ALLEN Aromatic Compounds 1

AROMATIC COMPOUNDS
q INTRODUCTION
Aromatic hydrocarbons are known generally as arenes. An aryl group is one derived from an
arene by removal of a hydrogen atom and its symbol is Ar—. Thus, arenes are designated ArH
just as alkanes are designated RH.
q SOME IMPORTANT AROMATIC COMPOUNDS

Cl

1. 2. 3.
Benzene Chlorobenzene Toluene

SO3H NH2
4. 5. 6. O

Benzene sulphonic Aniline Benzaldehyde

acid

COOH CONH2 COCl

7. 8. 9.
Benzoic acid Benzamide Benzoyl chloride

N
CN OH Nº
10. 11. 12. Cl

Benzonitrile Phenol Benzene

diazonium salt

NO2
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13. 14. 15.

Niterobenzene o-Xylene m-Xylene

O
16. 17. 18.

p-Xylene Anisole Styrene

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2 JEE-Chemistry ALLEN

NH2
19. 20. 21.
NH2
o-Toluidine m-Toluidine
NH2
p-Toluidine

O O
22. 23. 24.
NH
Acetophenone Acetophenone
Acetanialide
Cl
Cl O
Cl
Cl Cl
Cl NH
25. 26. 27.
Cl Cl Cl S
Cl Cl O O
DDT BHC Saccharin
(Dihlorodiphynl trichloroethane) (Benzene Hexachloride)

O
O
NHCOCH3
O O–C–CH3
28. 29. 30.
COOH
OH
HO OH
Phenolphtlalein Aspirine Paracetamol
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O
OH
C–OCH3 OH
31. 32. 33.
OH CH3 CH3
Oil of wintergreen o-Cresol m-Cresol

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 ALLEN Aromatic Compounds 3

OH OH

34. 35. 36.

Napthalene a-napthol
CH3
p-Cresol

OH
37. 38. 39.
b-napthol Anthracene
Phenonthracene

N
40. 41. S 42.
Thiphene H
Phenonthracene Pyrole

COOH

43. O 44. N 45. COOH

Furan Pyridine Pthalic acid

OH
OH OH
OH
46. 47. 48.
OH
OH
Catechol Resorcinol Quinol

OH
NH2
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O2N NO2 O2N NO2

N N
49. 50. 51. NH2
NO2 H2N N
NO2
TNT Picric acid Melamine

OH COOH

52. COOH 53. 54.

Salicylic acid Cinnamic acid Mesitylene

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4 JEE-Chemistry ALLEN

q REACTION OF AROMATIC COMPOUNDS

(A) Electrophilic substitution reaction :

E
+d –d catalyst
+ E–A + A– H

(1) General Mechanism for electrophilic Aromatic substitution :

+ E E E E
(slow) H H H H
Step I
+ º +
+

Arenium ion (s -complex)

+ E E
H (Fast)
+H–A

E
ˆˆˆˆ† K1 H + : A– (Slow step)
Step I ‡ˆˆˆ
K
ˆ +
-1

Arenium ion (s -complex)

E E
+ H k2 +E–A (Fast step)
Step II – ¾¾¾
®

d+
d+ d+
E H
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1 d+
+ E H
2
Potential Energy

E H

¹
DG1
¹ DG 2

E–A
E–A

Reaction coordinate
(Figure-1)

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 ALLEN Aromatic Compounds 5

The effects of various substituents on the reactivity of a benzene ring toward electrophilic
substituion:
Strong activating groups : —NH2, —NHR, —NR2, —OH, —OR.
O O
Ortho/para
Moderately activating groups : — NHCR , — OCR , directing
Weakly activating groups :—R, —Ar, —CH=CR2
Weakly deactivating groups :—F, —Cl, —Br, —I

Moderately deactivating groups : —CHO, —COR, —COOR,

—COOH, —COCl
+ + Meta
Strong deactivating groups : —CºN, —SO3H, — N H3 , — N H2R , directing
+ +
— NHR 2 , — NR3 ,—NO2
q NITRATION
Nitration reaction is generally carried out with a mixture of concentrated nitric acid and sulphuric
acid. The reagents which is used for nitration are called nitrating agents.
Other nitrating agents which are commonly used are :
(a) N2O5 in CCl4 in the presence of P2O5 is used when anhydrous conditions are required.
(b) Ethyl nitrate (C2H5ONO2) is used to carry out nitration in alkaline medium.
(c) In the case of polycyclic hydrocarbons N2O5 and nitronium salts such as NO2+ BF4– , NO2+ PF6– ,

NO2+SO3– , can be used.

The electrophile involved in nitration reaction is nitronium ion ( NO 2 ) .

Å

Mechanism :
Generation of electrophile from nitrating agent.
Step 1 :
(a) In a mixture of nitric acid and sulphuric acid an acid base reaction takes place in which nitric
acid acts as the base.
Å
HO–NO2 + H2SO4 H–O–NO 2 + HSO4
Base
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Å Å
H– O – NO2 NO2 + H2O

Å
H2O + H2SO4 H3O + HSO4
Å Å
HNO3 + 2H2SO4 NO2 + H3O + 2 HSO4
(b) N2O5 in CCl4 when used, results in a spontaneous dissociation reaction.
Å
ˆˆ† N O 2 + NO 3-
N 2 O 5 ‡ˆˆ

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6 JEE-Chemistry ALLEN
(c) With concentrated HNO3 alone
ˆˆ† NO2Å + NO3- + H 2 O
2 HNO3 ‡ˆˆ
The electrophile generated in this case is obtained by the behaviour of one nitric acid as the
base and other molecule as the acid, but the equilibrium lies in the reactant side.
Step 2 :
Attack of electrophile on aromatic System :

Å
H Å NO2 NO 2 NO2 NO2
NO2
H H H + H
Slow Å Å

Step 3 :
Transfer of Proton to a base/nucleophile
NO2 NO2
Fast
+ H + Nu –H+ + Nu–H

KEY POINTS:
l In nitration, electrophile is NO2+
l Conc. (H2SO4 + HNO3) is known as nitrating mixture.
l In nitrating mixture (HNO2) work as bronsted base and H2SO4 as bronsted acid.

q SULPHONATION
Sulphonation is another synthetically important reaction. It is often accomplished with concentrated
sulphuric acid or fuming sulphuric acid containing excess of SO3 or chlorosulphonic acid,
ClSO2OH.
H2 SO4 (SO3 + H2O) or H2S2O7)

ˆˆˆ†
2H2SO4 ‡ˆˆ – +
ˆ HSO4 +H3O + SO3
O H SO3 SO3H
SO3 ˆˆˆˆˆˆˆ †
ˆˆˆˆˆ† ˆˆˆˆˆˆ †
II,Slow
‡ˆˆˆˆˆˆ ˆ
K1 (Slow) III,(fast )
+ S ‡ˆˆˆˆ
k -1
ˆ + –
HSO 4 , - H 2SO4 ‡ˆˆˆˆˆ
H 3O+ ,- H 2O
ˆ
O O
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Potential Energy

–
H SO3
+
–
SO3
+ SO3 +H
+

Reaction coordinate
Figure-2

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 ALLEN Aromatic Compounds 7

KEY POINTS:
l In sulphonation, SO3 is electrophile.
l ClSO3H in CCl4 can also be used for sulphonation in some cases.
l Kinetic isotopic effect occurs here on rate of reaction. Hence benzene reacts more fast than C6D6
than C6T6.

q HALOGENATION
Halogenation is catalysed by a Lewis acid like AlCl3, or FeCl3, Reactivity of halogens has the
following order,
I2 < Br2 < Cl2
Let us take chlorination as a representative reaction to understand the mechanism of halogenation.
Chlorine, in the presence of AlCl3 or FeCl3 forms a complex, Cl2—AlCl3. This complex can itself
be the reactive electrophile or it may dissociate to give Cl+.
Å
Step 1 : Cl—Cl + AlCl3
••
Cl—Cl — AlCl3
• •

(anhydrous)

H Cl
Å
Å
Step 2 : + Cl — Cl— AlCl 3
slow + AlCl4

Cl H Cl

Step 3 : Å
+ AlCl4
Fast
+ AlCl3 + HCl

H Cl---Cl-AlCl3
+
H Cl
+
Potential Energy

intermediate
H Cl
+–
+ AlCl4

reactants

+ Cl2—AlCl3 Cl products
+ HCl + AlCl3

Reaction coordinate
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Schematic potential energy diagram for chlorination

of benzene with Cl2, AlCl3 as the electrophile
(Figure-3)

FRIDEL-CRAFT'S ALKYLATION

R
AlCl3
+R — X + HX

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8 JEE-Chemistry ALLEN
Mechanism for the Reaction :
Cl Cl
H 3C H 3C H3C
•• + Å
Step I : CH–Cl
••
• +
• Al CH—Cl—Al—Cl CH + AlCl4
H3 C Cl Cl H3C H3C
Cl
Å CH3
Å CH3
Step II + HC other canonical forms
CH3 H CH3

Å
Cl
CH3 CH3
Step III : + Cl—Al—Cl + HCl + AlCl3
H CH3 CH3
Cl
Some examples of Friddel-Craft's Alcylation :

anhy.
+ CH3Cl AlCl anhy.
1. 3
2. +
Cl AlCl3
(Toluene)

anhy.
3. + Cl AlCl 4. Cl anhy.
3 + AlCl3
(Cumene)

Cl ZnCl2 anhy.
5. + 6. + Cl AlCl3

anhy. anhy. Cl
7. + AlCl3 8. + CH2Cl2 AlCl
3

Cl
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anhy. anhy.
9. + CH2Cl2 AlCl 10. + CHCl3 AlCl
3
3

3:1

Cl
anhy. anhy.
11. + CCl4 AlCl3 Ph3C–Cl 12. AlCl3

Cl
anhy. Cl anhy.
13. AlCl3 14. + Cl AlCl3
bring

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 ALLEN Aromatic Compounds 9

anhy. anhy. AlCl3

15. + CH3Cl AlCl3 + 16. + CH3Cl D

m-xylene
(most stable)
NO2 NH2
anhy. AlCl3 anhy. AlCl3
17. + CH3Cl D No reaction 18. + CH3Cl D No reaction

FRIEDEL-CRAFTS ACYLATION
The reaction where an acyl group is introduced into an aromatic compound compound is called
an acylation reaction.
The Friedel-Crafts acylation reaction is an effective means of introducing an acyl group into an
aromatic ring. The reaction is often carried out by treating the aromatic compound with an acyl
halide.

O
O C CH2–CH3
+ C H3
Cl ¾¾¾ ®
AlCl 3

+ HCl

Friedel-Crafts acylations can also be carried out using carboxylic acid anhydrides. eg.

O
O
C CH3 O
H 3C
O ¾¾¾
® OH
AlCl3
+ + H 3C C
H3C
O
Mechanism of the Reaction :
In most Friedel-Crafts acylation reactions the electrophile appears to be an acylium ion formed
from an acyl halide in the following way.
O O
•• Å
Step I : R—C—Cl•• + AlCl3 R—C—Cl – AlCl3
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••

O
Å Å ••
Step II : H3C—C—Cl— AlCl3 R—C O•• + AlCl4

Å
R—C O

R
H
Å O
Step III : R—C O ¾¾® +

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10 JEE-Chemistry ALLEN

R
R
H C O
C
O
Step IV : + + AlCl4 ¾¾® + HCl + AlCl3

R R
••
C O •
• C O — A lC l 3
Å
–Cl –
Step V : + A lCl 3

In the last step, AlCl3 (a Lewis acid) forms a complex with the ketone (a Lewis base). After the
reaction is over, treating the complex with water liberates the ketone.

R R
Å
C O – AlCl3+ 2H2O ¾¾® C O + Al(OH)3 + 3HCl
C6H5 C6H5

Limitations of Friedel - Crafts Reactions :

(a) When the carbocation formed from an alkyl halide, alkene, or alcohol can rearrange to a
more stable carbocation, it usually does so and the major product obtained from the reaction
is usually the one from the more stable carbocation.
When benzene is alkylated with butyl bromide, for example, some of the developing butyl
cations rearrange by a hydride shift-some developing 1° carbocations (see following reactions)
become more stable 2° carbocations. The benzene reacts with both kinds of carbocations
to form both butylbenzene and sec-butylbenzene.

H
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H3 C Br AlCl3 H3 C d+ d- H3 C Å
[–AlCl3 Br]
CH2 ---Br---AlCl3 CH3
–AlCl3 Å
–H
–HBr

H2C—CH2-CH2-CH3 H3C—CH–CH2-CH3

minor major

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 ALLEN Aromatic Compounds 11
(b) A romatic ring containing –NH 2, –NHR, –NR2, groups do not undergo Friedal-Craft's
alkylation due to formation of anilinum complex which is meta directing and has more electron
withdrawing power than halogen in benzene ring.
H H
H—N: H—N—AlCl3
+

+ AlCl3

Meta directing group

and does not undergo
Friedal Craft's reaction

(c) Friedel-Crafts reactions (alkylationi and acylation) do not occur when powerful electron-
withdrawing groups are (like –NO2, –NR3 etc) present on the aromatic ring.
+ O
NO2 N(CH 3) 3 C OH

These do not undergo Friedel -Crafts reactions

(d) Aryl and vinylic halides can not be used as the halide component because they do not form
carbocations readily.
Cl/AlCl3

No reaction

No reaction

Cl/AlCl3

(e) Polyalkylations often occur because alkyl groups are electron releasing groups, and once
one is introduced into the benzene ring it activates the ring towards further substitution.

