B) 5. (D)
Numerical Type
1. [2] 2. [8]
Homework Problems
Subjectives
1. False
OH O
H
2. H
r
ka
3. Normally, benzene gives electrophilic substitution reaction rather than electrophilic
addition reaction although it has double bonds. Give reason.
4.
C(CH3)3 N(CH3)2
(i)
an N
O
5. CH3 C(CH3)2
al
(D)
6. The nitro group in nitrobenzene strongly deactivates the benzene ring. This
decreases the reactivity of benzene towards Friedel–Crafts alkylation.
dy
7. CH3 COCH3
OH NHCOCH3
> > >
ArSE  activating power of + M group

Vi
Objectives
1. (C) 2. (A) 3. (A) 4. (C) 5. (C) 6. (A)
7. (B) 8. (D) 9. (A) 10. (C) 11. (C) 12. (A)
13. (A) 14. (C) 15. (B) 16. (C) 17. (C) 18. (A)
19. (A) 20. (B) 21. (C) 22. (C) 23. (C)

1. (A), (C) 2. (A), (C) 3. (A), (D)
4. (A), (B), (C) 5. (A), (B), (C) 6. (A), (B), (D)
7. (B), (D) 8. (A), (D) 9. (C), (D)
10. (B), (C) 11. (A), (D) 12. (A), (C)
13. (B), (D) 14. (A), (B), (D) 15. (B), (C)
16. (A), (D)
r
ka
Paragraph Type
1. (B) 2. (C) 3. (C) 4. (C) 5. (B) 6. (D)
7. (C) 8. (A) 9. (C) 10. (D)
Numerical Type
an
1. [5] 2. [6]
al
dy
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MODULE 3
 Oxidation Reactions
It is not easily oxidized. Acidified KMnO4 , chromic acid, or very strong oxidizing
agents convert benzene slowly into CO2 and water on heating.
CHCOOH CHCO
O2  O
r
V2O5, 500 CHCOOH CHCO
Maleic Acid Maleic Anhydride
ka
COOH CO
O2  O
V2O5, 500
COOH CO
Phthalic Acid
an CH3
KMnO4/OH
COOH
Phthalic Anhydride

al
CH(CH3)2 COOH
KMnO4/OH

dy
 Oxidation of the Side Chain

An important characteristic of side chain oxidations is that oxidation takes place
initially at the benzylic carbon. Alkyl benzenes with alkyl groups longer than
methyl are ultimately degraded to benzoic acids.
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(i) KMnO ,OH /heat

PhCH2 CH2 CH2R 
4
  PhCO2H
(ii) H3O
An alkylbenzene Benzoic acid
Tert butyl benzene should be resistant to oxidation as it does not contain a benzylic
hydrogen and this has been found to be practically true also.
Side chain oxidation is not only restricted to alkyl groups but other groups in the side
chain can also be degraded to benzoic acid. Alkenyl, alkynyl and acyl groups are
oxidized by hot alkaline potassium permanganate in the same way.
CH = CH2 COOH

OH|KMnO


4
CCH COOH

OH|KMnO

4
r

ka
COCH3 COOH

OH|KMnO


4

Combustion : 2C6H6  15O2   12CO 2  6H2O

an
Reduction Reaction
2 + 12 HI D/P

 +
CH3
+ 6 I2
Benzene Cyclohexane
al
General Chemical Properties Of Arenes
Halogenation of The Ring
When halogenation of alkyl or alkenyl benzenes is to be carried out in ring, a lewis acid catalyst
dy
is required. Since alkyl and alkenyl groups are ortho and para directing, so the incoming
electrophile (Cl+ or Br+ in chlorination and bromination respectively) will be oriented at either
ortho or para position.
C H C2H5 C2H5
2 5
Cl /FeCl

2 3
 +
Cl Cl
Vi
(minor) (major)
CH  CH2 CH  CH2 CH  CH2
Br /FeBr

2 3
 +
Br Br
(minor) (major)
For the addition of Br2 to double bond of the side chain, the reaction should be carried out
in the presence of Br2 in CCl4.
Halogenation of the Side Chain

We have already seen that bromine and chlorine replace hydrogen atoms on the ring of
toluene when the reaction takes place in the presence of a Lewis acid. In ring
halogenations, the electrophiles are positively charged chlorine or bromine ions called as
chloronium or bromonium ions. These positive electrophiles attack the  electrons of the
benzene ring and aromatic substitution take place. Chlorine and bromine can also be
make to replace hydrogens of the methyl group of toluene. Side chain halogenation takes
place when the reaction is carried out in the absence of Lewis acids and under conditions
that favour the formation of radicals. When toluene reacts with Nbromosuccinimide
(NBS) in the presence of light, the major product is benzyl bromide. NBromosuccinimide
r
furnishes a low concentration of Br2 and the reaction is analogous to that for allylic
bromination. Here, it is referred as benzylic bromination.
ka
O O
|| ||
C C
H2C H2C
CH3 +  light
NBr  CH2Br +  NH
CCl 4
H2C H2C
an C
| | NBS
O
Benzyl bromide
Side chain chlorination of toluene can also takes place in the gas phase at 400  600C
C
||
O
or in the presence of UV light. When an excess of chlorine is used, multiple chlorinations

of the side chain occur.
al
CH3 CH2Cl CHCl2 CCl3
Cl Cl Cl
 2 
heat / light
  2    2 
heat / light

heat / light
dy
Benzyl chloride dichloromethyl trichloromethyl

benzene benzene
(Benzal Chloride)
Mechanism : (Benzylic halogenation)

Chain Initiation
Vi
Step 1 : peroxides,heat
X2 
or light
 2X .
Chain propagation
Step 2 : C6H5 CH3 X.C6H5 CH2 HX
Benzylradical
Step 3 : C6H5 CH2   X 2  C6H5 CH2 X  X 

Benzyl radical Benzyl radical
X
Fast
 X2

 CHCH 3 
 CH CH 3  X 
X Benzylic radical 1-halo-1-phenylethane

CH2CH3 (more stable) (major product)
( HX)
Slow X
  CH 2 CH 2  
2
 CH 2 CH 2 X  X 
1 radical 1-halo-2-phenylethane
(less stable) (minor product)
r
Benzylic halogenations are similar to allylic halogenation in that they involve the
formation of unusually stable radicals. Benzyllic and allylic radicals are even more stable
ka
than tertiary radicals.
Example :
Starting with toluene, outline a synthesis of (a) 1-bromo-2-trichloromethylbenzene,
and (b) 1-bromo-4-trichloromethylbenzene.
Solution :
Compound (a) and (b) can be obtained by ring bromination of toluene followed by
an
chlorination of the side chain using three molar equivalents of chlorine.
Cl  excess)

2
hv or heat
Br2
al
(Separate) (a)
Fe

Cl (excess)

2
dy
hv or heat
(b)
These halogenations takes place through the same radical mechanism as for
halogenation of alkanes. The halogens dissociate to produce halogen atoms and then the
halogen atoms initiate chains by abstracting hydrogens of the methyl group.
Vi
Example :
(a) Give the product of the reaction of pxylene with 2 moles of NBS or Br2 at 125C in
presence of light.
(b) Why dibromination does not occurs at the one methyl occur?
(c) Which reacts faster, pxylene or toluene? Explain.
Solution :
CH2Br
(a)
CH2Br
r
(b) Electronwithdrawal by one Br makes removal of an additional H. more difficult and
thus the second substitution occurs at other methyl group.
ka
(c) pXylene reacts faster than toluene as the electronreleasing methyl provides
additional stability to the radical.
Addition to the Double Bond of Alkenyl Benzenes

In the presence of peroxides, hydrogen bromide adds to the double bond of 1phenyl
propene to give 2bromo1phenyl propane as the major product
an CH  CHCH3 HBr

peroxides
 CH2 CHCH3
Br
In the absence of peroxides, HBr adds in just the opposite way.

 CH  CHCH 3  HBr
    CHCH2 CH3
al
(no peroxides) 
Br
The addition of hydrogen bromide to 1phenylpropene proceeds through a benzylic

radical in the presence of peroxides, and through a benzylic cation in their absence.
dy
Synthetic Applications
To synthesize obromonitrobenzene, introduce the bromine into the ring first as it is an
ortho-para director.
Br Br Br
NO2
Br HNO
2
  3
 +
Vi
FeBr 3 H SO
2 4
NO2
The ortho and para compounds obtained as products can be separated by various
methods. However, if we had introduced the nitro group first, we would have obtained
mbromonitrobenzene as the major product.
We can synthesize the ortho and paranitrobenzoic acids from toluene by nitrating it,
then separating the ortho and paranitrotoluenes, and then oxidizing the methyl groups to
carboxyl groups.
CH3 COOH
KMnO ,OH ,heat


4
 
H3 O
CH3 NO2
NO2
pNitrotoluene pNitrobenzoic acid
HNO

H SO
3

2 4
r
CH3 COOH
NO2
ka
NO2
KMnO 4 ,OH ,heat

 
H3 O
oNitrotoluene oNitrobenzoic acid
CH3 COOH COOH

an (i)KMnO ,OH ,heat

4
 
(ii)H3 O
 3
H SO ,heat
2
HNO
4
NO2
Benzoic acid mnitrobenzoic acid
al
We can synthesize m-nitrobenzoic acid by reversing the order of the reactions.
Example
Synthesis of mchloroethylbenzene from benzene.
Cl
dy
¾¾

CH2CH3
Solution :
Chlorinating benzene and then follow with a Friedel Crafts alkylation using CH3CH2Cl and
Vi
AlCl3, or one could begin with a Freidel Crafts alkylation followed by chlorination.
However, neither method will give the desired product. The product obtained in both the
cases in a mixture of ortho and para chloro ethyl benzene. Actually, there is a three-step
method that will work.
COCH3 COCH3 CH2 CH3
CH3COCl Cl2 / FeCl3 Zn -Hg / HCl

¾¾¾¾
AlCl3
 ¾¾ ¾¾  ¾¾ ¾ ¾
Cl Cl
Orientation in Disubstituted Benzenes :

The position of an electrophile attack is generally determined by the nature. When two
different groups are present on a benzene ring, the more powerful activating group
generally determines the outcome of the reaction.
Example :
Which one is the major product I or II ?
NHCOCH3 NHCOCH3
NHCOCH3
r
halogenation X 
 
ka
X
CH3 CH3
CH3
Solution : I II
The acetamido group is a much stronger activating group than the methyl group. So, the
orientation of electrophilic substitution of the acetamido group determines the outcome of
the reaction. Substitution occurs primarily at the position of ortho to the acetamido group.

an
Hence, product (I) is a major product.
 If the two substituents make one or two positions relatively active, the incoming
electrophile will take those positions.
All ortho-para directing groups are more activating than meta directors, the ortho-
para director determines the orientation of the incoming group.
The order of decreasing directing powers of the op directing group is :
al
O > NR2 > NH2 > OH > NH COR > OCOR > Ar > Me > CH(CH3)2 > (CH3)3 C > X
(Cl,Br,I)
 If both substituents groups belong to the deactivating group, than isomeric
compounds are formed. However, the order of decreasing deactivating powers is
dy

NMe3  NO2  CN  SO 3H  CHO  COMe  COOH
 If one substituent belongs to the activating group and the other to the deactivating
group, the activating group determines the orientations.
 A very-small substitution occurs between two m-substituents since the position is
highly sterically hindered. Thus, steric effects are also important in aromatic
substituents.
Vi
For example,
Cl Cl Cl Cl
NO2 NO2
HNO3

H2 SO4
  
Br Br Br Br
NO2
(62%) (32%) (1%)
OH OH NH2 NH2
Br Br Br Br
Br /H O Br /H O
 
2 2
 ; 
2 2

Br Br
OH OH
r
NO2
 NO2

ka
NO2 NO2
NO2 NO2
NO2
 an CN
NO2

CN
(meta w.r.t. CN group)
Solved Examples
Give the Conversion
al
1. Aniline to benzoic acid
Solution :
NH2 N2Cl CN COOH
dy
NaNO2 HCl HO
05C CuCN/ 
2 
  
KCN 
Diazotisation H
Aniline Benzene Phenyl cyanide Benzoic acid

diazonium chloride
Vi
2. Benzene or toluene to benzyl alcohol
Solution :
CH3 CH2Cl CH2OH
CH Cl/AlCl
3 3 Cl Aq. NaOH
 2
 

hv
Benzyl Benzyl
Benzene Toluene chloride alcohol
3. Benzene to m-bromophenol
Solution :
NO2 NH2 N2Cl Br
 3 HNO
 NH4 
2 
S
Diazotisation
H SO ,100C    CuBr
 
2 4 HBr
NO2 NO2 NO2 NO2
Benzaldehyde Benzaldehyde m-Nitroaniline m-Nitrobenzene m-Bromo-
r
diazonium chloride nitro benzene
Br
ka
Br Br
Sn/HCl
H O Diazotisation
2 
  
Warm
N2Cl NH2
OH
m-Bromobenzene m-Bromoaniline
m-Bromophenol
diazonium chloride

an
4. Benzene to sulphanilamide
Solution :
NH2 NHCOCH3 NHCOCH3
NH3
CH COCl
3 ClSO H
3 
 
al
SO2Cl
NH2 NHCOCH3
dy
NaOH
 
SO2NH2 SO2NH2
5. Complete the equation and give your reason :

C6 H 5 CH = CHCH3 + HI  ?
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Solution :
The addition of HI is a two step reaction. The first step is the addition of the proton to
give a more stable carbonium ion. There are, however, two possibilities.
 
CH CHCH3 HI
  CH CH2Me or CH2 CH Me
(I) (II)
(I) can be written as a resonance hybrid :


 ....
CH2 CH2 CH3 CH3 CH2CH3
Carbonium ion (II) cannot be written as a resonance hybrid, and so (I) is more stable
than (II), hence this addition proceeds through (I).
HI
C6H5 CH  CHCH3   C6H5 CH CH2  CH3  I  C6H5 CHCH2 CH3
|
I
r
6. Explain tertbutylbenzene does not give benzoic acid on treatment with acidic KMnO4 .
ka
Solution :
In tertbutylbenzene the carbon atom attached to benzene ring is 4, hence tert butyl
benzene does not have any benzylic hydrogen atom necessary for oxidation. Hence
it can't be oxidized by KMnO4 to C6H5 COOH .
an
7. Out of benzene, mdinitrobenzene and toluene which will undergo nitration most
easily and why?
Solution :
Out benzene, mdinitrobenzene and toluene, toluene would undergo nitration most
easily because methyl group in toluene is electron releasing group and hence, it
activates the benzene ring towards electrophilic reactions such as nitration. On the
al
other hand, nitro groups in dinitrobenzene are electron withdrawing in nature. They
deactivate the benzene towards electrophilic substitution reactions. Thus, ease of
nitration in these compounds is in the order.
Toluene > Benzene > mDinitrobenzene.
dy
Classwork Problems
Subjectives
1. Account for the following order of reactivity towards free radical chlorination of
p-substituted toluene
P  CH3C6H4CH3 > C H CH > p  ClC H CH > p  NCC H CH
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6 5 3 6 4 3 6 4 3
2. Convent Benfzene to m-brome toluene.
Objectives
1. Benzophenone can be prepared from
(A) Chlorobenzene and benzaldehyde (B) Benzoyl chloride and chlorobenzene
(C) Benzene and benzoyl chloride (D) Benzene and benzoic acid
2. Product on monobromination of this compound is

H O
N
H3C CH3
Fe/Br

2

H O H O
N N
r
H3C CH3 H3C CH3
(A) (B)
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Br Br
H O H O
N N
H3C CH3 H3C CH3
(C) (D)
an Br

Br
1. Toluene, when treated with Br2/Fe, gives p-bromotoluene as the major product
al
because the CH3 group :
(A) is para-directing
(B) is meta-directing
(C) activates the ring by hyperconjugation
(D) deactivates the ring
dy
2. The products obtained in the reaction,
is/are :
(A) C6H5CHCl  CH3 (B) C6H5CH2  CH2Cl
(C) C6H5CCl2  CH3 (D) C6H5CHClCH2Cl
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Paragraph Type
Alkylation of aromatic compounds with aliphatic compounds like halides in presence of