CH(CH3)2 CH(CH3)2
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H3 C
CHOH ¾¾¾ ®
BF3
+ 60° C +
H3 C
24% Isopropyl benzene
CH(CH3)2
14% diisopropylbenzene

Polyacylations are not a problem in Friedel-Crafts acylations. The acyl group (RCO–) by
itself is an electron-withdrawing group, and when it forms a complex with AlCl3 in the last
step of the reaction, it is made even more electron withdrawing. This strongly inhibits further
substitution and makes monoacylation easy.

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12 JEE-Chemistry ALLEN
Some examples of Friedel-Craft's Acylation reaction

O
O C
AlCl3 R
Q.1 + R–C–Cl

O
O O O
AlCl3 CH3
Q.2 + CH3–C C–CH3 + HO–C–CH3
O

O
O C
AlCl3
Q.3 + Ph–C–Cl

O
O C–Cl
AlCl3
Q.4 + Cl–C–Cl
(1 eq.)

O O
O
C–CH2–CH2–C–OH
AlCl3
Q.5 + O ¾¾¾¾ ®

Cl
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AlCl3
Q.6 O
O

OH
1. SOCl2/AlCl2
Q.7 O 2. Conc. H2SO4/D

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 ALLEN Aromatic Compounds 13

q COUPLING REACTION
Coupling reaction is used for formation of coloured compound dye & indicator. In this reaction
benzene diazonium salt is electrophile.

N N
N= Nº
Cl

Resonating structures of Benzene diazonium chloride.

Since PhN +2 is weak electrophile hence couples only with highly activated ring.

NH2 NHR NR2

OH
OH OH
in alkaline
condition

OR

There are two kinds of coupling :

(a) C–N coupling :
The reaction in which coupling occurs between carbon & nitrogen is called C–N coupling.
(b) N–N coupling :
The reaction in which coupling occurs between nitrogen & nitrogen is called N–N coupling.

Me
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N N2Cl
Me Me
1. + N N=N
Me
(Major)

OH N2Cl
alkaline medium
2. + HO N=N
(Major)

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14 JEE-Chemistry ALLEN

OH OH
N2Cl
Basic medium
+
3.
N=N–Ph

N=N–Ph
OH OH
Basic medium
4. + PhN2Cl

(Red colour dye)

NH2 N2Cl NH–N=N–Ph (N–N coupling)

5. +

mild acidc
medium

NH2

(C–N coupling)

N=N–Ph

NHMe N2Cl
6. + N–N=N (N–N coupling)
Me
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NHMe
mild acidc
medium (C–N coupling)
Ph–N=N

C–N coupling takes place in acidic medium on the other hand N–N coupling takes place in absence
of acidic medium.

Ph
D
7. + [PhN2]Cl [Gomerb reaction] + Na2 (­) + HCl

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 ALLEN Aromatic Compounds 15

q NUCELOPHILIC AROMATIC SUBSTITUTION

Possible mechanism for nucleophilic aromatic substitution.
(i) SN2–Ar/SNAE–mechanism
(ii) SN1–Ar/Aryl cation mechanism
(iii) SNEA/Sine substitution/Benzyme mechanism.
SN2–Ar mechanism : (Biomolecular nucleophilic substitution on aromatic ring mechanism)

Cl
NaOH
r.t.
X

L Nu
Z Z Z Z
Nu

Z Z
where, L, Z, NQ4 / Na may be

–L –Z – Nu / Nu
–F –CN NaOH
–Cl –CHO KOH
–Br –COR H2O
–I –NO2 NH3
–OR –F N2H4
–NO2 –Cl RO
–Br ROH
q Some examples of SN2–Ar reaction :
Cl OH
NO2 NO2 O2N NO2
NaOH
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1.
NO2 NO2
Mechanism :
Step-1
Cl Cl OH Cl OH
NO2 NO2 NO2 NO2 NO2 NO2
OH other
resonating –
slow RDS
structure
NO2 NO2 NO2
Carbanion intermediate / m-complex

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16 JEE-Chemistry ALLEN

Cl OH OH
Step-2 : NO2 NO2 NO2
O2N
– fast
+ Cl

NO2 NO2
Note :
(i) Carbanion intermediate (M-complex)
(ii) Step-1 is rate determining step / slow step.
(iii) Rate of SN2–Ar depends on stability of M-complex.
(iv) M-complex can be stabilized by
(a) EWG at ortho & para position.
(b) –I effect of leaving group.
(v) Order of substitution in following
F Cl Br I
NO2 NO2 NO2 NO2
> > >

(vi) Rate expression for above reaction is

L
Z Z
Rate = K Nu

Z
(vii) Bimolecular IInd order

(viii)
PE M-complex

Cl Cl
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NO2 NO2
NaOH
2. D 95°C

NO2 NO2

Cl Cl

NaOH
3. D 170°C

NO2 NO2

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 ALLEN Aromatic Compounds 17

q SN1–Ar mechanism :

N2Cl OH
Boil steam
1.

Mechanism :

N2Cl
r.d.s.
Step-1 : slow step + N2 + Cl

OH2 OH
H2O –H
Step-2 :
fast

N2Cl I
KI/D
2.

N2Cl Cl
CuCl/ArCl
3. Sandmayer reaction

N2Cl Br
CuCl/HBr
4. Sandmayer reaction

N2Cl N2BF4 NO2

NaBF4 NaNO2
5.
D

N2Cl F
HBF4 (Boltz scheimern reaction)
6.
D

N2Cl
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H3 PO2
7. + H3PO3

N2Cl OH
H2O/D
8.

N2Cl
OH
9. + CH3–CH=O + HCl

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18 JEE-Chemistry ALLEN
q AROMATIC REARRANGEMENTS
1. Dienone-phenol rearrangement :
O OH
+H/D
(i)
R
R R R
O OH
+H/D
(ii)

O
OH
+H/D
(iii)

2. Fries rearrangement

OH O OH
O CH3
(i) AlCl3
C–CH3
+
O D
Phenyl acetate
O

Mechanism :

AlCl3
OAlCl3 OH
O O
AlCl3 CH3CO
O D O
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

O
3. Claisen rearrangement

14
O OH OH
14
D
+

Major Minor

14

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 ALLEN Aromatic Compounds 19

Mechanism :

O O O OH
14
H14 14
14
Tautomerism

6–MCTS

O O O
H 14
Tautomerism

H
14
14

Note :
(i) Ortho is major as latter MCTS is strained
(ii) Reaction occure 6-MCTS
(iii) Para dominates when both ortho are blocked.

14
O OH
14
D
(i)

(Major)

14
O OH
D
(i)
14
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Oxidation of some aromatic compounds

1. By V2O5

V2O5
OH
(i) 250º

O
V2O5
(ii) 500ºC
O

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20 JEE-Chemistry ALLEN

O
V2O5
(iii) 500ºC
O

OH O
O
OH
V2O5
(iv) 500ºC
O

O
2. By K2Cr2O4

K2Cr2O7
(v) ××
D

OH O
K2Cr2O7
(vi) D
O
NH2 O
K2Cr2O7
(vii) D
O
OH O
K2Cr2O7
(viii) D
H2N O

OH O
K2Cr2O7
(ix) D

NO2 NO2 O
K2Cr2O7
(x) D

O
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O
K2Cr2O7
(xi)
D

(xii) K2Cr2O7
D

O O

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 ALLEN Aromatic Compounds 21

3. By KMnO4
KMnO4
(xiii) ×
D

KMnO 4 COOH
(xiv) D

KMnO4 COOH
(xv) D

KMnO4 COOH
(xvi)
D

KMnO4 COOH
OH
(xvii) D

AROMATIC HYDROXY DERIVATIVES

q Phenolic compounds :
Compounds in which —OH group is directly attached to sp2 carbon of benzene ring
OH OH OH
CH3 COOH

Phenol o-cresol Salicylic acid

OH
OH OH
OH
OH OH
catechol resorcinol quinol
All phenolic compounds give characteristic colour with neutral FeCl3.
Ph—OH neutral FeCl
¾¾¾¾¾¾
3
® Violet colour
CH3CH 2—OH neutral FeCl
¾¾¾¾¾¾
3
® No colour
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PHENOL (C6H5OH)
Phenol is also known as carbolic acid or Benzenol or hydroxy benzene or carbinol.In phenol —OH
group is attached with sp2 hybridised carbon.It was discovered by Runge in the middle oil fraction of
coaltar distillation and named it carbolic acid (carbo = coal; oleum = oil) .It is also present in traces in
human urine.
q General Methods of preparation :
(1) From benzene sulphonic acid :
When sodium salt of benzene sulphonic acid is fused with NaOH, phenol is obtained.

C6H5SO3Na ¾¾¾¾ ® C H OH + Na SO
(i) NaOH
Å
(ii) H 6 5 2 3

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22 JEE-Chemistry ALLEN
(2) From benzene diazonium chloride :
When benzene diazonium chloride solution is warmed, phenol is obtained with evolution of nitrogen.

N2Cl OH
( Steam distilled) H O
¾¾¾¾¾¾¾¾
D
2
® + N2 + HCl

(3) By distilling a phenolic acid with sodalime (decarboxylation):

OH OH
COOH NaOH + CaO
¾¾¾¾¾¾
D
® + Na2CO3

Salicylic acid
(4) From Grignard reagent : (The Grignard reagent on reaction with oxygen and subsequent hydroly-
sis by acid yields phenol)
Br
C6H5MgBr ¾¾¾
[O]
® C6H5OMgBr ¾¾¾
HO
® C6H5OH + Mg 2

OH

(5) From benzene :

OH
V2 O5
+ [O] ¾¾¾¾
300°C
®

(6) From chloro benzene :

Ph—Cl Aq. NaOH
¾¾¾¾¾ ® No NSR at normal condition
Stable by resonance
R—Cl Aq. NaOH
¾¾¾¾¾ ® R—OH [NSR]
Aq. NaOH
Ph—Cl ¾¾¾¾¾ o
® Ph—ONa
300 C

Order of NAS (Nucleophilic Aromatic substitution, ArSN or NSR) :

Cl Cl Cl Cl
NO2 NO2 NO2 NO2
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

< < <

NO2 NO2
max. –I, –M
Aq. NaOH min. ed Aq. NaOH
300°C min. ESR 25°C
max. NSR
OH OH
NO2 NO2

NO2
2, 4, 6–Trinitrophenol (Picric acid)

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 ALLEN Aromatic Compounds 23

(7) Industrial preparation of phenol:

Phenol can be prepared commercially by :
(a) Middle oil fraction of coaltar distillation
(b) Cumene
(c) Raschig process
(d) Dow's process
(a) Middle oil fraction of coaltar:

Fractional
Coaltar ¾¾¾¾® Middle oil (170-230°)
distillation
(Phenol, cresols, Naphthalene)

Coal

Naphthalene liquid
(Solid crystals separate out) NaOH (dil.)

C6H5ONa
CO 2/H 2O or sulphuric acid

C6H5OH + Na2CO3

(b) From cumene (Isopropyl benzene) : Cumene is oxidised with oxygen into cumene
hydroperoxide in presence of a catalyst. This is decomposed by dil. H2SO4 into phenol and
acetone.
O OH
CH3 CH3
CH C(CH3)2 OH
O
¾¾¾¾¾
H SO ,H O
® + CH3 C CH3
¾¾¾¾2
130° C
® 2 4 2
H + / 100° C
O
Cumene Cumene hydroperoxide

(c) Raschig process : Chlorobenzene is formed by the interaction of benzene, HCl and air at
o
300°C in presence of catalyst CuCl2 + FeCl3. It is hydrolysed by superheated steam at 425 C
to form phenol and HCl.
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

1 CuCl FeCl
C6H6 + HCl + O2 ¾¾¾¾¾
2 3
® C6H5Cl + H2O
2 0
300 C

C6H5Cl + H2O 425 C

¾¾¾¾
0
® C6H5OH + HCl
(super heated steam)
(d) Dow process : This process involves alkaline hydrolysis of chloro benzene-(large quantities of
phenol formed).
OH
Cu — Fe
C6H5Cl + NaOH ¾¾¾¾
300 C
® 0 + NaCl

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24 JEE-Chemistry ALLEN

q Physical properties :
(i) Phenol is a colourless, hygroscopic crystalline solid.
(ii) It attains pink colour on exposure to air and light. (slow oxidation)

C6H5OH O O H – O – C6H5

Phenoquinone (pink colour)

(iii) It is poisonous in nature but acts as antiseptic and disinfectant.
(iv) Phenol is slightly soluble in water , readily soluble in organic solvents.
(v) Solublity of phenol in water is much lower than alcohols because of larger hydrocarbon part in
the molecule.
(vi) Due to intermolecular H-Bonding, phenol has relatively high boiling point than the
corresponding hydrocarbons, aryl halides etc. but intermolecular H-bonding in o–derivatives is
used in the preparation of dyes, drugs, bakelite and it's melting point (MP) is 43° C and boiling
point (BP) is 182° C .
q Chemical Properties :
(A) Reactions due to –OH group :
u Acidic Nature : Phenol is a weak acid. The acidic nature of phenol due to formation of stable
phenoxide ion in solution. The phenoxide ion is stable due to resonance. The negative charge
is spread through out the benzene ring which is stabilising factor in the phenoxide ion. Electron
withdrawing groups (–NO2, –Cl) increase the acidity of phenol while electron releasing groups
(–CH3 etc.) decrease the acidity of phenol.
1 Å
C6 H5 OH ˆˆˆ
†
‡ˆˆˆ C 6 H 5 O + H3 O
Phenol is stronger acid than alcohols but weaker than the carboxylic acids and even carbonic
acid
The acidic nature of phenol is observed in the following:
(i) Phenol changes blue litmas to red.
(ii) Highly electro positive metals react with phenol.
2C6H5OH + 2Na ¾¾® 2C6H5ONa + H2
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

(iii) Phenol reacts with strong alkalies to form phenoxides.