Lewis acid catalyst is known as Friedel Crafts alkylation. It is an example of electrophilic
substitution.
In the process of acylation, group is introduced to the ring. Compounds having

(+ mesomeric groups) like  NH2 do not give FriedelCrafts reaction because these
r
compounds undergo conjugation with the catalyst. In the alkylation process, most
branched alkyl group is substituted because isomerization of carbonium ion takes place.
ka
In some FriedelCrafts reactions, the nature of product changes with the solvent used in
the reaction.
Predict whether the following statements are true or false :
1. AlCl3(aq.) is used as catalyst in FriedelCrafts reaction :

(A) True (B) False
an
2. When benzene is treated with CHCl3 in presence of AlCl3 catalyst, the following
reaction takes place :
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(A) True (B) False
3. Carbocations undergo isomerization in FriedelCrafts reaction. In each of the

following alkyl halides the isomerization takes place :
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CH3  CH2  CH2  Cl, CH3  CH2  CH2  CH2  Cl

(A) True (B) False
4. Following compounds easily give FriedelCrafts reaction :

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(A) True (B) False
5. Diphenyl methane is obtained when benzene is treated with dichloro methane in

presence of anhydrous AlCl3 :
(A) True (B) False
Numerical Type
O
Br /h
C CH2 
2
no.ofHalogenatedproduct.
1.
OMe
1
r
2
2. Monobromo substituted product. In the product, Br is present
Br2 / CS2
ka
3 at C  ………..
4
CH3
Matrix Match Type
an
1. Match the following columns :
(A)
Column I
(p)
Column II
p-substitution
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(B) (q) m-substitution
dy
(C) (r) Substitution at faster rate than

benzene
(D) (s) Substitution at slower rate than

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benzene
Homework Problems
Subjectives
1. The rings of each of the following compounds were nitrated where would you expect
the NO2 group to enter?
OH
CH3 CN NHCOCH3
r
N(CH3)2 OH
C(CH3)3
ka
NH2 OH
2. C OCl AlCl . Identify (X) and (Y).

an  |
COCl
 Zn (Hg)
3  X 
HCl
 Y
3. Give the mono-substitution product in the following reactions.

al
NO BF 
(i) 
2 4
NO BF 

2 4
dy
(ii) CH2
NO2
O
(iii) Br /Fe
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C O 
2

+
N (CH3)3 NH2
Br /Fe
(iv) 2Cl
(v) 
2

AlCl 3
4. Convert :
COOH COOH
(not more than 3 steps)
5. What happens when excess chlorine is passed through boiling toluene in the
presence of sunlight ?
r
6. Answer the following with suitable equation wherever necessary :
How will you convert toluene to m-nitrobenzoic acid ?
ka
(i)Br ,Heat,Light
C6H5 C2H5 2
(ii)NaCN


7. Predict the structures of the intermediates/products in the following reaction

sequence:
an OMe O
1. AlCl3
O  Zn(Hg)/HCl H3PO4
  A  B 
2. H3O

MeO
O
O
al
8. Predict the major product in each of the following reactions :
o
CCl3
dy
Br2 (1 equivalent) / OH

CH3 Cl2/Fe
(a) H2O (b)
9. Monosubstituted alkyl benzene of the formula C10H14 resists vigorous oxidation to an

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aryl carboxylic acid. Name the compound and write its various monosubstituted
isomers which on oxidation gives aryl carboxylic acid.
10. Identify the final product
CH3 NO2
KMnO  KMnO 
(A) 4
 X. (B) 4
 Y.
 O O 
11. Each of the following reactions gives two products. Write the structures of the
products.
Alc.KOH,Heat
(a) C6H5 CH2 CH(Cl)C6H5  
NHCOCH3
(b) Br ,Fe

2 
r
12. Each of the following reactions gives two products. Write the structures of the
products.
ka
Alc.KOH,Heat
(a) C6H5 CH2 CH(Cl)C6H5  
NHCOCH3
(b) Br ,Fe

2 
an
Objectives
1. In benzyne intermediate, the triple bond consists of :

al
(A) one sp-sp sigma bond and two p-p pi-bonds
(B) one sp2-sp2 sigma bond and two p-p pi-bonds
(C) two sp-sp sigma bonds and one p-p pi-bond
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(D) one sp2-sp2 sigma bond, one sp2-sp2 pi-bond and one p-p pi-bond.
2. Consider the following reaction :

ZnDust CH3 Cl AlkalineKMnO4
Phenol (X)
(anhyd.)AlCl
(Y) (Z);theproudct(Z)is:
3
(A) benzaldehyde (B) benzoic acid (C) benzene (D) toluene

Vi
3. Benzene reacts with n-propyl chloride in the presence of anhydrous AlCl3 to give
predominantly
(A) n-Propyl benzene (B) iso-Propyl benzene
(C) 3-Propyl-1-chlorobenzene (D) No reaction
4. Which reaction sequence would be best to prepare 3-chloroaniline from benzene ?
(A) Chlorination, nitration, reduction
(B) Nitration, chlorination, reduction
(C) Nitration, reduction, chlorination
(D) Nitration, reduction, acylation, chlorination, hydrolysis
5. In the chlorination of benzene the catalyst used is

(A) V2O5 (B) Al2O3 (C) FeCl3 (D) Cr2O3
6. Which of the following structures corresponds to the product expected, when excess
of C6H6 reacts with CH2Cl2 in presence of anhydrous AlCl3 ?
(A) (B)
r
(C) (D)
ka
7. Which xylene is most readily nitrated?
(A) Ortho-xylene (B) Para-xylene (C) Meta-xylene (D) All at the same rate
an
8. In the reaction for dinitration,
al
the major dinitrated product (X) is :
(A) (B) (C) (D)

dy
9. Product; Product of this reaction will be :

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(A) (B)
(C) (D)
10. In which of the following cases, the nitration will take place at meta-position?
(A) II and IV (B) I, II and III (C) II and III (D) I only
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11. Chlorination of boiling toluene in presence of light followed by treatment with
aqueous NaOH gives :
ka
(A) ortho-cresol (B) para-cresol
(C) 2,4-dihydroxy toluene (D) benzoic acid
12. Consider the following reactions I and II,
I. II.
anProducts ‘X’ and ‘Y’ are respectively :
(A) picric acid, styphnic acid (B) styphnic acid, picric acid
(C) picric acid, benzoic acid (D) picric acid, salicylic acid
al
13.
The product formed in above reaction is :
dy
(A) (B)
Vi
(C) (D)
14.
‘X’ is
(A) ortho-chlorobenzotrichloride (B) para-chlorobenzotrichloride
(C) meta-chlorobenzotrichloride (D) none of the above
r
15. When is treated with nitrating mixture (HNO3 + H2SO4), we get:
ka
(A) (B)
an(C) (D)
16. In which reaction, polysubstitution takes place?

al
(A)
dy
(B)
(C)
Vi
(D)
Bromination NaNO2 Boiling

17. In the following reaction X Y
HCl
Z
C H OH
 Tribromobenzene, X is :
2 5
(A) benzoic acid (B) salicylic acid (C) phenol (D) aniline
18. In the following reaction,
The structure of major product ‘X’ is :
(A) (B)
r
ka
(C)
(D)
an
19. In the following reaction sequence,
The compounds (X) and (Y) respectively are :

al
(A) (B)
dy
(C) (D)
Vi
Mononitration
20. Dichlorobenzoic acid   Product (only one).
The structure of reactant can be :
(A) (B) (C) (D)
21. The compound that is not a Lewis acid is