1 Å
C6 H5 OH + NaOH ¾¾® C6 H5 O N a +H2 O
(iv) However phenol does not decompose Na2CO3 or NaHCO3 because phenol is weaker than carbonic
acid.
C6H5OH + Na2CO3 or NaHCO3 ¾¾® No reaction
Ph—OH + NaHCO3 Ph—ONa + H2CO 3
Acid-I Base-I Base-II Acid-II
Acid-I < Acid-II
Reaction in reverse direction .
Base-I < Base-II

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 ALLEN Aromatic Compounds 25

(v) Phenol does not react with NaHCO3.

CH3 C OH + NaHCO3 CH3 C ONa + H2CO 3 [H2O + CO2­]
O O
Acid-I Base-I Base-II Acid-II
Acid-I > Acid-II
Reaction in forward direction .
Base-I > Base-II
(vi) Acetic acid reacts with NaHCO3 and gives effervesence of CO2.
Q. Identify the compound which release CO2 with NaHCO3 ?
OH COOH
NO2 NO2
(A) (B)
NO2
SO3H OH
(C) (D)
Ans. (A, B, C)
u Reaction with Zn dust: When phenol is distilled with zinc dust benzene is obtained.
C6H5OH + Zn ¾¾® C6H6 + ZnO
CH2 OH
Q. Zn
¾¾¾ ®?

Sol. No reaction

CH3
OH
Q. Zn
¾¾¾ ®?

CH3

Sol.

CH3
CH3
Q. Zn
¾¾¾ ® ?
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

Sol. No reaction

COOH
OH
Q. Zn
¾¾¾ ® ?

COOH

Sol.

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26 JEE-Chemistry ALLEN

u Reaction with NH3( Bucherer reaction): Phenol reacts with NH3 in presence of anhydrous
ZnCl2 to form aniline.

Anhydrous ZnCl2 or (NH 4 )2 SO3 / NH 3 150°C

C6H5OH + NH3 ¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾ 300° C
¾
® C6H5NH2 + H2O

u Reaction with FeCl3: Phenol gives violet colouration with FeCl3 solution (neutral) due to forma-
tion of a complex.
C6H5OH + FeCl3¾¾® Voilet colour
This reaction is used to differentiate phenol from alcohols.
u Acetylation (Schotten-Baumann reaction) : Phenol reacts with acid chlorides or acid
anhydrides in alkali solution to form phenyl esters.
NaOH
C6H5OH + ClCOCH3 ¾¾¾¾
- HCl
® C6H5O—C CH3

O
NaOH
C6H5OH + Cl C C6H5 ¾¾¾¾ ® C6H5O C—C6H5
- HCl

O O

u Ether formation (Alkylation) : Phenol reacts with alkyl halides in alkali solution to form phenyl
ethers. (Williamson's synthesis)
RX
C6H5OH + NaOH alkali solution
¾¾¾¾¾¾ ® C6H5ONa ¾¾¾¾
- NaX ® C6H5OR

Sodium phenoxide
u Ether can also be formed when phenol react with diazomethane.
C6H5OH + CH2N2 ¾¾® C6H5OCH3 + N2 ­
(B) Reaction of Benzene Ring : The —OH group is ortho and para directing. It activates the benzene
nucleus.
u Halogenation : Phenol reacts with bromine in CCl4 to form mixture of ortho–and para–bromo
phenol.
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

OH OH OH
CHCl or CS or CCl Br
+ Br2 ¾¾¾¾¾¾¾¾3 2
low.temp.
® 4
+

Br

Phenol reacts with bromine water to form a white ppt. of 2,4,6 tribromo phenol.

OH
OH Br Br
+ 3Br2 ¾¾¾
2 H O
® + 3HBr
Br

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 ALLEN Aromatic Compounds 27

u Nitration : Phenol reacts with dil. HNO3 at 0°–10° C to form ortho- and para- nitro phenols.

OH OH OH
dil.HNO NO2
¾¾¾¾¾
0-10°C
3
® +
(40%) NO2 (10%)

When phenol is treated with nitrating mixture to form 2,4,6- trinitro phenol (picric acid)

OH
OH NO2 NO2
Conc.HNO3
¾¾¾¾¾¾
Conc.H2 SO4 ® [2, 4, 6–Trinitrophenol (Picric acid)]
NO2

u Sulphonation: Phenol reacts with fuming H2SO4 to form ortho–and para–hydydroxy benzene
sulphonic acid at different temperatures.
OH
25°C
SO3H
OH

+ conc. H2SO4
OH
100°C

SO3H
u Friedel-Craft's reaction : Phenol when treated with methyl chloride in presence of anhydrous
AlCl3, p-cresol is main product.
OH
OH OH
CH3
+ CH3Cl Anhydrous AlCl
¾¾¾¾¾¾¾
3
® +

CH3
o-cresol p-cresol

OH OH OH
COCH3
+ CH3COCl Anhydrous AlCl +
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

¾¾¾¾¾¾¾
3
®

COCH3
o – and p – hydroxy acetophenone

u Gattermann aldehyde synthesis : When phenol is treated with liquid HCN and HCl gas in
presence of anhydrous AlCl3 yields mainly p- hydroxy benzaldehyde (formylation)
HCl + HCN AlCl3
¾¾¾¾ ® HN CHCl
OH OH OH
AlCl H2 O
+ HN CHCl ¾¾¾ ¾
® 3 ¾¾¾¾
®
- NH3
HCl

CH NH CHO

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28 JEE-Chemistry ALLEN

u Gatterman Koch reaction :

OH OH

HCl + CO + AlCl3

C H
O
Major
u Riemer-Tiemann reaction : Phenol on refluxing with chloroform and NaOH (aqueous)
followed by acid hydrolysis yields o–hydroxy benzaldehyde (As major product). When CCl4
is used salicylic acid is formed.
OH ONa OH O
CHCl2 CHO + C H
CHCl3
¾ ¾NaOH
¾¾® ¾ ¾H¾ ®
60°C NaOH (aq.) H2O
OH
Salicylaldehyde

OH ONa OH O
CCl4
CCl3 COONa + C OH
¾ ¾NaOH
¾¾® ¾ ¾H¾ ®
60°C NaOH (aq.) H2O

Salicylic acid

Mechanism : CCl2 is neutral attacking electrophile (formed by a- elimination reaction)

KOH
CHCl3 ¾¾¾® :CCl2 (dichloro carbene)
1
O–H O O O
1 H 1 Cl
¾¾¾®
HO1
¬¾¾® :CCl
¾¾¾® 2 C
–H O 2 Cl

1
1
OH O O
CHO 1 OH Cl
1
OH CH OH CH
¬¾¾¾ ¬¾¾¾ Cl
–H O 2 OH

Asprin formation :
O
OH O
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

O–C–CH3
C–OH O O COOH O
H 3PO 4
+ CH3–C–O–C–CH3 Catalyst + CH3–C–OH
Salicylic acid Asprin (pain killer)

u Kolbe 's Schmidt reaction : This involves the reaction of C6H5ONa with CO2 at 1400 C
followed by acid hydrolysis salicylic acid is formed followed.

O NaÅ OCOONaÅ OH OH
Å
COONa COOH
140° C Rearrangement H+
+ CO2 ¾¾¾¾¾® ¾¾¾¾¾® ¾¾®
6 atm. pressure H 2O
Sodium phenyl carbonate Sodium salicylate Salicylic acid

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 ALLEN Aromatic Compounds 29
u Asprin fomation
O
OH O O C CH3
O COOH O
C OH H 3PO 4
+ CH3 O C CH3 Catalyst + CH3 C OH

Salicylic acid Asprin (pain killer)

u Hydrogenation: Phenol when hydrogenated in presence of Ni at 150-200 0C forms
cyclohexanol.
OH OH
Ni
+ 3H2 ¾¾¾¾®
150 – 200° C

Cyclohexanol. (C6H11OH)
(used as a good solvent)
u Fries rearrangement reaction :
C6H5OH + CH3COCl ¾¾¾¾¾¾¾
Anhydrous AlCl3
® C6H5OCOCH3

OH
60°C

anhydrous AlCl COCH3

C6H5OCOCH3 ¾¾¾¾¾¾® 3

OH
Phenyl ester (acetate)
COCH3

u Coupling reactions: Phenol couples with benzene diazonium chloride in presence of an alka-
line solution to form a dye (p- hydroxy azobenzene) red only.
NaOH ( pH 9 to 10)
N2Cl + OH –HCl
N N OH
p–hydroxy azobenzene (Orange dye or Red dye)

pH = 9 to 10
N2Cl + NH2 0 to 5°C
N N NH2
p–amino azobenjene (orange dye)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

Phenol couples with phthalic anhydride in presence of conc. H2SO4 to form a dye
(phenolphthalien) used as an indicator.

O O OH
O C C OH OH H SO
O C C
+ ¾¾¾®
2 4
OH
–H2O
H OH

Phenol (2 molecules) Phenolphthalien (Colourless in acidic

medium and pink in alkaline medium)

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30 JEE-Chemistry ALLEN
u Lederer Manasse (Condensation with formaldehyde) : Phenol condenses with HCHO (ex-
cess) in presence of NaOH or weak acid (H+) to form a polymer known as bakelite (a resin).

OH OH OH
CH2OH
NaOH
+ HCHO ¾¾¾® +
(20%)
CH2OH

¾¾¾®
(40%) Polymerisation
condensation with HCHO

HO CH2 OH

CH2 CH2

OH CH2 OH

CH2 CH2

Polymer bakelite (Phenol formaldehyde resin)

u Leibermann's nitroso reaction : When phenol is reacted with NaNO2 and conc. H2SO4 it
gives a deep green or blue colour which changes to red on dilution with water. When made
alkaline with NaOH original green or blue colour is restrored.
This reaction is used as a test of phenol.
2NaNO2 + H2SO4 ¾¾® 2HNO2 + Na2SO4

OH OH O
HONO C H OH H2 O NaOH
¾¾¾®
6 5
Green phenol¾¾® Red ¾¾® Blue Sodium
H2SO4
or blue colour Indophenol Salt (original
H NO N OH ion green or blue
colour is restored)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

u Reaction with acetone: (Condensation with acetone)

OH OH OH OH
con. HCl
¾¾¾®
–H2O

H H CH3 C CH3
O Bis - Phenol-A
p-p'– Isopropylidene diphenol
CH3 C CH3

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 ALLEN Aromatic Compounds 31
u Oxidation:
Air [O]
O O + H2O p-Benzo quionone (Red)
CrO2Cl2

OH
(O)

(Phenol)
K2S2O8/KOH
HO OH (Quinol)
(Elb's persulphate reaction)
1, 4 – Dihydroxy benzene

q Test of Phenol :

(i) Phenol turns blue litmus to red.

(ii) Aqeous solution of phenol gives a violet colour with a drop of ferric chloride.

(iii) Phenol gives Lieber mann 's nitroso test.

NaNO
Phenol in conc. H 2SO4 ¾¾¾¾¾¾
excess of water
¾
® Red colour ¾¾¾¾¾¾
2
NaOH excess
® Blue colour

(iv) Aqeous solution of phenol gives a white ppt. of 2,4,6 tribromophenol with bromine water.

(v) Phenol combines with phthalic anhydride in presence of conc. H2SO4 to form phenolphthalein
which gives pink colour with alkali.

(vi) With ammonia and sodium hypochlorite , phenol gives blue colour.

q Differences between phenol and alcohol (C2H5OH) :

(i) Phenol is more acidic than aliphatic alcohol due to resonance in phenoxide ion.

(ii) Phenol gives violet colour with FeCl3 while aliphatic alcohol does not give.

(iii) Phenol gives triphenyl phosphate with PCl5 while aliphatic alcohol gives alkyl chloride.

(iv) Phenol has phenolic odour whereas alcohol has pleasent odour.
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

(v) Phenol on oxidation gives quinone while alcohol gives aldehyde or ketone and acids.

q Uses of Phenol : Phenol is used :

(a) As an antiseptic in soaps and lotions. "Dettol" (2,4-Dichloro-3,5-dimethyl phenol)

(b) In manufacture of azodyes, phenolphthalein , picric acid (explosive), cyclohexanol (Solvent

for rubber), plastics (bakelite) etc.

(c) In manufacture of drugs like aspirin salol, phenacetin etc.

(d) As preservative for ink.

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32 JEE-Chemistry ALLEN
ANILINE (C6H5NH2)
Aniline is also called aminobenzene or phenyl amine. Aniline was first prepared by Unverdon 1826
by the distillation of indigo which is called anil in spanish and hence the name aniline. In aniline —
NH2 group is directly attached to benzene ring.
q General Methods of Preparation :
(1) Lab method : Aniline is prepared in the lab by reduction of C6H5NO2 with Sn + HCl.
(i)Sn + HCl
C6H 5NO 2 ¾¾¾¾¾
(ii) NaOH
® C6H5NH2 + H2O

(2) Industrial method : Aniline is obtained by reduction of nitrobenzene in presence of Fe/HCl.

(i) Fe + HCl
C6H5—NO2 ¾¾¾¾¾
(ii ) NaOH
® C6H5 —NH2 + H2O

(3) From Phenol : Aniline is obtained when phenol is treated with ammonia in presence of ZnCl2 at 300°C.
ZnCl2
C6H5OH + NH3 ¾¾¾¾
300° C
® C6H5NH2 + H2O

(4) From benzamide (Hofmann's reaction): Aniline is formed when benzamide is treated with Br2 and
KOH.
C6H5CONH2 + Br2 + 4KOH ¾¾® C6H5NH2 + K2CO3 + 2KBr + 2H2O
(5) From benzoic acid (Schmidt reaction) : Benzoic acid is dissolved in conc. H2SO4 and hydrazoic
acid is dissolved in chloroform. When both solutions are mixed aniline obtained.