(A) BF3 (B) AlCl3 (C) BeCl2 (D) SnCl4
22. Chlorination of toluene in the presence of light and heat followed by treatment with
aqueous NaOH gives
(A) ocresol (B) pcresol
(C) 2,4dihydroxytoluene (D) benzoic acid
23. When nitrobenzene is treated with Br2 in presence of FeBr3, the major product formed
is mbromonitrobenzene. Statements which are related to obtain the misomer are
r
(A) The electron density on meta carbon is more than that on ortho and para
positions.
ka
(B) The intermediate carbonium ion formed after initial attack of Br+ at the meta
position is least destabilised
(C) Loss of aromaticity when Br+ attacks at the ortho and para positions and not at
meta position
(D) Easier loss of H+ to regain aromaticity from the meta position than from ortho and
para positions
24.
an(excess)
(A)
AlCl
 CH2 Cl2 
3
A,A is
(B)
CH2 Cl
al
(C) CH2 (D) CHCl2
25. Chlorination of toluene in the presence of light and heat followed by treatment with
dy
aqueous NaOH gives

(A) o–Cresol (B) p–Cresol
(C) 2, 4–Dihydroxytoluene (D) Benzoic acid
26. Nitrobenzene can be prepared from benzene by using a mixture of conc. HNO3 and
conc. H2SO4. In the nitrating mixture, HNO3 acts as a
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(A) base (B) acid (C) reducing agent (D) catalyst
27. 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 toluene 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
OH

28. OC H
 C2H5I  2 5
Anhydrous (C H OH)

2 5
(A) C6H5OC2H5 (B) C2H5OC2H5 (C) C6H5OC6H5 (D) C6H5I
29. Benzene reacts with excess of chlorine in sunlight to form

(A) Hexachlorobenzene (B) m-Dichlorobenzene
r
(C) Chlorobenzene (D) Benzene hexachloride
ka
30. H C KMnO4
3 CH3 A, A is :
(A) H3C CH3 (B) HOOC CH3
an(C) HOOC
NO2
COOH (D) none of these

al
(A) Although benzene contains three double bonds, normally it does not undergo
addition reaction.
(B) mchlorobromobenzene is an isomer of mbromochlorobenzene.
(C) In benzene, carbon uses all the three p orbitals for hybridization.
(D) An electron donating substitutent in benzene orients the incoming electrophilic
dy
group to the meta position.

(A) Benzene readily docolourises dilute KMnO4 solution.
(B) The inductive effect is the only factor which decides the orientation effects in the
monosubstituted benzene.
(C) The number of isomers of aromatic compound tribromobenzene is four.
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(D) The dipole moment of pnitrotoluene is expected to be larger than

pchloronitrobenzene.

(A) The principal mononitration product of ocresol is 2methyl4nitrophenol.
(B) The carbonhydrogen hemolytic bond dissociation energy for benzene is
considerable smaller than for cyclohexane.
(C) The number of isomers of mononitration of odichlorobenzene is 4.
(D) A tribromobenzene gives two isomers when it is mononitrated. The compound is
1, 2, 4tribromobenzene.

(A) The NH2 group is a better o, pdirector as compared to  NH2COCH3.
(B) The nitrosogroup (N= O) deactivates the benzene ring inductively but is an
ortho and para director due to the donation of the paired electrons on nitrogen.
(C) Benzenewater forms a higher boiling azeotrope.
(D) Though  N(CH3)2 is an orthoand paradirector yet it gives meta nitrated
product with the more powerful electrophilic regent HNO3/H2SO4.
35. Naphthalene is treated with permanganate solution to give
r
(A) Benzoic acid (B) Quinoline
(C) 2-methyl benzoic acid (D) Pthalic acid
ka
36. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with
(A) SO2 Cl2 (B) SO Cl2 (C) Cl2 (D) NaOCl

1. Which of the following reactions will produce benzene ?
an
(A) (B)
(C) (D)
al
(A) Monobromination of ptoluenesulphonic acid followed by treatment with acid and
superheated stream gives mbromotoluene.
O 2N
dy
(B) The mononitration of CH2 gives the product CH2
NO2 NO2
(C) The reactivity towards ring nitration of 2, 4dinitrotoluene is greater than that of
mdinitrobenzene.
(D) The reactivity towards ring nitration of 2, 4dinitrophenol is smaller than that of
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2, 4dinitrochlorobenzene.
3. Toluene, when treated with Br2/Fe, gives p–bromotoluene as the major product
because the CH3 group
(A) is para directing
(B) is meta directing
(C) activates the ring by hyperconjugation
(D) deactivates the ring
4. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with
(A) SO2Cl2 (B) SOCl2 (C) Cl2 (D) NaOCl
Paragraph Type
On the basis of aromaticity, there are three types of compounds i.e. aromatic, non-
aromatic and antiaromatic. The increasing order of stability of these compounds are is
under:
Anti-aromatic compound < non-aromatic compound < aromatic compounds. Compounds

to be aromatic follow the following conditions (according to valence bond theory)
r
(i) The compounds must be cyclic in structure having (4n + 2) e, where
ka
n = Huckel’s number = 0, 1, 2, 3 etc
(ii) The each atoms of the cyclic structure must have unhybridised p-orbital i.e. the
atoms of the compounds have unhybridised p-orbital i.e. usually have sp hybrid or
planar.
(iii) There must be a ring current of  electrons in the ring or cyclic structure i.e. cyclic
structure must undergo resonance.
an
Compounds to be anti-aromatic, it must have 4ne where n = 1, 2... and it must be
planar and undergo resonance. Non-aromatic compounds the name itself spells that
compounds must be non-planar irrespective of number of  electrons. Either it has 4ne
or (4n + 2) electrons it does not matter.
The rate of reaction of any aromatic compounds depends upon the following factors:
(i) Electron density
al
(ii) stability of carbocation produced
Higher the amount of electron density of the ring, higher will be its rate towards aromatic
electrophilic substitution and vice-versa. Similarly, higher will be the stability of the
produced carbocation after the attack of electrophile, higher will be its rate towards
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aromatic electrophilic substitution. There is a great effect of kinetic labelling on the rate of
aromatic electrophilic substitution. As we known that higher the atomic weight or,
molecualr weight, higher will be the van der Waal’s force of attraction or, bond energy.
Since there will be effect of kienetic labelling if the 2nd step of the reaction will be the slow
step, (r.d.s.) otherwise there will be no effect of kinetic labelling.
1. Which of the following is correct order of the rate of reaction of C6H6, C6D6 and C6T6
Vi
towards sulphonation?
(A) Same rate of reactions of C6H6, C6D6 and C6T6
(B) C6T6 > C6D6 > C6H6
(C) C6H6 > C6D6 > C6T6
(D) C6H6 > C6D6 = C6T6
2. Which of the following is the correct order of rate of reaction of C6H6, C6D6 and C6T6
towards nitrations?
(A) C6H6 > C6D6 > C6T6 (B) C6H6 = C6D6 = C6T6
(C) C6H6 > C6D6 = C6T6 (D) C6T6 > C6D6 > C6H6
Benzyne i.e.1,2-didehydro benzene is formed by treating an aryl halide with a base by

the elimination process.
3. Benzyne is a highly unstable intermediate whose structural facts are being laid down.
Mark the correct ones-
r
(A) The triple bond in this structure is complete.
(B) The triple bond is an abnormal -bond formed due to overlap between two sp
ka
hybridized orbitals.
(C) The p-orbitals are outside the plane of the ring.
(D) The triple bond also involves the participation of d-orbitals to some extent.
4. Below given are the random steps/intermediates involved in the formation of the
benzyne intermediate. Mark the correct option which will give the correct orderly
steps.
an A
H
NH 2  
 Br
slow
B

(A) A  B  C D (B) B  C  D  A
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(C) D  A  B  C (D) C  D  A  B
The Birch reduction involves the reduction of alkynes to alkenes. The reagent used in th
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is reduction is Li or Na in liquid NH3 and EtOH. An alkali metal in liquid NH3 is a source of
solvated electron which is responsible for reduction. Even benzene undergoes reduction
by this method.
5. The rate controlled product in Birch reduction of benzene is
(A) (B) (C) (D)

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6. Birch reduction of toluene gives

(A) 50 % yield of 1methyl1, 4cyclohexadiene free from its isomeric 3methyl1,
4cyclohexadiene.
(B) 50 % yield of 3methyl1, 4cyclohexadiene free from its isomeric 1methyl1,
4cyclohexadiene.
(C) 50 % yield of both 3methyl1, 4cyclohexadiene and 1methyl1,
4cyclohexadiene.
(D) 1methylhexaene as the only product.
7. Birch reduction of benzoic acid gives

(A) 1, 4cyclohexadiene1carboxylic acid.
(B) a mixture of 1, 4cyclohexadiene1carboxylic acid and
2, 5cyclohexadiene1carboxylic acid.
(C) 2, 5cyclohexadiene1carboxylic acid
(D) 1cyclohexaene1carboxylic acid.
1. If the groups reinforce each other, there is no problem

For example,
r
ka
2. If an orthopara director and meta director are not reinforcing, the orthopara director
controls the orientation. The incoming group goes mainly to ortho to the meta
director. For example,
an
3. A strongly activating group, competing with a weakly activating group, controls the
al
orientation. For example,
dy
4. When two weakly (or strongly) activating or deactivating groups compete, substantial
amounts of both isomers are obtained for example,
Vi
5. Very little substitution occurs in the sterically hindered position between meta
substituents.
8. Which of the following statements are correct ?

(A) The main product in the electrophilic substitution of mnitrotoluene will occur at
para position to methyl group and ortho position to nitro group.
(B) The IUPAC name of mesitylene is 1, 3, 5trimethylbenzene.
(C) In the mononitration of pnitrobiphenyl , the nitro group

enters in the phenyl.
r
(D) In the mononitration of phenyl benzoate , the nitro group
ka
enters in the phenyl group attached to oxygen atom.
9. The treatment of pH2NC6H4SO3H with bromine in water gives
an (A) (B)
al
(C) (D)
dy
Numerical Type
O
O
O
Vi
1. 6 1
Br2 / FeBr3
Major
5 2
4 3
Bromo substituted product in which Br atom is present at C  ……….
2. Pyridine is treated with chlorine in presence of ferric chloride. 4

3
The incoming electrophile enters into the position.
2
1N
Matrix Match Type
1. Match the Following:

Match a reaction from column-I with appropriate product/s from column-II.
Column I Column II
(Reaction) (Product)
(a) (p)
r
ka
(b) (q)
(c) (r)
an
(d) (s)
(t)
al
dy
Classwork Problems
Subjectives
CH 2 CH 2 CH 2 CH2
1.
Vi
CH 3 Cl CN
(I) (II) (III) (IV)
CH3 is electron donating group, thus increases stability of free radical (I) compared
to (II). Cl and CN are electron withdrawing group, thus decreases the stability of
free radicals. CN is stronger electron withdrawing than Cl as CN exerts both (I) as
well as (R) effect.
CH3 CCl3
CH Cl 3Cl
2. 
3
AlCl
 

2

3
(Friedel Craft's reaction)

Br2/Fe
CH3 CCl3
r
Zn/HCl
 
ka
reduction
Br Br
(m-bromo toluene)
Objectives
an
1. (C) 2. (B)
1. (A), (C) 2. (A) ,(C)

al
Paragraph Type
1. (B) 2. (A) 3. (A) 4. (B) 5. (A)

dy
Numerical Type
1. [1] 2. [2]
Matrix Match Type
1. (A)  (p), (s) ; (B)  (p) , (s) ; (C)  (p) , (r) ; (D)  (q), (s)
Vi
Homework Problems
Subjectives
CH3 CN NHCOCH3
1.
N(CH3)2 OH
r
C(CH3)3
ka
NH2 OH
2.  
 
an

 

In Naphthalene, electrophilic attack occurs preferentially at - position rather than

-position.

COCl CO
| AlCl3
 |
al
COCl COCl
(electrophile)
This electrophile adds to - position to give

dy

(+)
C O C O
Vi
O O Cl
This again in presence of AlCl3 generates the electrophile
and consequently adds to - position of

Naphthalene to give the desired product. Farther the
product undergoes clemenson reduction to given
acenapthene. O O
NO2
3.
(i) (ii) CH2 NO2
NO2
Br
O
O
(iii) C O and C O Br
r
+
ka
N(CH3)3 NH2 NH2
Br
(iv) (v) +
Cl
Br
4.
an COOH
HNO

H SO
3

2 4
COOH
NO2
Sn/HCl
 
COOH
NH2
(i)NaNO /HCl
 2
(0  5C)

(ii)HBF4
COOH
COOH
al
CH3 COOH
K Cr O conc.HNO
6. 
2 2 7
 3
[O] conc.H SO 2 4
NO2
dy
Toluene Benzoic acid m-nitro benzoic acid
Br2
7. C6H5 CH2CH3 
Heat,light
 C H CHCH 
NaCN
 C6H5CHCH3
6 5 3
Br CN
2Phenyl propane nitrile
Vi
OCH3 OCH3
8. A : COO B : COO
C CH2 H2C CH2

O CH2 CH2
CCl3 CCl3
9. (a) (b)
+ CHBr3
Cl Cl
10. Since the compound resists oxidation means it has no hydrogen on benzylic carbon.
C(CH3)3
r
ka
Tert. butylbenzene
Other monosubstituted isomers are
CH3 CH3
an CH2CH2CH2CH3
n butyl benzene
CH CH2CH3
sec. butyl benzene

CH2CHCH3
2 methyl propyl benzene

al
NO2
COOH COOH
11. X= ; Y=
COOH COOH
dy
NHCOCH3 NHCOCH3
12. (a) C6H5 H C6H5 C6H5 (b) Br
C C + C C +
H C6H5 H H
(Major product)
Vi
Br
13. (a) C6H5 H C6H5 C6H5 (b) NHCOCH3 NHCOCH3

C C + C C Br
H C6H5 H H +
(Major product) Br
Objectives
1. (D) 2. (B) 3. (B) 4. (B) 5. (C) 6. (D)

7. (C) 8. (A) 9. (C) 10. (B) 11. (D) 12. (A)
13. (A) 14. (C) 15. (A) 16. (B) 17. (D) 18. (B)
19. (B) 20. (B) 21. (C) 22. (D) 23. (A) 24. (C)
r
25. (D) 26. (A) 27. (A) 28. (A) 29. (D) 30. (C)
31. (A) 32. (D) 33. (A) 34. (C) 35. (D) 36. (C)
ka
1. (A), (B), (D) 2. (A), (B), (D) 3. (A), (C)

4. (A), (C)
an
Paragraph Type
1. (C)
7. (C)
2. (B) 3. (C)
8. (A), (B), (C), (D)
4. (C)
9. (D)
5. (B) 6. (A)
Numerical Type
al
1. [3] 2. [3]
Matrix Match Type

dy
1. (A)  (q) ; (B)  (r), (t) ; (C)  (p), (s) ; (D)  (q)
Vi
MODULE 4
Role of protecting gr :
NH2 NHCOCH3 NHCOCH3 NH2
CH COCl NO  
 
3

2
H3O
NO2
r
NO2
NH2 O OH
ka
HNO [O]

3 
[O]
O
Role of Blocking Reagent :
an
CH3
Me3CCl/AlCl3


CH3
NO 2
 
CH3
NO2


dil.HClAlCl3
 (CH3 )3 CCl
CH3
NO2
CMe3 CMe3
al
Ipso Substitution :
SO3H SiMe3
H
H /H O H /HClO

2
 + H2SO4 ; 
4

dy
OH OH
C(CH3)3
AlCl /HCl

3
 + CH3 C CH2
CH3
Vi
Elimination  Addition Cine  Substitution :

X NH2
NaNH

NH
2

3
NH2 NH2 /NH3
X

X
 
OMe OMe OMe

Li
Phli H O

 
2 
Ph
Ph
OMe OMe OMe

X

r
NaNH NH

2
 
2

NH2
ka
(more stable)
NH3
OMe
an NO2
X
NaNH
NO2 (major)
NH2

2

al
NH2
NO2 NO2
NH2 NH2
dy
NH3


(major) (more stable)
ArSN2 (Aromatic Substitution Nucleophillic Bimolecular)