C 6 H5 COOH + N 3 H Conc.
¾¾¾¾ ® C6H5NH2 + N2­ + CO2­
H2 SO4
(Hydrazoic acid)

(6) From chloro benzene : Aniline can be manufactured by the action of ammonia on chloro benzene in
presence of cuprous oxide (Cu2O).
2C6H5Cl + Cu2O + 2NH3 ¾¾® 2 C6H5NH2 + 2CuCl + H2O
(7) From Grignard reagent :

C6H5MgBr + ClNH2 ¾¾® C6H5NH2 + Mg Br + C6H6

node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

Cl

(8) From Benzene:

FeCl 3
C6H6 + NH2OH ¾¾¾¾ ® C6H5NH2 + H2O
(9) From phenyl isocyanide :
C6H5N C + 2H2O ¾¾® C6H5NH2 + HCOOH
(10) From phenyl isocyanate:-
C6H5N C O + 2KOH ¾¾® C6H5NH2 + K2CO3

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 ALLEN Aromatic Compounds 33

q Physical Properties :
(i) Fresh, aniline is a colourless oily liquid. On standing the colour becomes dark brown due to
action of air and light.
(ii) It's B.P. is 183° C.
(iii) It is heavier than water.
(iv) It has characteristic unpleasent odour. It is toxic in nature.
q Similarities and Differences between Aromatic and Aliphatic amines :
(A) Similarities :
(i) Both are basic, although aliphatic amines are more basic than the aromatic amines.
(ii) Both form salts with acids, however salts of aromatic amines are easily hydrolysed.
(iii) Both undergoes alkylation and acylation.
(iv) Both react with Grignard reagents forming hydrocarbons.
(v) Both forms schiff's bases.
(B) Differences :
(i) Aniline is insoluble in water while aliphatic amines are soluble in water (due to H-bonds)
(ii) Aniline gives diazonium salt with HNO2 while aliphatic amines gives alcohol and nitrogen
(except CH3NH2)
(iii) Aniline undergoes coupling and electrophilic substitution reactions in benzene ring while
aliphatic is not.
(iv) Aniline has characteristic aromatic smell while aliphatic amines have smell like ammonia
(v) Aniline gives aniline black dye with acidic K2Cr2O7 while aliphatic does not form dye.
q Chemical Properties :
(i) Aniline is a primary amine it shows properties of both of benzene nucleus and —NH2 group.
(ii) Aniline has weak basic nature as compared to aliphatic amine.
(ii) Weaker basic nature of aniline as compared to aliphatic amines can be explained on the basis of
resonance. In aniline the non-bonding electron pair of N is delocalised in to benzene ring by resonance.
Thus electron density is less on N atom due to which aniline is less basic than aliphatic amines
+d
H ¾¾®
:

N N H
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

-d

H H
Order of basic strength : RNH2 > NH3 > C6H5NH2
(iv) Electron withdrawing group decreases the basic strength where as electron donating groups
increases the basic strength
NH2 NH2 NH2

< <

NO2 CH3

(v) Aqueous solution of aniline is neutral to litmus

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34 JEE-Chemistry ALLEN
(A) Reactions due to —NH2 group :
(1) Basic nature : Aniline is weak base but it forms salt with strong acids. It a accepts a proton.
Å

:
C6H5NH2 + H+ ¾¾® C6H5NH3

Å 1
C6H5NH2 + HCl ¾¾® C6H5NH3Cl Aniline hydro chloride
2C6H5NH2 + H2SO4 ¾¾® (C6H5NH2)2H2SO4 Aniline sulphate
2C6H5NH2 + H2PtCl6 ¾¾® (C6H5NH2)2H2PtCl6 Aniline platinic chloride
Chloro platinic acid
Chloro platinic method : This is used to determination of molecular weight of organic compounds.
(2) Alkylation :
Aniline reacts with alkyl halides forming secondary, tertiary and quaternary ammonium salts depending
on the concentration of alkyl halides.
C6H5NH2 + CH3I ¾¾® C6H5—NH—CH3 + HI
(N–methyl aniline)
C6H5NH — CH3 + CH3I ¾¾® C6H5N(CH3)2 + HI
(N,N–dimethyl aniline)
Å1
C6H5N(CH3)2 + CH3I ¾¾® C6 H5 (CH3 )3 N I

(Trimethyl phenyl ammonium iodide)

(3) Acylation :
Aniline reacts with acid chlorides or anhydrides to form corresponding amides called anilides. The
reaction of C6H5NH2 with benzoyl chloride is called "Schotten Baumann reaction".

C6H5NH2 + Cl C CH3 ¾¾® C6H5 NH C CH 3 (Acetanilide)

O O

C6H5NH2 + (CH3 C )2O ¾¾® C6H5 NH C CH3 + CH3COOH

O O
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

C6H5NH2 + Cl C C6H5 ¾¾® C6H5 NH C C6H5 (Benzanilide)

O O

(4) Carbylamine reaction : When aniline is heated with CHCl3 and KOH it gives isocyanide having
unpleasent smell which can be easily detected.
C6H5NH2 + CHCl3 + 3KOH ¾¾® C6H5NC + 3KCl + 3H2O
Phenyl isocyanide
u Note : (i) Intermediate species is dichloro carbene [: CCl2].
(ii) This is a test of aniline and other primary amines and is known as isocyanide test.

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 ALLEN Aromatic Compounds 35
(5) Hoffmann's mustard oil reaction :
When aniline is heated with alc. CS2 and excess of HgCl2 phenyl isothiocyanate having a characteristic
smell of mustard oil is formed.
HgCl2
C6H5NH2 + S C S ¾¾¾¾
- H2 S ® C 6H 5 N C S

Phenyl isothiocyanate
If the above reaction is carried out in presence of solid KOH diphenyl thiourea is formed (Used as
accelerator for vulcanisation of rubber).

C6H5NH2 C6H5NH
+ S=C=S ¾¾® C S + H2S
C6H5NH2 C6H5NH

When diphenyl thiourea is treated with HCl it gives phenyl isothiocyanate.

C6H5NH Å 1
C S + HCl ¾¾® C6H5 N C S + C6 H5NH3Cl
C6H5NH

(6) Reaction with aldehydes : Aniline condenses with aldehydes to form schiff's base.
Å
H C6H5N CHC6H5 + H2O
C6H5NH2 + H C C6H5
O Benzylidene aniline
(schiff's base)

(7) Reaction with Heinsberg's reagent :

C6H5—SO2Cl + HNHC6H5 -HCl
¾¾¾ ¾
® C6H5SO 2NHC6H 5
(N– Phenylbenzene sulphonamide)
(8) Acidic nature :
C6H5NH2 + Na ¾¾® C6H5NHNa + 1/2H2
N-Phenyl sodamide
(9) Diazotisation :
Diazotisation is a reaction in which ice cooled solution of aniline in a inorganic acid with sodium
nitrite solution leading to the formation of diazonium salt.
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

°
0 -5 C°
C6H5NH2 + NaNO2 + HCl ¾¾¾¾
–H O ®
2
C6H5N2Cl

Å 1
C6H5NH2 + HCl ¾¾® C6H5NH3Cl

NaNO2 + HCl ¾¾® HNO2 + NaCl

Å 1
C6H5NH3Cl + HNO2 ¾¾® C6H5N2Cl + 2H2O
Benzene diazonium chloride
Benzene diazonium chloride is a useful synthetic reagent. It is used in the preparation of many organic
compounds
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36 JEE-Chemistry ALLEN

u Note :

Coupling between arenediazonium cations and amines take place most rapidly in slightly acidic solution
(pH 5 to 7). Under these conditions the concentration of the arenediazonium cation is at a maximum
; at the same time an excessive amount of the amine has not been converted to an unreactive aminium
salt.
C6H5 OH
C6H5N2Cl ¾¾¾® C6H5N=NC6H4OH [p-hydroxy azobenzene (orange dye)]

C H NH
C6H5N2Cl ¾¾¾¾ ® C6H5N=NC6H4NH2 [p-amino azobenzene (aniline yellow)]
6 5 2

N2C6H5
OH
C6H5N2Cl ¾¾¾¾
b-Naphthol
10%NaOH
® (Red colour)

(10) Oxidation : Aniline forms a number of products depending upon the nature of oxidising agent:-
[O]
—NH2 ¾¾¾ ® —NHOH ¾¾¾
[O]
® —NO ¾¾¾
[O]
® —NO2

S.N. Oxidant Product

1. Acidic KMnO4 Aniline black (a dye)
2. Alkaline KMnO4 Azobenzene C6H5N = NC6H5
3. Neutral KMnO4 Azobenzene + Nitro benzene
4. Caro's acid (H2SO5) Nitrobenzene + Nitroso benzene
5. CF3 COOOH Nitrobenzene

6. K2Cr2O7 + conc. H2SO4 p–Benzo quinone O O

7. NaOCl p- Amino Phenol (Violet colour)

8. HNO 3 Decomposes
Atmospheric air
9. Aniline ¾¾¾¾¾¾¾ ¾
® Dark red colour
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

& light

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 ALLEN Aromatic Compounds 37
C H OH
¾¾¾ ¾¾®
2 5

H PO
¾ ¾ ¾3 ¾2¾ ®
C6H6 Benzene
HCOOH
¾¾¾¾¾®

Na/NaOH
¾ ¾ ¾2H¾ ¾ ®

Cu Cl /HCl
¾¾¾ ¾¾®
2 2
C6H5Cl + N2 + HCl

Cu Br /HBr
¾ ¾ 2¾ ¾
2
¾® C6H5Br + N2 + HCl Sandmeyer reactions

Cu (CN) /HCN
¾ ¾2 ¾ ¾
2
¾® C6H5CN + N2 + HCl

KI (aq.)
C6H5N2Cl ¾ ¾ ¾ ¾ ¾ ® C6H5I + N2 + KCl

NaBF /D
¾¾¾¾
4
¾® C6H5F + BF3 + NaCl Balz–Schiemann reaction
Sodium tetrafluoro
borate

H O
¾ ¾ ¾D2¾ ¾ ® C6H5OH
Cu
¾¾¾¾¾® C6H5Cl Gattermann reactions

+4H
¾¾¾¾¾® C6H5NHNH2 (Phenyl hydrazine)
SnCl2 + HCl
N2 C6H5
OH
¾¾ ¾¾¾®
10% NaOH
(Red colour)

SnCl /NaOH
¾ ¾ ¾2 ¾ ¾ ® C6H6
C H OH
¾¾¾ ¾¾®
6 5
C6H5N N— C6H4OH
p-Hydroxy azobenzene (Orange dye) Coupling
C6H5NH2 reactions
¾¾¾¾¾® C6H5N N C6H4NH2
p-Amino azobenzene (aniline yellow)
(B) Reactions due to benzene ring :
Å Å Å Åd
:

NH2 NH2 NH2 NH2 NH2 NH2

node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

1
:
1 -d/3 -d/3

1 -d/3
:

Resonance hybrid

u Note :
(i) In aniline 2, 4, 6 or ortho and para positions are electron rich so electrophile attacks here.In
aniline 3, 5, or meta position is electron deficient so nucleophile attacks here.
(ii) The benzene ring of aniline undergoes halogenation, sulphonation and nitration.
(iii) The NH2 group is o-, p-directing.

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38 JEE-Chemistry ALLEN
(1) Halogenation : Chlorine and bromine react with aniline and form trichloro and tribromo aniline
respectively
NH2 NH2
NH2
Br Br Cl Cl
+ 3Br2 or 3Cl2 Polar solvent
¾¾¾¾¾¾ ® or
e.g. (H2O)

Br Cl
2,4,6– Tribromo aniline
(white ppt.)
u Note :
However, monobromo or chloro derivative of aniline can be prepared if -NH2 group is first protected
by acetyl group. Here the reactivity decreases due to -I effect of acetyl group.
NHCOCH3 NHCOCH3
Br
+

NH2 NHCOCH3 Br
CH3COCl Br2
H2O

(Acetanilide)
NH2 NH2
Br
+

(minor)
Br
(major)
(2) Nitration :
(a) Direct nitration : The direct nitration of aniline by conc. HNO3 and conc. H2SO4 give meta-
nitroaniline. Due to positively charged N, m-position becomes electron rich as compared to o,
p–position.

Å 1
NH2 NH3 HSO4 NH2
+
H2 SO 4
¾¾¾¾
HNO
® + N O2
¾¾¾¾ ¾
®
3 –H SO
2 4
NO2
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

(b) Indirect nitration : In indirect nitration amino group is protected by acetylation to give
acetanilide, which on nitration and subsequent hydrolysis give o- and p- nitro-aniline.
NH2 NHCOCH3 NHCOCH3 NHCOCH3 NH2 NH2
Å
NO
NO2 NO2
+ CH3COCl ¾ ¾ ® ¾ ¾ ¾2¾ ® + ¾ H¾O®
2
+
(HNO3+H2SO4)

NO2 NO2
(major)
Ex. Azo dye test is given by
(A) All amines (B) Only secondary amine
(C) Only primary aliphatic amine (D) Only primary aromatic amine
Sol. (D)

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 ALLEN Aromatic Compounds 39

(3) Sulphonation : Aniline reacts with fuming H2SO4 to give sulphanilic acid.(p-Amino-benzene
sulphonic acid)
Å 1
NH2 NH3 HSO4 NHSO3H NH2

+ H2SO4 (Fuming) ¾¾® - H2 O

¾¾¾
180°C
¾
® Rearrangement
¾¾¾¾¾¾¾¾¾ ®

SO3H
Sulphanilic acid

u Note : (i) The compounds in which both proton donating & proton accepting groups present are
called ampholite (dipolar ion).