Cl OH
Vi
OH

300C/1520cm Hg

Cl OH

OH

200C

NO2 NO2
Cl
OH
NO2
NO2
OH

100C

NO2
NO2
Cl OH
O2N NO2 O2N
r
NO2
OH

25C

ka
NO2 NO2
Cl OH OH OH OH
Cl Cl
Cl
OH
   
an  /P

(  Complex)
 Cl

Cl OH OH
Cl Cl OH
al
OH
   Cl

NO2 N
N
dy
NO2
O O O O
Meisenheimur Complex
NO2 OMe
Br Br Br Br
Vi
OCH

3


NO2 NO2

PhLi

110C
 (Chichibabin Reaction)

N N Ph
NO2
CN
 alc.KCN
  (Von Ritcher Reaction)
Br Br
ArSN 1 :
+
r
NH2 N2Cl OH
ka
NaNO
 2
HCl/C
 boiling
 
H O 2
SO2Cl CN
HCN/CuCN
SO /CuCl

2 2

an NO2

NaNO
Cu O
2
 
2
2 2 HBr /Cu Br
Br
F
al
H PO HBF

3 2
 
4
Some Important Reaction


dy
Wurtz Fittig Reaction :
ether
Br2NaBrCH3  CH3  2NaBr
Bromobenzene Toluene
Vi
CH3 CH3
Soda lime
 NaOH  

Toluene
COONa
CH3 CH3
OH
heat
  Zn  
Toluene
CH3 CH3
r
ka
boil
  HOH  
Stean
Toluene
SO3H
CH3 CH3 CH3

an 
NaNO
HCl
2

C H OH

2 5
Toluene
NH2 N2Cl
CH3
al

Cr O / Al O
CH3  (CH2 )7  CH3 
2 3 2 3

 500  550C at 150 atm
CH3
dy
H3C
Mesitylene
CH3 CH3
Cl

 Cl2 +
CH3
Vi
 AlCl3

 Cl
CH2Cl CHCl2 CCl3
Cl2
h
Cl2 Cl2

h

h
Benzyl Benzal Benzo

chloride Chloride Chloride
CH 3 COOH CH 2 CH 3

 KMnO /H  KMnO /H 

   
4  [O
4
]

[O ]

H 3C CH 3
H KMnO4
C KMnO4 CH CH 2
OH
[O]
r
Etard Reaction :
ka
CH3 CHO
CrO Cl

2 2
 [O]
Ulmann Reaction :

anCH2CH2CH3
Br  2Cu  Br
2Cl

CH2CH2CH3

2
h

Cl


CHClCH2CH3
Alc.KOH

Heat

 Cu2Br2
CH CH CH3
 FeCl 3
Cl
al
Cl Cl
Benzene diazonium chloride is obtained from benzene, nitrobenzene or aniline as follows:


N2 Cl
NO2 NH2
HNO Sn NaNO
 3
    2
dy
H SO
2 4 HCl HCl, 0C
Benzene Nitrobenzene Aniline Benzene diazonium

Cl
chloride
CuCl/HCl

Heat

Chlorobenzene

N2 Cl Br
Vi
CuBr /HBr

Heat

Bromobenzene
Benzene diazonium I
chloride
KI

Heat

Iodobenzene
F
NaBF

Heat
4

Fluorobenzene
Synthetic Route Map for Aromatic Compounds
SO3H OH
conc. H2SO4 H2O/he OH
NO2 NH2
r
Sn/HCl N
ka
HNO3
fuming
N 2 Cl N
Cl
NaNO2/HCl coupling
Cl2/FeCl3 5 C with phenol
CuCl . dil HCl
an CH3X
AlCl3
CH3
dil. KMnO4/OH
KCN
CN
H+/H2O
COR Cl2/hv
al
CH2Cl CH2OH CHO COOH
AlCl3
RCOCl
aq. [O] [O]
chromic KMnO4
acid (dil)
dy
Cl2/hv
CH2Cl2
Cl2/hv
Vi
CCl3
OH aq.
Solved Examples
1. Why does phenol form o-hydroxybenzene sulphonic acid at 15-20C but

p - hydroxybenzene sulphonic acid at 100C?
Solution :
o-position has spatial congestion but p-position is free from this. The reaction at
o-position is kinetically controlled; it occurs at a low temperature. At an elevated
temperature the spatial congestion increases and the bulky SO3H group leaves the
r
substrate and it attacks the p-position which give rise to thermodynamically stable
ka
product. Thus, the latter reaction is thermodynamically controlled.
2. 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).
an
Solution :
(A) is
CH2CH3
while (B) is
CH3
CH3
al
CH3 COOH CO O
CH3 COOH CO
 [O] 

H2 O
dy
CH2CH3 COOH

[O]
Vi
(A) (Benzoic acid)
Classwork Problems
Subjectives
1. Convert Toluene to 2methyl 5 chlorobenzoic acid.
CH3
fumingH SO CH Cl AlCl dilH SO

2. 
2 4
 X 
3 3
 Y 
2 4
 Z.
r
Objectives
ka
Oxidation NaOH Sodalime
1. In the reaction C6H5CH3   A   B   C, the product C is
(A) C6H5OH (B) C6H6 (C) C6H5COONa (D) C6H5ONa
2. The major product of the following reaction,
an
al
(A) (B) (C) (D)
dy

1. Oxidation of (A) gives para benzoquinone (A) is :
Vi
(A) (B) (C) (D)
2. Find out correct statements regarding nucleophilic aromatic substitution reaction :

(A) There should strong electron withdrawing group at ortho and para position with
respect to leaving group
(B) Nucleophilic atom should be of N, S, O, etc.
(C) Rate of reaction is fastest with fluoro derivative
(D) All are incorrect.
Paragraph Type
Using the following paragraph, solve Q. 1 to 3
For a typical nucleophilic aromatic substitution reaction to take place.
1. Nucleophilic atom should be of Oxygen, Nitrogen or Sulphur
2. Leaving groups should be halide.
3. There should be strong electron withdrawing group at ortho and para position to
leaving group.
r
ka
1. Fastest nucleophilic aromatic substitution reaction take place in :
an
(A) (B) (C) (D)
2. Find out correct product of following reaction :

al
dy
(A) (B) (C) (D)

Vi
3. Compare rate of nucleophilic aromatic substitution reaction in following reactants :
(A) S > Q > P > R (B) R > S > P > Q (C) S > R > P > Q (D) P > S > R > Q
Numerical Type
1. The number of reagents are used for given conversion

NH2 OH
NO2
r
ka
OH
COOH
2. . In the product, how many Br  atoms are present ?
Br /H O

2 2
Product
Matrix Match Type

an
1. Match the following :
Column I Column II
(Reactions) (Intermediates in the reaction)
(A) (p) Carbocation
al
(B) (q) Carbanion
dy
(C) (r) Carbene

Vi
(D) (s) Enol
Homework Problems
Subjectives
1. What would be the major product in each of the following reactions ?
O
F
NaOCH Br /Fe(1e.q.)
(i) 
3
(ii) N 
2

r
D
NO2
ka
Objectives
1. Which undergoes hydrolysis most easily?
an
(A) (B)
al
(C) (D)
dy
2. The following sequence of reactions on ‘A’ gives :

Vi
(A) (B) (C) (D)
3. When benzene sulphonic acid and pnitrophenol are treated with NaHCO3, the
gases released respectively are :
(A) SO2, NO2 (B) SO2, NO (C) SO2, CO2 (D) CO2, CO2
4. The reaction
is an example of :
(A) Wurtz reaction (B) Williamson reaction
(C) Ulmann reaction (D) Witting reaction
5. The reaction of with HBr gives predominantly :
r
ka
(A) (B)
an
(C)
C(CH3)3
(D)
KMnO4
  product (formed under vigorous oxidation) is
al
6. 
(A) Benzoic acid (B) (CH3)3CCOOH

(C) Both are correct (D) None of these
7. In the reaction of p–chlorotoluene with KNH2 in liq. NH3 the major product is :
dy
(A) o–toluidine (B) m–toluidine (C) p–toluidine (D) p–chloroaniline
8.
Vi
‘A’ and ‘R ’ are :
(A) ,elimination addition (B) ,elimination addition
(C) ,nucleophilic substitution(D) none of the above
9. The alongside reaction proceeds through :

(A) electrophilic addition
(B) benzyne intermediate
(C) activated nucleophilic substitution
(D) oxirane
10. An aromatic compound C7H6Cl2 (A), gives AgCl on boiling with alcoholic AgNO2
solution and yields C7H7OCl on treatment with sodium hydroxide. (A) on oxidation
gives monochlorobenzoic acid. The compound (A) is :
r
(A) (B) (C) (D)
ka
11. Reactivity order of following towards NaOEt, EtOH :
(A) III > II > I
(B) II > I > III
(C) I > II > III
an
(D) III > I > II
COOH
Li/NH (  )
12. 
3 Majorproduct
al
COOH COOH COOH COOH
(A) (B) (C) (D)

dy

1. Which of the following can be prepared by Reimer-Tiemann reaction directly ?
(A) (B) (C) (D)

Vi
2. Identify the compounds that will easily undergo nucleophilic aromatic substitution
reaction :
(A) (B) (C) (D)
Paragraph Type
ArX + Nu  ArNu + X
For this reaction to take place, there should be strong electron withdrawing groups such

as NO2,CF3, N H 3 etc., at ortho or para or at both the positions at the benzene ring.
r
1. Let us consider the following reactions :
ka
(i)
an
(ii) OC2H5
NO2
al
NO2
NO2
(iii)
dy
NO2
NO2
Where T1, T2, T3 are temperatures while P1, P2, P3 are pressures. Select the correct
one.
Vi
(A) T1 is the lowest temperature and P3 is the highest pressure.

(B) T3 is the highest temperature and P3 is the lowest pressure.
(C) T2 is the lowest temperature and P2 is the lowest pressure.
(D) T3 is the lowest temperature and P3 is the lowest pressure.
2. Aromatic nucleophilic substitution reaction is

(A) A bimolecular first order reaction
(B) A bimolecular second order reaction
(C) An unimolecular first order reaction
(D) An unimolecular second order reaction
3. Which of the following compound will undergo aromatic nucleophilic substitution

reaction most easily ?
(A) (B) (C) (D)
r
Numerical Type
ka
CH2COOH CH3
Br
1. , no. of steps used in this reaction are ………..
OH N2Cl
2.
an + Hydroxy substituted azobenzene. The position
of OH in azobenzene is at C 
OH
al
3. CxHy Oz . What is value of z ?
CrO2Cl2

dy
NO2 NO2 NO2 NO2

1
2 Br NH2
NaNH2 NH2 
4. +
3

4 NH2
Vi
In the product, the negative charge is more stable at C  ……….
NO2
5. (NH4)2 Sx Product. (C6N3HxOy). What is the value of x ?
O 2N NO2
NO2
Br Br
OCH3
6. Product. (CxHyNzOmBrn). What is the value of x ?
NO2
NO2
r
4
3 alc.KCN
7. Product. In the product, the  CN group is present at C 
ka
2
1
Br
Matrix Match Type
an
1.
(A)
Column I

1.CH ClAlCl
3 3
2.Cl Sunlight
2

(p)
Column II
3.aq.KOH

al
(B) (q)
1.C H ClAlCl

2 5
2.Br Fe
3

2
3.Cl2 hv
4.alc.KOH
dy
(C) (r)
1.CH3ClAlCl3



2.HNO 3 H2 SO 4
3.Cl2 hv
4.C6H6 AlCl3
Vi
(D) (s)
1.CH3 ClAlCl3

2.Cl2 hv
3.KCN
4.H3 O 
2. Column I Column II
(A) (p)
1.CH3 COClAlCl3

2.CH3MgI

3. 
4.H2 O/ 
5.H2 /Ni
(B) (q)
1.CH3 ClAlCl3 
 
r
2.Br2 Fe
3.KMnO4
ka
(C) (r)
1.CH ClAlCl 

3
2.KMnO
3

4
3.Br2 Fe
(D) (s)
 CH2 CH2
1.HF
an
2.Br2 heat
3. alc. KOH
4.Br2 CCl4
5.alc.KOH
6.NaNH2
7.CH3I

al
(A) (p)
1.CH3 ClAlCl3

2.Br2 /Fe

3.Cr2 O3 / Ac 2 O
4.H2 O /H
dy
(B) (q)
 /Fe
1.Br

2
2.Mg

3.CH2 CH2 
4. C5H5NH CrO3Cl

Vi
(C) (r)

2. HNO3 H2 SO4 (dinitration)

3.Cl2 heat(dichlorination)
Aq.NaOH
(D) (s)
1.CH ClAlCl

3 3
2. CrO Ac O

3 2

3.NaCN NaHSO 3
 
4.H 2O H
(A) (p)
 2 Fe
1.Br

2.Mg

3.CH3 CHO
4.HCl,Mg
5.CO2
(B) (q)

2.Br2 Fe

3.Mg
r
4.CO 2
(C) (r)
ka

3
2.KMnO
3

4
3.Cl2 Fe
(D) (s)

2.Cl2 Fe

an
5.
3.KMnO 4
Column I Column II
(A) (p)
al
 1.CH COClinpyridine

3
2.HNO H SO

3 2 4
3.H3 O 
dy
(B) (q)
 H O
1.Br
2 2
2.NaNO /HCl

2
3.H3PO2 /H2 O
(C) (r)
Vi
1.HNO3 /H2 SO4 80C


2.Sn/HCl


3.NaNO 2 /HCl0  C
4.CuCl
(D) (s)

3
2.KMnO
3

4
3.Br2 Fe
4.SOCl2
5.NH3
6.Br2 /KOH
(A) (p)

2.CrO3 Ac 2O


 2OH
3.H

4.HNO 3 /H2SO4 0C
5.SnCl2 /HCl

6.NaNO 2 /HCl0C
 2OH
7.H
(B) (q)

1.HNO /H SO
 3 2 4
(X)
r
2.Sn/HCl
ka


3
2.KMnO
3
(Y)
4
3.SO2Cl
Pyridine
XY 
(C) (r)

3 3

an 
2.HNO H SO
 H
3.Fe
3
4.(CH3CO)2 O
 2
5.Br
 2OH
6.H

7.NaNO
 3PO2
8.H
2 HCl
2 4
(D) (s)

1.HNO 3 H2 SO 4
 
al
 2 Fe
2.Br
3.SnHCl

4.NaNO 2 HCl
 2OH
5.H
dy
(A) (p)
1.(CH CO) O

3 2
2.HNO H SO

3 2 4
3.H2 OH
Vi
4.Br2 CH3 COOH

5.NaNO2 ,HClCuBr
6.Sn,HCl
7.NaNO2 ,HClH3PO2
(B) (q)


3
2.HNO
3
H SO

3 2 4
 2 Fe
3.Br
  
4.Fe,H
(C) (r)


3
2.HNO
3
H SO

3 2 4
  
3.Fe,H
 2 Fe
4.Br
(D) (s)

3 3

r

2.HNO H SO
3 2 4
  
3.Fe,H
4.(CH3CO)2 OPyridine
ka

5.KMnO 4 warm

6.HNO 3 H2 SO4
 2OH
7.H
(A) (p)
an 1.H


2.NaNO /HBF

3.NaNO2 Cu
4.I 2 /HgO
2 4
(B) (q)
 
al

2.HNO 3 H2 SO4
3.Cl2 heat
 3
4.NH
 H
5.Fe
(C) (r)
dy

1.NaOH

2.CO 125C,47atm

2
 
3.H
4.(CH3CO)2 O
5.CH3COOH
(D) (s)
 SO
1.H

2 4

Vi

2.NaOHfuse
 
3.H
(A) (p)
1. 2H2SO4 (di sulphonation)




2.HNO 3 H2 SO4

 2O,H
3.H  heat
(B) (q)
r

1.HNO 3 H2 SO4

2.Cl 2 Fe

ka
(C) (r)
1.Cl Fe


2
2.HNO H SO

3 2 4
(D) an 
 Fe
1.Br

2
2.HNO H SO
3
 2 Fe
3.Br

2 4
(s)

al
(A) (p)

2.Cl2 Fe

3.Cl2 heat
4.aq.KOH

dy
(B) (q)