Å
NH2 NH3

(Zwitter ion)
1
SO3H SO3

(4) Catalytic hydrogenation :

Aniline undergoes hydrogenation in presence of Ni at high temp. to form amino cyclohexane.
NH2 NH2
Ni
+ 3H2 ¾¾¾¾¾
High Temp.
¾
®

(5) Mercuration : When treated with alc. solution of mercuric acetate aniline undergoes mercuration.
NH2 NH2
HgOCCH3
+ (CH3COO)2Hg ¾¾® + CH3COOH
O

o– Amino phenyl
mercuric acetate
q Tests of aniline :
u Carbylamine test : Aniline gives carbylamine test or Isocyanide test.
C6H5NH2 + CHCl3 + KOH ¾¾® C6H5NC
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

(Bad smelling)
u Dye test : Aniline is first diazotised. On adding alkaline soln. of b-naphthol to the diazotised
product a scarlet red dye is formed.
u On heating with bromine water, a ppt. is formed.
q Uses of Aniline : Aniline is used in
(i) The manufacture of dyes and dye intermediates
(ii) The manufacture of accelerators and antioxidants in rubber industry.
(iii) The manufacture of acetanilide, sulphuric acid and indigo
(iv) The Manufacture of sulpha drugs.

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40 JEE-Chemistry ALLEN
ARYL HALIDE

If halogen atom is directly attached to the benzene ring, then compound is called as Haloarene.
CH3
CH3 Cl
Cl Cl
Example :
Cl
(Chlorobenzene) (2–Chlorotoluene) (2,4–Dichlorotoluene)
q GENERAL METHODS OF PREPARATION
u Halogenation of Benzene :
Cl

AlCl
+ Cl2 ¾¾¾®
3
+ HCl

u From Phenol :

OH Cl

+ PCl5 ¾¾¾® + POCl3 + HCl

(minor)

3C6H5OH + POCl3 ¾¾® (C6H5)3 PO4 + 3HCl

(major)
u Sandmeyer's reaction :

N2Cl Cl
HCl
+ CuCl ¾¾¾® + N2

N2Cl Br
HBr
+ CuBr ¾¾¾® + N2

u Reaction with KI :

N2Cl I
+ KI ¾¾¾® + N2 + KCl
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

u Balz-schiemann's reaction :

Å 1
F
N2Cl N2BF4
D
+ HBF4 ¾¾¾® ¾¾¾® + BF3 + N2

u Hunsdicker reaction :

COOAg Cl
+ Cl2 ¾¾¾® + CO2 + AgCl

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 ALLEN Aromatic Compounds 41
Nucleophilic Aromatic Substitution by the addition Elimination Mechanism :
(i) The generally accepted mechanism for nucleophilic aromatic substitution in nitro-substituted
aryl halides.

Cl OCH3

CH3OH
+ NaOCH3 + NaCl
85°C

NO2 NO2
p-Chloronitrobenzene p-Nitroanisole

(ii) An ortho - nitro group exert a comparable rate-enhancing effect, m-chloronitrobenzyne while
much more reactive than chlorobenzyne itself, is thousand of times less reactive than either o-or
p-chloronitrobenzene.
(iii) The effect of o- & p-nitro substituents is cummulative, as the rate data for substitution with
methoxide ion in a series of nitro-substituted chlorobenzene derivative demostrate increasing
rate of reaction as :

Cl Cl Cl Cl

NO2 O2N NO2

NO2 NO2 NO2

Chlorobenzene 1-Chloro-4-nitrobenzene 1-Chloro-2, 4-dinitrobenzene 2-Chloro-1, 3, 5-trinitrobenzene
Relative rate : 1.0 7 × 10
10
2.4 × 10
15
(too fast to measure)

(iv) In contrast to nucleophilic substitution in alkyl halides, where alkyl fluorides are exceedingly
unreactive, aryl fluorides undergo nucleophilic substitution readily when the ring bears an o-
or a p-nitro group.
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

F OCH3

CH3OH
+ KOCH3 85°C
+ KF

NO2 NO2
p-Fluoro Potassium p-Nitroanisole Potassium
nitrobenzene methoxide (93%) fluoride

(v) Indeed, the order of leaving group reactivity in nucleophilic aromatic substitution is the opposite
of that seen in alphatic substitution.

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42 JEE-Chemistry ALLEN
(vi) Fluoride is the best reactive leaving group in nucleophilic aromatic substitution, iodide the least
reactive.

Relative reactivity towards sodium methoxide in methanol (50°C)

X = F Cl Br I
312 1.0 0.8 0.4
NO2

(vii) Kinetic studies of many of the reactions described in teh section have demostrated that they
follow a second-order rate law.
Rate = k[aryl halide] [nucleophile]
(viii) Second order kinetics is usually interpreated in terms of a bimolecular rate determining step.
F OCH3

+ NaOCH3 + NaF

NO2 NO2
p-Fluoronitrobenzene Sodium methoxide p-Nitroanisole Sodium Fluoride
Mechanism :
Step -1 - Addition stage. The nucleophile, in this case methoxide ion, adds to the carbon atom that
bears the leaving group to give a cyclohexadienyl anion intermediate.
.. .. ..
:F: :F: :OCH3

H H H .. H
.. slow
+ :OCH
.. 3
H H H H

NO2 NO2
p-Fluoronitrobenzene Methoxide ion Cyclohexadienyl anion intermediate

Step -2 - Elimination stage. Loss of halide form the cyclohexadienyl intermediate restores the aromaticity
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

of the ring and gives the product of nucleophilic aromatic substitution.

.. .. ..
:F: :OCH3 :OCH3
H .. .. H H H .. –
+ F
..
..
..

– Fast
Fluoride ion
H H H H
NO2 NO2

Cyclohexadienyl p-Nitroanisole
anion intermediate

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 ALLEN Aromatic Compounds 43
(a) Dow process :

Cl OH

300°C
+ Aq.NaOH ¾¾¾¾¾®
High pressure + NaCl (via benzyne mechanism)

Presence of deactivating group in ortho and para position makes the nucleophilic substitution easier.
Reactivity Order : (Towards nucleophilic substatitution)

Cl Cl Cl Cl
NO2 NO2 NO2
> > >

NO2 NO2 NO2

Br NH2

liq. NH3
(b) + KNH2 ¾¾¾¾¾® + KBr
low temperature
Strong base

Cl CN

(c) Pyridine, 300°C

¾¾¾¾¾¾®
+ CuCN high pressure
+ CuCl

u Fitting reaction :

dry ether
Cl + 2Na + Cl ¾¾¾¾® + 2NaCl
D

(Diphenyl)

u Wurtz fitting reaction :

dry ether
Cl + 2Na + ClCH2CH2CH3 ¾¾¾¾®
D
CH2CH2CH3 + 2NaCl

u Formation of aryl megnisium halide :

THF
Cl + Mg ¾¾¾¾® MgCl

u Reduction :
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

X
Ni—Al/NaOH
¾¾¾¾¾®

u With Chloral :

H Cl Cl
H2SO4, D
CCl3CHO + ¾¾¾¾® Cl3C —CH
–H2O
H Cl Cl

DDT (insecticide)
p,p–Dichloro diphenyl trichloroethane

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44 JEE-Chemistry ALLEN
u Electrophilic Substitution Reaction :
Cl Cl Cl
Cl
FeCl3
(i) + Cl 2 ¾¾¾¾® +

Cl is o– and p– directing group. Cl

Cl Cl Cl
NO2
(ii) + HNO3
H SO
¾¾¾¾® 2 4
+
D

NO2
Cl Cl Cl
SO3H
(iii) + H2SO4
D
¾¾¾¾® +

SO3H
(iv) Friedal Craft Reaction :
Cl Cl Cl
CH3
AlCl
+ CH3Cl ¾¾¾¾® 3
+
SOLVED EXAMPLES
CH3
Q.1 Which of the following undergoes Hydrolysis most easily :
Cl Cl
Cl Cl NO2 NO2 NO2
NO2
(A) (B) (C) (D)
NO2 NO2
Ans. (D)
Sol. If there is more m-directing group then there will be more nuclephilic substitution reaction.
Q.2 The product in the following reaction is :
Ph – Cl + Fe / Br2 ¾¾¾® Product
(A) o– bromo-chloro benzene (B) p– bromo-chloro benzene
(C) (A) and (B) both (D) 2, 4, 6-tribromo chloro benzene
Ans. (C)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\01_Theory.p65

Q.3 Since – Cl group is deactivating and o/p directing group so only o– and p– products are formed.
Q.4 The most reactive towards SN1 is :
(A) PhCH2Cl (B) Ph–Cl (C) CH3CHCl(CH3) (D) p–NO2—Ph—CH2—Cl
Ans. (A)
Q.5 SN1 the intermediate carbocation is formed.
Å
C6H5—CH2Cl ¾¾® C6H5CH2 is maximum stable due to resonance.
Q.6 Which of the following is used as insecticide :
(A) D.D.T. (B) Chloritone (C) Chloropicrin (D) (A) and (C) both
Ans. (D)

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  Aromatic Compounds 45

AROMATIC COMPOUNDS
EXERCISE # O-I
1. Which of the following is not an aromatic compound :

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

+
AH0001
2. Which of the following group is divalent:
(A) Benzoyl (B) Benzyl (C) Benzal (D) p-Tolyl
AH0002
3. Benzene is a resonance hybrid mainly of two Kekule structures. Hence :
(A) Half of the molecules correspond to one structure, and half of the second structure
(B) At low temperatures benzene can be separated into two structures
(C) Two structures make equal contribution to resonance hybrid
(D) An individual benzene molecule changes back and forth between two structures
AH0003
4. How many  electron are there in the following species :

(A) 2 (B) 4 (C) 6 (D) 8

AH0004
5. The number of benzylic hydrogen atoms in ethylbenzene is:
(A) 3 (B) 5 (C) 2 (D) 7
AH0005
CHCl3 / KOH
6. Trans-Butene-2 Product
Solvent

Cl Cl Cl Cl
H3C Cl
(A) H3C CH3 (B) H3C H (C) (D) Both (A) & (B)
H H H CH3 H H
AH0006
AlCl
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

7. + CH 3CH 2CH 2CH 2Cl 3  hydrocarbon (X) major product X is:

CH 3
|
(A) CH 2CH  CH3 (B) C  CH 3
| |
CH3 CH 3

(C) CH2CH2CH2CH3 (D) None is correct

AH0007

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46 JEE-Chemistry 
8. In the sulphonation, acetylation and formylation of benzene the group of effective electrophiles would
be :
   
(A) SO3 ,CH 3C  O, HCO (B) SO3 , CH3  C  O, HC O
(C) SO3, CH3CHO, CO + HCl (D) HSO3, CH3CO, HCO
AH0008
9. o/p ratio in highest for nitration of which of the following compound ?
(A) Ethyl benzene (B) Toluene
(C) Isopropyl benzene (D) Tertiarybutyl benzene
AH0009
10. Which can be used to generate NO2+ in nitration of benzene ring
(A) HNO3 + H2SO4 (B) HNO3 + HClO4 (C) N2O5 (D) All
AH0010
11. For the electrophilic substitution reaction involving nitration, which of the following sequence regarding
the rate of reaction is true?

(A) k C6 H6 > k C6 D6 > k C (B) k C6 H6 < k C6 D6 < k C

6 T6 6 T6

(C) k C6 H6 = k C6 D6 = k C (D) k C6 H6 > k C6 D6 < k C

6 T6 6 T6

AH0011
12. For the electrophilic substitution reaction involving sulphonation, which of the following sequence regarding
the rate of reaction is true?

(A) k C6 H6 > k C6 D6 > k C (B) k C6 H6 < k C6 D6 < k C

6 T6 6 T6

(C) k C = kC = kC (D) k C > kC < kC

6 H6 6 D6 6 T6 6 H6 6 D6 6 T6

AH0012
Zn Hg
13. C6H6 CH COCl
3 A    B
AlCl 3 HCl

The end product in the above sequence is:

(A) Toluene (B) Ethyl benzene (C) Both the above (D) None
AH0013
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

14. p-Nitrotoluene on further nitration gives:

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

AH0014
15. Reaction of SO3 is easier in:
(A) Benzene (B) Toluene (C) Nitrobenzene (D) chlorobenzene
AH0015

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  Aromatic Compounds 47

16. Which order is correct for the decreasing reactivity to ring monobromination of the following compounds:
(I) C6H5CH3 (II) C6H5COOH (III) C6H6 (IV) C6H5NO2
(A) I > II > III > IV (B) I > III > II > IV (C) II > III > IV > I (D) III > I > II > IV
AH0016
17. The highest yield of m-product is possible by the electrophilic substitution of the following:
(A) C6H5CH3 (B) C6H5CH2COOC2H5
(C) C6H5CH(COOC2H5)2 (D) C6H5C(COOC2H5)3
AH0017
18. Which of the following will undergo sulphonation at fastest rate ?

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

AH0018
19. Aniline under acidic medium, when chlorinated, produces:
(A) o-Chloro aniline (B) m-Chloro aniline
(C) p-Chloro aniline (D) Mixture of ortho and para-chloro aniline
AH0019
20. When sulphonilic acid (p-H2NC6H4SO3H) is treated with excess of bromine water, the product is:
(A) Tribromo product (B) Dibromo product
(C) Monobromo product (D) Tetrebromo product
AH0020
21. In a reaction of C6H5Y, the major product (>60%) is m-isomer, so the group Y is:
(A) –COOH (B) –Cl (C) –OH (D) –NH2
AH0021
22. An aromatic compound of molecular formula C6H4Br2 was nitrated then three isomers of formula
C6H3Br2NO2 were obtained. The original compound is:
(A) o-Dibromobenzene (B) m-Dibromobenzene
(C) p-Dibromobenzene (D) Both A & C
AH0022
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

23. Which of the following is most reactive towards sulphonation?

(A) m-Xylene (B) o-Xylene (C) Toluene (D) p-Xylene
AH0023
24. Ring nitration of dimethyl benzene results in the formation of only one nitro dimethyl benzene. The dimethyl
benzene is :
CH3
CH3
(A) (B) (C) (D) None of these
CH3 CH3
AH0024

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48 JEE-Chemistry 
25. If meta-nitroaniline is chlorinated, the major product is:
NH2 NH2 NH2 NH2
Cl Cl
(A) (B) (C) (D)
NO2 NO2 Cl NO2 NO2
Cl
AH0025
26. If p-methoxy toluene is nitrated, the major product is:

CH3 CH3
NO2
(A) (B) (C) (D) No reaction
NO2
OCH3 OCH3
AH0026
2 2CrO Cl
2 H O
27. C6H5CH3   A 
 B
The functional group present in B and name of the reaction would be
(A) –CHO, Gattermann aldehyde synthesis (B) –CHO, Etard reaction
(C) –COCH3, Friedel Crafts reaction (D) –CHO, Oxo reaction
AH0027

Br KMnO
28. A 2 4  B
 

Compound A and B respectively are:

(A) o-Bromostyrene, benzoic acid (B) p-Bromostyrene, benzaldehyde
(C) m-Bromostyrene, benzaldehyde (D) Styrene dibromide, benzoic acid
AH0028
29. If the mixture of the following four aromatic compounds on oxidation by strong oxidising agent gives:
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

, , and

(A) Mixture of C6H5CH2OH + C6H5COOH (B) Mixture of C6H5CHO + C6H5COOH

(C) Only C6H5COOH (D) None of the above
AH0029
30. Which of the following is/are produced when a mixture of benzene vapour and oxygen is passed over
V2O5 catalyst at 775 K?
(A) Oxalic acid (B) Glyoxal (C) Fumaric acid (D) Maleic anhydride
AH0030

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  Aromatic Compounds 49

31. Benzene on reaction with 'A' forms which on reaction with 'B' forms
'A' and 'B' are:

(A) Zn(Hg) + conc. HCl, (B) , LiAlH4

(C) , NaBH4 (D) , Zn(Hg) + conc. HCl

AH0031
32. Which chloroderivative of benzene among the following would undergo-hydrolysis most readily with
aNaOH to furnish the corresponding hydroxy derivative.

(A) O2N (B) O2N Cl (C) Me2N Cl (D) Cl

AH0032
33. Major product of this reaction will be :

CH Cl
3
AlCl 3 , 

(A) o-Xylene (B) p-Xylene (C) Both (D) m-Xylene

AH0033
34. For preparing monoalkyl benzene, acylation process is preferred than direct alkylation because
(A) In alkylation, a poisonous gas is evolved
(B) In alkylation, large amount of heat is evolved
(C) In alkylation, polyalkylated product is formed
(D) Alkylation is very costly
AH0034
35. Phenol and ethanol are distinguished by the reaction with
(A) Red litmus (B) NaHCO3 (C) FeCl3 (D) Na
AH0035
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

36. An aromatic compound 'A' C7H6Cl2, gives AgCl on bonding with alcoholic AgNO3 solution, and yields
C7H7OCl on treatment with sodium hydroxide. 'A' on oxidation gives a mono chlorobenzoic acid which
affords only one mononitro derivative. The compound A is:

CHCl2

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

AH0036
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50 JEE-Chemistry 

Ni, high temp.

37. + H2 
High pressure 
(A). Which of the following can be isolated as the product of this reaction.

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

AH0037

38. Chloral + Cl Conc

 
. H 2SO 4
 product. The product is:

(A) Lindane (B) DDT (C) Teflon (D) Ethaneperchlorate

AH0038
 Pthalic Anhydride
HCO 3H H3O
39. Acetophenone   A   B + C   

 Indicator (D) ; C & D are
H

(A) CH3OH & (B) PhOH &

(C) PhOH & (D) CH3OH &

AH0039
40. Select the reaction giving correct major product :
NO2 NH 2 CH 3
Br Br
(i) Fe or Sn / HCl (i) Red hot Fe tube
(A) (B) C2H2 (ii) Me–Cl / AlCl
(ii) Br2 / water 3
(iii) Cl2 / hv
Br Cl
:

OH OMe NH 2 OH
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(i) NaHCO3 (i) (NaNO2 + HCl) / 0-5ºC

(C) (ii) Me–I (D) (ii) H3PO2

AH0040
 Al O
H / H 2O
41. Phenol (
i ) NaOH
 A    B 23  C
( ii ) CO 2 / 140C CH 3COOH , 

In this reaction, the end product C is:

(A) Salicylaldehyde (B) Salicylic acid (C) Phenyl acetate (D) Aspirin
AH0041

E
  Aromatic Compounds 51
42. m-Aminophenol on treatment with NaOH and CO2 gives which of the following as major product?

NH2
(A) (B) (C) (D)

AH0042
43. Stability order of following singlet halocarbene is

(A) CF2 > CCl2 > CBr2 > CI2 (B) CI2 > CBr2 > CCl2 > CF2

(C) CCl2 > CF2 > CBr2 > CI2 (D) CF2 > CI2 > CCl2 > CBr2
AH0043
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

E
52 JEE-Chemistry 
EXERCISE # O-II
1. In which of the following reaction t-butylbenzene is formed:
BF . HF
(A) Benzene + iso-butyl chloride, AlCl3 (B) Benzene + (CH3)2C = CH2 3 


(C) Benzene + t-butyl alcohol H2SO

4 
 (D) Benzene + (CH3)2 C= CH2 AlCl
3 
AH0044
2. The replacement of a hydrogen atom in benzene by alkyl group can be brought about with the following
reagents :
(A) Alkyl chloride and AlCl3 (B) Alkene and AlCl3
(C) Alkanol and alkali (D) Alkanol and acid
AH0045
3. Benzene reacts with n-propyl chloride in the presence of anhydrous AlCl3 to give predominantly:
(A) n-Propylbenzene (B) Isopropylbenzene
(C) 3-Propyl-1-chlorobenzene (D) Cumene
AH0046
4. The structure of the compound that gives a tribromo derivative on treatment with bromine water is:

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

AH0047
5. Electrophilic attack of NO 
2 at meta position is observed in:

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

AH0048
6. The good method for converting benzene into n-propyl benzene is:
(A) C6H6 + CH3CH2CH2Cl + Anhyd. AlCl3
(B) C6H6 + CH3CH2COCl + Anhyd. AlCl3 and then treatment with Zn/Hg/HCl
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(C) C6H6 + CH3CH2COCl + Anhyd. AlCl3 and then treatment with H2 Ni

(D) C6H6 + Anhyd. AlCl3 + cyclopropane
AH0049
7. Which of the following can be used as reagent in Friedel Crafts reaction?
NO2

(A) (B) CH2=CH–Cl (C) CH3CH2Cl (D) CH2=CH–CH2–Cl

AH0050

E
  Aromatic Compounds 53

O O
|| ||
8. Of the species PhSR, PhSR , PhSR and Ph  S  OR the meta-substituted product is obtained from
|| || ||
O O O
O O
|| ||
(A) PhSR (B) PhSR (C) PhSR (D) Ph  S  OR
|| || ||
O O O
AH0051
9. Amongst the following, the moderately activating group is
R
||
(A) —NHR (B) —NHCOCH3 (C) – O – C – R (D) —CH3
AH0052
10. False statement is / are :
(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 group to the
meta position.
AH0053
11. Benzoic acid may be prepared by the oxidation of:

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

AH0054
12. Identify reactions give ketone product ?
OEt O O
1. BF3 Anhydrous
(A) + R—C —OEt + (B) + O
2. H3O AlCl3
OEt
O
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

+ Me–C–O
H3O Dry distillation
(C) PhMgBr + Me–C N (D) Ca
Me–C–O
O
AH0055

E
54 JEE-Chemistry 
13. Which of the following reaction(s) will give aromatic product ?

H
Cl
C=O H2 N + SbCl5
(A) H (B)
+
C=O H2 N
H
O O

HBr H
+
(C) (D) + H 2N–OH

AH0056
14. Which of the following statements is/are not true?
(A) All ortho-para directing groups activates the ring towards electrophilic substitution.
(B) Halobenzene is ortho para directing but deactivating in nature
(C) All meta-directing groups have -bond on the atom directly attached to the ring
(D) All meta directing groups are deactivating.
AH0057
15. Which of the following is not an ortho-para directing group?

(A) CF3 (B) CCl3 (C) –CH=CH–COOH (D) – N  C
AH0058
16. Which of the following does not gives Fridel-Crafts reaction?

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

AH0059
17. Which of the following reactions of benzene proves the presence of three carbon–carbon double bonds in
it :
(A) Formation of a triozonide
(B) Hydrogenation of benzene to cyclohexane
(C) Formation of C6H6Cl6 by addition of chlorine
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(D) Formation of nitrobenzene on heating benzene with a mixture of concentrated nitric acid and
sulphuric acid
AH0060
18. Which of the following are classified as aromatic ?
(A) 1, 2, 3-Triphenylcyclopropenium cation (B) Cyclooctatetraenyl dianion
(C) Azulene (D) Annulene [10]
AH0061
19. Which of the following is/are name of 1,2,3,4,5,6 - hexachloro cyclohexane :
(A) Lindane (B) Gammexane (C) 666 (D) BHC
AH0062

E
  Aromatic Compounds 55
20. Among the following reaction sequences identify incorrect step :
COOMe COOMe COOMe CH2–OH Br
Cl Cl Cl Cl Cl
NaOH NaH/Me–I LiAlH4 PBr3
(I) (a) (b) (c) (d)
Cl OH OMe OMe OMe
Cl Cl Cl Cl Cl
+ –
NO2 NO2 NH2 N2Cl I

Br2 +FeBr3 H2/Pd NaNO2+HCl KI

(II) (a) (b) (c) (d)

Br Br Br Br
Me Me Me Me COOH
Br +
Br +
Br
SO3 NBS/hv H / KMnO4 / H
(III) H2SO4 (b) (c) (d)
(a)
SO3H SO3H

O O
Br COOH C–OMe C–OMe
Br2 + Fe (1) Mg/Dry-ether + Na / Liq. NH3
H / MeOH
(IV) (a) (2) CO / H+
2
(c) (d)
(b)

(A) I–a ; II – b ; III – c ; IV – d (B) I–b ; II – a ; III – d ; IV – d

(C) I–a ; II – a ; III – b ; IV – d (D) I–b ; II – a ; III – d ; IV – c
AH0063
21. How many of following compounds are less reactive than benzene for sulphonation by
conc. H2SO4 :
O
+
OH CH3 NO2 Cl COOPh NMe3 NH–C–CH3 D
D D

D D
D
(A) 2 (B) 4 (C) 6 (D) 8
AH0064
22 . Decide the correct order of reactivity of following compounds towards halogenation with (Cl2 + AlCl3).
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

COOPh CH3 Et

I II III IV

(A) I > II > III > IV (B) II > III > IV > I
(C) III > II > IV > I (D) II > III > I > IV
AH0065

E
56 JEE-Chemistry 
23 Which of the following method(s) is/are not used to prepare p-bromo aniline as major product :
NH 2 NH2 NH 2 NH2
Br2 CH3COCl Br2 NaOH/H2O
(A) H2O
(B) FeBr3 

NH 2 Br NH2 NH 2 Br NH2

H2SO4 Br2 KCN LiAlH4 Br2

(C) FeBr3 (D) NaNO2/HCl CuCN FeBr3
0-5°C 

Br Br
AH0066
OH OH OH
COOH
(i) NaOH
24. + X +
(ii) Acidification

COOH
X is/are -
(A) CHCl3 (B) CCl4 (C) CO2 (D) HCOOH
AH0067
25. Which product is/are not obtained in following reaction.
(i) CH3COCl/Anhy.AlCl3
(ii) Ph3P = CH–CH3
(iii) BH3 / THF
–
(iv) H2O2 / OH

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

OH OH OH
OH
AH0068

NH2
Ac2O HNO3 Chromatographic
A B + C separation B
Pyridine + H2SO4
(Major)
26. +
H3O
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

Zn
E + HCl D + Acid
E is :

NH2 NH2

(A) (B) (C) H2N NH–C–CH3 (D) NH2

O NH2
NH2 NO2

AH0069

E
  Aromatic Compounds 57
O2 conc.
27. Cumene A Acetone + B C.
hv H2SO4 O
C +
O, H
C
O
Identify correct statement :
(A) Product C is phenophthalein indicater
(B) Product B gives CO2 effervescence with NaHCO3
(C) Product A formation involves carbocation intermediate
(D) Product B gives no colour with neutral FeCl3
AH0070

AlCl
28. 3  ? Major Product is :

(A) (B) H3COC OH

(C) (D)

AH0071
Paragraph for 29 to 30
Identify reagent used and intermediate products in following conversion.