 HNO3 H2SO4
2.
3.CrO3 (CH3CO)2 O
4.H 2OH2SO4
(C) (r)
1.Sn/HCl[H]
Vi


2.NaNO /dil.HCl273  278K

2

3.KCN
 
4.H
 3 heat
5.NH
(D) (s)

1.HNO H SO
 3
  Br 
2.Fe
2 4

2
 H
3.Fe

4.HNO 2
 3PO2
5.H

(A) (p)

1.HNO H SO

3

2 4

 H
2.Fe
3.2Br2

4.HNO 2
 3PO2
5.H
(B) (q)

1.HNO 3 H2 SO 4
 
r
2.SnHCl
3.(CH3CO)2 OPyridine

4.HNO 3 H2 SO4
 2OH
ka
5.H

6.HNO 2
 3PO2
7.H
(C) (r)

1.HNO 3 H2 SO4

 2 Fe
2.Br

3.SnHCl

4.NaNO 2 HCl
5.CuBr
an
(D)


1.NaNO

2

/HCl5C
2.Cl /CuCl
(s)

al
(A) (p)

1.KMnO


2.NH
4
heat

3
 2O5 heat
3.P
(B) (q)
dy

1.HNO 3 H2 SO 4

 2 Fe
2.Br

3.SnHCl

4.NaNO 2 HCl0C
5. KI
(C) (r)
Vi
1.[O]KMnO
 4
2.sodalim e / 

(D) (s)
 hv
1.Br


2
2.KCN

 3O
3.H

(A) (p)

1.NaNO /dil.HCl273  283K

2.CuCN
2

 2 /Ni
3.H
(B) (q)
r

1.HNO  SO
.H

3 2 4

ka

2.NaOCH 160C
3
 2 .Pt
3.H

4.NaNO 2 .HCl5C
  H2O
5.H
(C) (r)

1.HNO H SO
 
(D)
an 3
2.Sn/HCl
2 4
3.(i)NaNO2 /HCl
0C5C
(ii)HBF
(s)

1.HNO /H SO 100C

3 2 4

al
2.(NH ) S 100C
4 2 x

3.NaNO 2 /dil.H2SO4
0C5C
4.H 2O( N2 ),H
 2SO4

dy
O
O
C
CH C AlCl3
(A) + O O (p)
CH C C
O O
Vi
(B) + CH3COCl C 6H 5 C CH3 (q) CHCl3  aq.NaOH

O
CH3
(C) Ph CH C Ph COOH (r) KMnO4
CH3
OH OH
(D) (s) Heat
CHO
Classwork Problems
Subjectives
CH3 CH3 CH3

Br
1. Cl

2
Fe
 

Br2 /Fe
r
Cl Cl
ka
Mg/ethen
CH3 CH3
COOH
Mg Br
CO

2

H3 O
an Cl
(C  Br is more reactive than C  Cl)
Cl
CH3 CH3 CH3 CH3

CH3 CH3
al
formingH2SO4 CH3 Cl dilH2SO4
2.   
AlCl
 
3
SO3H SO3H
dy
Objectives

1. (B) 2. (A)

1. (A), (B), (C) 2. (A), (B), (C)
Vi
Paragraph Type
1. (A) 2. (B) 3. (C)
Numerical Type
1. [5] 2. [3]
Matrix Match Type
1. (A)  (q), (r) ; (B)  (p), (s) ; (C)  (q) ; (D)  (p)
Homework Problems
Subjectives
O
OCH3 ||
1. (i) (ii) N Br
NO2
r
Objectives
ka
1. (A) 2. (C) 3. (D) 4. (B) 5. (A) 6. (B)
7. (B) 8. (C) 9. (B) 10. (A) 11. (A) 12. (B)
an
1. (A), (B), (C)
Paragraph Type
1. (D) 2. (B)
2. (A), (C), (D)
3. (D)
Numerical Type
1. [3] 2. [4] 3. [2] 4. [3] 5. [5] 6. [7]
al
7. [3]
Matrix Match Type

1. (A)  (r) ; (B)  (p) ; (C)  (s) ; (D)  (q)
dy
2. (A)  (q) ; (B)  (s) ; (C)  (p) ; (D)  (r)

3. (A)  (r) ; (B)  (p) ; (C)  (q) ; (D)  (s)
4. (A)  (s) ; (B)  (p) ; (C)  (q) ; (D)  (r)
5. (A)  (q) ; (B)  (s) ; (C)  (p) ; (D)  (r)
6. (A)  (r) ; (B)  (p) ; (C)  (s) ; (D)  (q)
7. (A)  (s) ; (B)  (r) ; (C)  (q) ; (D)  (p)
Vi
8. (A)  (r) ; (B)  (p) ; (C)  (s) ; (D)  (q)

9. (A)  (r) ; (B)  (s) ; (C)  (p); (D)  (q)
10. (A)  (r) ; (B)  (s) ; (C)  (p); (D)  (q)
11. (A)  (s); (B)  (r); (C)  (q); (D)  (p)
12. (A)  (q) ; (B)  (s) ; (C)  (p); (D)  (r)
13. (A)  (s) ; (B)  (r) ; (C)  (q) ; (D)  (p)
14. (A)  (s); (B)  (p); (C)  (r); (D)  (q)


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Aromatic Compounds

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IIT - 2022 : Chemistry

Ch. 17 : Aromatic Compounds

Furan Thiophene Pyrrole Pyridine Pyrimidine

(b) Benzene forms a triozonide.

Hobserved = 55.6 k cal/mole

Hobserved = 49.8 k cal/mole

Difference (Resonance energy) = Hcalculated  Hobserved

Benzene is aromatic since ring is planar, there is complete delocalization of  electrons

Delocalization taking place.

Cyclopropenyl anion Cyclopentadienyl cation

Cycloheptatrienyl anion Cyclooctatetraene

• Aromaticity is shown by 1, 3  cyclopentadienyl anion but not by 1, 3  cyclopentadiene.

6e, Non planar Cyclopentatrienyl cation

1. Decarboxylation of Sodium benzoate

Sodium benzoate Benzene

3. From chlorobenzene : Chlorine of the benzene nucleus can be substituted by

and NaOH or absolute ethyl alcohol or hypophosphorus acid (H3PO2 ) .

+ HNO2 + HCl + 2H2O

Aniline Benzene diazonium

+ C2H5OH + N2 + HCl + CH3CHO

3. Write IUPAC names of the following compounds :

(a) CH2 CH2 CHCH2 (b) OH

4. Explain why the following systems are not aromatic ?

(i) CH2 (ii) (iii)

(iii) Cyclooctatetraene is not planar but is tub-shaped.

5. How would you convert the following compound into benzene ?

Ethene 1, 2, Dibromoethene Vinyl bromide Ethyne Benzene

Hexane Cyclohexane Benzene

1. How can you convert Ethylbromide to benzene.

2. Convert cyclohexanol into cyclohexa1, 3, 5triene.

(A) (B) (C) (D)

Multiple Correct Answer Type

1. Benzene can be obtained by

2. Benzene can be prepared by

(B) reduction of benzyl chloride with Ni-Al alloy and NaOH

Using the following Paragraph, solve Q. 1 & 2

1. Which of the following is aromatic?

2. Which of the following is nonaromatic?

Matrix Match Type

(C) (r) Nonaromatic

(D) (s) Dipolar

1. 7  Bromo  1, 3, 5  cycloheptatriene exists as ionic compound while 5  bromo  1,

2. How can you prepare benzene from lime ?

Single Correct Answer Type

1. Oil of vanilla bean is :

(A) (B) (C) (D)

(A) (B) (C) (D)

3. The bond order of individual carbon-carbon bonds in benzene is

6. Hybridization of nitrogen atom in pyridine is:

(A) sp3 (B) sp2 (C) sp (D) sp3d

Multiple Correct Answer Type

1. An aromatic molecule will

2. Which of the following is/are aromatic?

3. Choose the compounds below that are aromatic :

(A) (B) (C) (D)

(A) (B) (C) (D)

6. Dipole moment of which compound is not zero ?

(A) (B) (C) (D)