SO3 HNO3
H2SO4 H2SO4
II I

A
Br

C B

CO2H
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

Mg

+
D then H

+
H
E F heat
III + IV
major minor
CH2OH CHO product product
HO
alkenes

E
58 JEE-Chemistry 
29. Identify II product -
NO2 SO3H CH3 N=O

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

AH0072
30. (III) major product is ?
COOH

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

AH0072
31. Match the following :
Column-I Column-II
(Properties) (Compound)
O–H

(A) CO2is evolved from NaHCO3 (P)

OH
O2N NO2
(B) Gives libermann nitroso test (Q)

NO2

:
H–N–Me

(C) Gives yellow oily liquid with NaNO2+HCl (R)

H
(D) Evolve a colourless gas with active metals (S) N
:

AH0073
32. Match the following :
Column I Column II
(Compound) (Properties)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

Cl

(A) (P) o-p directing

CH3

(B) (Q) m-directing

E
  Aromatic Compounds 59

SO3H

(C) (R) Activating towards electrophile

ONa
(D) (S) Deactivating towards electrophile

AH0074
33. Match the column :
Column I Column II
(Reaction) (Product & its property)

(A) + CrO3 in CH3COOH  ? (P) Tropylium ion

(B) + Ph3C? (Q) Benzaldehyde

(C) + n-Pr Br + ZnCl2  ? (R) Product can oxidise by KMnO4/H+

AlCl
(D) C6H6 + CO + HCl 3  ? (S) Aromatic product obtained
AH0075
34. Column - I Column - II
(Reactions (Intermediate formed or type of reaction)

O – O
OH
(A) (P) Product obtained as racemic mixture
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

O
+ H+
(B) OH OH O O (Q) Substitution reaction

E
60 JEE-Chemistry 

conc conc
(C) + HNO + H SO (R) Nu– Addition takes place during reaction
3 2 4

NO2

O OH
(1) LAH
(D) (2) H2O (S) Carbocation intermediate

(T) Carbanion intermediate

AH0076

node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

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  Aromatic Compounds 61

EXERCISE # S-I
\ 1. Write the most stable resonating structure for the cyclohexadienyl anion formed by reaction of methoxide
ion with o-fluoronitrobenzene.
AH0077
2. Write the principal organic product in each of the following reactions:

H NNH ( i ) HNO , H SO
3 2
(i) 2 2  B (ii)    4  C
triethylene ( ii ) NaOCH 3 ,CH 3OH
glycol

(iii) + CH3CH2ONa  D (iv) + C6H5CH2SNa  E

AH0078
Cl NH2

(i) NaNO2 ,HBr ( i ) NBS, Benzoyl peroxide ,CCl , heat

3. (i)     E (ii) 4
          F
( ii ) CuBr (ii ) NaSCH 3

AH0079
4. Reaction of 1,2,3-tribromo-5-nitrobenzene with sodium ethoxide in ethanol gave a single product,
C8H7Br2NO3, in quantitative yield. Suggest a reasonable structure for this compound.
AH0080
5. Compare the given characteristics of aniline and cyclohexanamine :
(i) Both are primary amine
(ii) Both can be acylated by RCOCl
(iii) Both reacts with CHCl3/KOH
(iv) Both reacts with NaNO2 + HCl at 0-5ºC
(v) Both reacts with PhSO2Cl to give a compound which is soluble in KOH
(vi) Both gives coupling reaction with phenol
(vii) Both gives electrophilic substitution reaction
How many of the given characteristics are correct?
AH0081
6. Number of compounds which can show faster rate of nucleophilic substitution of halogen
Br
than :
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

NO2
NO2 F Cl NO2
Cl I
(i) (ii) (iii) (iv)
NO2 NO2
NO2
F
Br
NO2

(v) (vi) AH0082

NO2
NO2
E
62 JEE-Chemistry 
7. Identify total number of reactions incorrectly match with its product ?

+
(a) N2Cl + NO2 N=N

NO2

NH2 NH2 NH2

Me
AlCl3
(b) + Me–Cl +

Me

conc.
(c) Et–OH + NaI H SO Et – I
2 4

Me Me Me
Br
+ Br2 Fe +
(d)
Me Me Me
Major
product Br
Minor
product

(e) Me–CCH + Na/Liq NH3  Me–CH = CH2

O O Br
(f) + Br2 / CCl4
Br
100 % product [Stereo specific reactions] / 100 % 
[ 
]

Me Me + Me Me
H /
(g)

SO3H
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(h) Conc.
H2SO4, 150ºC
Major product

AH0083

E
  Aromatic Compounds 63

Paragraph for No. 8 to 9

For given reaction sequence molecular formula for compound 'U' is C7H6O2 & P gives negative Fehling
test.

NaOH O3
P + Q R Zn, H2O
S + P

HgSO4
H2SO4 CrO2Cl2

KMnO4
W HotRed
Fe tube
V NaOH
CaO,
U T

8. Compound which is not a hydrocarbon

(A) W (B) R (C) T (D) V
AH0084
9. Compound S is :

CH = O
(A) CH3 – CH = O (B) Ph – CH = O (C) (D) CH – CH2 – CH
CH = O
O O
AH0084
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

E
64 JEE-Chemistry 

EXERCISE # (MAINS)
OH
– +
O Na
1. + CHCl3 + NaOH 
CHO
The electrophile involved in the above reaction is [AIEEE-2006]

(1) dichlorocarbene ( :CCl2) (2) trichloromethyl anion (C Cl3 )
 
(3) formyl cation (C HO) (4) dichloromethyl cation (C HCl 2 )
AH0085

2. The electrophile, E attacks the benzene ring to generate the intermediate  –complex. Of the
following, which  –complex is of lowest energy ? [AIEEE-2008]
NO 2 NO 2 NO 2

H
H
(1) + (2) + E (3) (4) + H
+ E
E
H E
AH0086
3. In the chemical reactions, [AIEEE-2010]
NH2
NaNO2 HBF 4
HCl, 278 K
A B

the compounds 'A' and 'B' respectively are :-

(1) Nitrobenzene and chlorobenzene
(2) Nitrobenzene and fluorobenzene
(3) Phenol and benzene
(4) Benzene diazonium chloride and fluorobenzene
AH0087
4. In the chemical reactions
NH2
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

NaNO2 CuCN

HCl,278K
 A 
 B, the compounds A and B respectively are : [AIEEE-2011]

(1) Fluorobenzene and phenol

(2) Benzene diazonium chloride and benzonitrile
(3) Nitrobenzene and chlorobenzene
(4) Phenol and bromobenzene
AH0088

E
  Aromatic Compounds 65

5. Sodium phenoxide when heated with CO2 under pressure at 125ºC yields a product which on
acetylation produces C. [JEE(Main)-2014]
ONa
+
+ CO2 125º H
5 atm. B Ac2O
C

The major product C would be :

OH OCOCH3 OCOCH3 OCOCH3
COOCH3 COOH COCH3
(1) (2) (3) (4)
COOH
COCH3
AH0089
6. In the reaction [IIT-2015]

NH3

NaNO2/HCl CuCN/KCN
0–5°C
D 
E+N2

CH3

the product E is :-

CN CH3 COOH

(1) (2) (3) (4) H3C CH 3

CH 3 CH 3

AH0090
7. In the following sequence of reactions : [IIT 2015]
KMnO 4 SOCl2 H2/Pd
Toluene A B C
BaSO4

the product C is :-
(1) C6H5CH2OH (2) C6H5CHO (3) C6H5COOH (4) C6H5CH3
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

AH0091
8. Which of the following compounds will significant amont of meta product during mono-nitration reaction
? [JEE(Main)-2017]
OH OCOCH 3 NH2 NHCOCH 3

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

AH0092

E
66 JEE-Chemistry 
9. Phenol on treatment with CO2 in the presence of NaOH followed by acidification produces compound
X as the major product. X on treatment with (CH3CO)2O in the presence of catalytic amount of H2SO4
produces : [JEE(Main)-2018]

O CO2H
O CH3 O O CH3 O
C
O CO2H O CH3
(1) (2) OH (3) (4)
O CH3
CO2H
CO2H O

AH0093
10. Phenol reacts with methyl chloroformate in the presence of NaOH to form product A. A reacts with Br2
to form product B. A and B are respectively : [JEE(Main)-2018]

O O O O O O O O
(1) and (2) and O
O O O Br
Br

OH OH
OH Br OH
OCH3 OCH3
(3) and (4) OCH3 and OCH3
O Br O
O O

AH0094
11. The increasing order of nitration of the following compound is :-[JEE(Main)-2018(ONLINE)]

NH2 Cl OCH3 CH3

node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(a) (b) (c) (d)

(1) (b) < (a) < (c) < (d) (2) (b) < (a) < (d) < (c)
(3) (a) < (b) < (c) < (d) (4) (a) < (b) < (d) < (c)
AH0095

E
  Aromatic Compounds 67

12. The major product of the following reaction is : [JEE(Main)-2018(ONLINE)]

O
(i) ClCH2CH2CCl
(ii) AlCl3(anhyd.)
MeO OH

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

AH0096
13. Products A and B formed in the following reactions are respectively : [JEE(Main)-2018(ONLINE)]

NH3CH3COO
C6H5NH2
+ HNO2 A B

SO3H
N = N COCH3

and HO3S N NH2

(1) H
SO3H

O
H
N = N – OCCH3 N=N–N

(2) and

SO3H SO3H

O
N = N – O–CCH3 N=N NH2
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(3) and
SO3H SO3H

N = N COCH3 N=N

(4) and
SO3H SO3H
AH0097

E
68 JEE-Chemistry 
14. The major product of the following reaction is : [JEE(Main)-2018(ONLINE)]

(i) OHC CH2COCl

(ii) H2SO 4, heat
MeO OH

OMe O OMe O

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

MeO O O
O O MeO O O

AH0098
15. The compounds A and B in the following reaction are, respectively: [JEE-Mains (JAN)-2019]
HCHO+HCI AgCN
A A

(1) A = Benzyl alcohol, B = Benzyl isocyanide

(2) A = Benzyl alcohol, B = Benzyl cyanide
(3) A = Benzyl chloride, B = Benzyl cyanide
(4) A = Benzyl chloride, B = Benzyl isocyanide
AH0099
16. The major product of the following reaction is: [JEE-Mains (JAN)-2019]
O OH
CH3
O+
AlCl3,

OH OH
H 3C CH3

(1) O (2)
O

OH OH
CH3 CH3
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(3) (4)
O
O
AH0100
17. Which of the following compounds is not aromatic ? [JEE-Mains (JAN)-2019]

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

 N  H
AH0101

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  Aromatic Compounds 69
18. The major product of the following reaction is: [JEE-Mains (JAN)-2019]

CH3O
(i) AlCl 3 (anhyd.)
CH2Cl (ii) H O

2

CH3O CH3O
CH3O
CH3O CH3
(1) (2) (3) (4)
CH3
AH0102
19. What will be the major product in the following mononitation reaction ?
O
N HNO3 [JEE-Mains (JAN)-2019]
H Conc. H2SO4

O NO2 O
(1) N (2) O 2N N
H H

O 2N O
O
N
(3) N (4) H
H O2N
AH0103
20. Which compound(s) out of the following is/are not aromatic ? [JEE-Mains (JAN)-2019]

 
(A) (B) (C) (D)

(1) C and D (2) B, C and D (3) A and C (4) B

AH0104
21. The major product of the following reaction is : [JEE-Mains (JAN)-2019]
OH
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

Br2 (excess)
 
SO3 H
OH OH OH OH
Br Br Br Br Br
(1) (2) (3) Br Br (4)
Br SO3H Br SO3H
AH0105

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70 JEE-Chemistry 
22. Which of the following compounds will produce a precipitate with AgNO3?
[JEE-Mains (JAN)-2019]
Br Br Br
Br
(1) (2) (3) (4)
N
AH0106
23. The major product of the following reactionis :- [JEE-Mains (JAN)-2019]
HO (1) HCl
(2) AlCl3 (Anhyd.)

Cl HO Cl HO
(1) (2) (3) (4)

AH0107
24. Among the following four aromatic compounds, which one will have the lowest melting point ?
[JEE-Mains (JAN)-2019]
O CH3
OH
OH O
(1) (2) (3) O (4)
OH
O CH3
AH0108
25. The major product of the following reaction is : [JEE-Mains (JAN)-2019]
CH3O (1) Cl2/CCl4
(2) AlCl3(anhyd.)
Cl Cl
CH3O CH3O
(1) CH3O (2) CH3O (3) (4)
Cl
Cl

AH0109
26. The major product in the following reaction is : [JEE-Mains (April)-2019]
NH2
N N
Base
+ CH3 I  
N
H N
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

NH2
NH2
+ N N
N NCH3
(1) (2) N
N N
H N CH3
NH2 NHCH3
N N N N
(3) (4)
N + N
N H N
H
CH3
AH0110

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  Aromatic Compounds 71
27. Coupling of benzene diazonium chloride with 1-napthol in alkaline medium will give

N
OH ||
N
HO
(1) (2) [JEE-Mains (April)-2019]
N=N

N
||
N
(3) (4)

OH

AH0111
28. The major product of the following reaction is: [JEE-Mains (April)-2019]

O Cl

O+ (i)AlCl3 ,heat

(ii)H 2O


O
CO2H
Cl
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(1) (2)
Cl
O O

O Cl
O

(3) (4)
CO2H Cl O

AH0112

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72 JEE-Chemistry 
29. The mojor product of the following reaction is : [JEE-Mains (April)-2019]

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

AH0113
30. The increasing order of reactivity of the following compounds towards aromatic electrophilic substitution
reaction is : [JEE-Mains (April)-2019]

Cl OMe Me CN

A B C D

(1) D < B < A < C (2) A < B < C < D (3) D < A < C < B (4) B < C < A < D
AH0114
31. Aniline dissolved in dilute HCl is reacted with sodium nitrite at 0ºC. This solution was added dropwise
to a solution containing equimolar mixture of aniline and phenol in dil. HCl. The structure of the major
product is : [JEE-Mains (April)-2019]

(1) (2)

(3) (4)
AH0115
32. p-Hydroxybenzophenone upon reaction with bromine in carbon tetrachloride gives:
[JEE-Mains (April)-2019]
O Br O
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

Br
(1) (2)
HO HO
O O
Br
Br
(3) (4)
HO HO
AH0116

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  Aromatic Compounds 73
33. The major product of the following reaction is : [JEE-Mains (April)-2019]
O
 
HI excess
 

NC O

OH I OH I

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

NC I NC OH NC OH NC I
AH0117
34. The increasing order of the reactivity of the following compounds towards electrophilic aromatic substitution
reactions is :- [JEE-Mains (April)-2019]

Cl CH3 COCH3

(I) (II) (III)

(1) I < III < II (2) II < I < III (3) III < I < II (4) III < II < I
AH0118
35. Which of the following is NOT a correct method of the preparation of benzylamine from cyanobenzene
? [JEE-Mains (April)-2019]
(1) (i) HCl/H2O (ii) NaBH4
(2) (i) LiAIH4 (ii) H3O+
(3) (i) SnCl2+HCl(gas) (ii) NaBH4
(4) H2/Ni
AH0119
36. Compound A (C9H10O) shows positive iodoform test. Oxidation of A with KMnO4/KOH gives acid
B(C8H6O4). Anhydride of B is used for the preparation of phenolphthalein. Compound A is :-
[JEE-Mains (April)-2019]

CH3 CH3
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

CH3
(1) (2)
O O CH3

O
CH3
CH2–C–H
(3) (4) O
CH3

AH0120

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74 JEE-Chemistry 
37. The major product obtained in the given reaction is :- [JEE-Mains (April)-2019]
CH3 AlCl3
O CH2 CH3 Product
CH2 CH
Cl

H 3C O CH CH3 H 3C O CH2
(1) CH2 CH (2) CH2 CH = CH2

CH3
H 3C O
(3) CH3 O (4)

CH3

AH0121
38. In the following reaction sequence [JEE-Mains (Jan)-2020]

NH2
Ac2O Br2
A B
AcOH

CH3

the major products B is -

NHCOCH3 NHCOCH3 NHCOCH3 NHCOCH3
Br Br COCH3
(1) (2) (3) (4)
Br
CH3 CH 2Br CH3 CH3
AH0122
39. Consider the following reactions : [JEE-Mains (Jan)-2020]
anhyd.AlCl3
(a) + Cl

Cl Cl
anhyd.AlCl3
+ Cl2 Cl Cl
(b)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

dark
(excess)
Cl Cl
anhyd.AlCl3
(c) + CH2=CH–Cl CH=CH2

anhyd.AlCl3
(d) + CH2=CH–CH 2Cl CH2–CH=CH2

Which of these reactions are possible ?

(1) (a) and (d) (2) (b) and (d)
(3) (a) and (b) (4) (b) , (c) and (d)
AH0123

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  Aromatic Compounds 75
40. A solution of m-chloroaniline, m-chlorophenol and m-chlorobenzoic acid in ethyl acetate was extracted
initially with a saturated solution of NaHCO3 to give fraction A. The left over organic phase was extracted
with dilute NaOH solution to give fraction B. The final organic layer was labelled as fraction C. Fractions
A, B and C, contain respectively : [JEE-Mains (Jan)-2020]
(1) m-chlorobenzoic acid, m-chloroaniline and m-chlorophenol
(2) m-chloroaniline, m-chlorobenzoic acid and m-chlorophenol
(3) m-chlorobenzoic acid, m-chlorophenol and m-chloroaniline
(4) m-chlorophenol, m-chlorobenzoic acid and m-chloroaniline
AH0124
41. Consider the following reaction : [JEE-Mains (Jan)-2020]
CH 3     OH–
N +Na SO3 N2Cl 'X'
CH 3

The product 'X' is used :

(1) in acid base titration as an indicator
(2) in protein estimation as an alternative to ninhydrin
(3) in laboratory test for phenols
(4) as food grade colourant
AH0125
42. In the following sequence of reactions the maximum number of atoms present in molecule 'C' in one plane
is _________. [JEE-Mains (Jan)-2020]
Re d hot CH Cl(1.eq.)
A 
Cu tube B  3
Anhydrous AlCl

C
3

(A is a lowest molecular weight alkyne)

AH0126
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

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76 JEE-Chemistry 
EXERCISE # (ADVANCE)
1. The chlorination of toluene in presence of ferric chloride gives predominatly: [JEE 1986]
(A) Benzyl chloride (B) m-Chlorotoluene (C) Benzal chloride (D) o-and p-Chlorotoluene
AH0127
2. The most basic compound among the following is: [JEE 1990]
(A) Benzylamine (B) Aniline (C) Acetaniline (D) p-Nitro aniline
AH0128
3. When nitrobenzene is treated with Br2 in presence of FeBr3 the major product formed is
m-bromonitrobenzene. Correct statements are : [JEE 1992]
(A) The electron density on meta carbon is more than on ortho and para position.
(B) The intermediate carbonium ion formed after initial attack of Br+ attack the meta position
is least destabilized.
(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 form the meta position than from ortho and para position.
AH0129
4. Choose the correct statement from the ones given below for two aniline in: [JEE 1993]

(A) II is not an acceptable canonical structure because carbonium ions are less stable than
ammonium ions
(B) II is not an acceptable canonical structure because it is non aromatic
(C) II is not an acceptable canonical structure because the nitrogen has 10 valence electrons
(D) II is an acceptable canonical structure
AH0130
5. Most stable carbonium ion is: [JEE 1995]
(A) p – NO2 – C6H4 – CH2 + +
(B) C6H5 CH2
(C) p – Cl – C6H4– CH2 + (D) p – CH3O – C6H4 – +CH2
AH0131
6. Arrange in order of decreasing trend towards SE reactions: [JEE 1995]
(I) Chlorobenzene (II) Benzene (III) Anilinium chloride(IV) Toluene
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(A) II > I > III > IV (B) III > I > II > IV (C) IV > II > I > III (D) I > II > III > IV
AH0132
7. Among the following statements on the nitration of aromatic compounds, the false one is:
(A) The rate of benzene is almost the same as that of hexadeuterobenzene [JEE 1997]
(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
AH0133

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  Aromatic Compounds 77

8. Nitrobenzene can be prepared from benzene by using a mixture of conc. HNO3 and conc. H2SO4. In the
nitrating mixture HNO3 acts as a: [JEE 1997]
(A) Base (B) Acid (C) Reducing agent (D) Catalyst
AH0134
9. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with: [JEE 1998]
(A) SO2Cl2h (B) SOCl2 (C) Cl2 h (D) NaOCl
AH0135
10. The most unlikely representation of resonance structure of p-nitrophenoxide ion is:[JEE 1998]

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

AH0136
11. Benzenediazonium chloride on reaction with phenol in weakly basic medium gives: [JEE 1998]
(A) Diphenyl ether (B) p-hydrooxyazobenzene
(C) Chlorobenzene (D) Benzene
AH0137
12. 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 [JEE 1999]
(C) activates the ring by hyperconjugation (D) deactivates the ring
AH0138
13. Amongst the following the strongest base is: [JEE 2000]
(A) C6H5NH2 (B) p-O2NC6H4NH2 (C) m-O2NC6H4NH2 (D) C6H5CH2NH2
AH0139
14. Identify the correct order of reactivity in electrophilic substitution reactions of the following compounds:

(I) (II) (III) (IV) [JEE 2002]

(A) I > II > III > IV (B) IV > III > II > I (C) II > I > III > IV (D) II > III > I > IV
AH0140
( CH ) NH
15. F 3 2
NO2    A (i)
 
NaNO 2 HCl 05 C
   B [JEE 2003]
DMF (ii) H 2 Catalytic Reduction
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(A) O2N NH2 (B) N NH2

H3 C
(C) N NO2 (D) N NO2
H2 C
NH2
AH0141

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78 JEE-Chemistry 

Br
16. 2
 [JEE 2004]
Fe
Major product of above reaction is:

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

AH0142
17. Which of the following is obtained when 4-Methylbenzenesulphonic acid is hydrolysed with excess of
sodium acetate? [JEE 2005]
—
(A) CH3 CO O N a (B) CH3 + SO3

(C) CH3 SO 3 N a + CH3COOH (D) CH3 SO2O. COCH3 + NaOH
AH0143
AlCl (i) O / 
18.  Cl  CH 2CH 2  CH 3 3  P 
2
 Q  Phenol [JEE 2006]
(ii ) H3O
The major products P and Q are

(A) and CH3CH2CHO (B) and CH3COCH3

(C) and CH3COCH3 (D) and CH3CH2CHO

AH0144
Question No. 19 to 21 ( 3 questions)
Comprehension I
RCONH2 is converted into RNH2 by means of Hofmann bromamide degradation.
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

O O O
Cl Cl Cl
NH2 NH–Br N–Br
••
(i) (ii) (iii)

O–M+ O
O C
H2N Cl N Cl N Cl
H
(vi) (v) (iv)

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  Aromatic Compounds 79

In this reaction, RCONHBr is formed from which this reaction has derived its name. Electron donating

group at phenyl activates the reaction. Hofmann degradation reaction is an intramolecular reaction.

19. How can the conversion of (i) to (ii) be brought about? [JEE 2006]

(A) KBr (B) KBr + CH3ONa (C) KBr + KOH (D) Br2 + KOH
AH0145
20. Which is the rate determining step in Hofmann bromamide degradation? [JEE 2006]

(A) Formation of (i) (B) Formation of (ii) (C) Formation of (iii)

(D) Formation of (iv)
AH0145
21. What are the constituent amines formed when the mixture of (i) and (ii) undergoes Hofmann bromamide
degradation ? [JEE 2006]
15
CONH2 CONH2
D
(i) (ii)

15 15
(A) NH2 , NH2 , NH2 , NH2
D D

15
(B) NH2 , NH2
D
15 15
(C) NH2 , NH2

15
(D) NHD ,
AH0145
Paragraph for Question Nos. 22 to 25 (4 questions)
Riemer-Tiemann reaction introduces an aldehyde group, on to the aromatic ring of phenol, ortho to the
hydroxyl group. This reaction involves electrophilic aromatic substitution. This is a general method for the
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

synthesis of substituted salicylaldehydes as depicted below.

OH ONa OH
CHO CHO
aq. HCl
[I]
[Intermediate]
CH3 CH3 CH3
(I) (II) (III)

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80 JEE-Chemistry 
22. Which one of the following reagents is used in the above reaction ? [JEE 2007]
(A) a NaOH + CH3Cl (B) a NaOH + CH2Cl2
(C) a NaOH + CHCl3 (D) aNaOH + CCl4
AH0146
23. The electrophile in this reaction is [JEE 2007]
(A)  CHCl (B) +CHCl2 (C)  CCl 2 (D)  CCl 3
AH0146
24. The structure of the intermediate I is [JEE 2007]
ONa ONa ONa ONa
CH2Cl CHCl2 CCl3 CH2OH
(A) (B) (C) (D)

CH3 CH3 CH3 CH3

AH0146
25. In the following reaction, [JEE 2007]

conc . HNO
   3  X
conc. H SO
2 4

the structure of the major product 'X' is

O2N
O O
(A) (B)
N NO2 N
H H

O O
(C) (D)
N O2N N
H H
NO2
AH0147
26. Statement - 1 : Bromobenzene upon reaction with Br2 / Fe gives 1, 4-dibromobenzene as the major
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

product.
and
Statement-2 : In bromobenzene, the inductive effect of the bromo group is more dominant than the
mesomeric effect in directing the incoming electrophile.
(A) Statement-1 is True, Statement-2 is True ; Statement-2 is a correct explanation for Statement-1
(B) Statement-1 is True, Statement-2 is True ; Statement-2 is NOT a correct explanation for Statement1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True [JEE 2008]
AH0148

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  Aromatic Compounds 81
27. Statement-1 : Aniline on reaction with NaNO2 / HCl at 0°C followed by coupling with -naphthol
gives a dark blue coloured precipitate.
and
Statement-2 : The colour of the compound formed in the reaction of aniline with NaNO2 / HCl at 0°
followed by coupling with -naphthol is due to the extended conjugation.
(A) Statement-1 is True, Statement-2 is True ; Statement-2 is a correct explanation for Statement-1
(B) Statement-1 is True, Statement-2 is True ; Statement-2 is NOT a correct explanation for Statement1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True [JEE 2008]
AH0149
OH

In the reaction NaOH(aq) / Br

28.   the intermediate(s) is(are) –
2 [JEE 2009]

O O O O
Br
(A) (B) (C) (D)
Br
Br Br Br Br
AH0150
29. The compounds P, Q and S [JEE 2009]

O
COOH OCH3 C
O
HO H3 C
P Q S
were separately subjected to nitration using HNO3 / H2SO4 mixture. The product formed in each case
respectively, is
COOH OCH3 O
(A) C
HO H3C O
NO2 NO2 O2 N

COOH OCH3 O
(B) C
HO NO2 H3C O
NO2 NO2
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

O NO2
COOH OCH3
C
(C) O
HO H3C NO2
NO2
O
COOH OCH3
C
(D) O NO2
HO H3C NO2
NO2
AH0151

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82 JEE-Chemistry 
30. The correct acidity order of the following is : [JEE 2009]

OH OH COOH COOH

(I) Cl (III) CH 3
(II) (IV)

(A) (III) > (IV) > (II) > (I) (B) (IV) > (III) > (I) > (II)
(C) (III) > (II) > (I) > (IV) (D) (II) > (III) > (IV) > (I)
AH0152
31. Match the reactions in Column–I with appropriate options in Column–II.
Column–I Column–II [IIT-JEE-2010]
NaOH/H2O
(A) N 2Cl + OH N=N OH (P) Racemic mixture

OH OH O
H2SO4
(B) H3C–C—–C–CH3 C CH3 (Q) Addition reaction
CH3 CH3 CH3 C
CH3
CH3

O OH
C 1. LiAlH 4
(C) + CH (R) Substitution reaction
CH3 2. H3O
CH 3

(D) HS Cl Base S (S) Coupling reaction

(T) Carbocation intermediate

AH0153
O
(1) NaOH/Br2
32. In the reaction H3C C O T.
(2) C
NH2 Cl
(i)
The structure of the Product T is : [JEE 2010]
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

O
(A) H3C C O (B) NH
O–C C CH3
O
O
(C) H3C NH (D) H3C C O
C NH–C
O

AH0154

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  Aromatic Compounds 83
33. Match the reactions in Column-I with appropriate types of step/reactive intermediate involved in these
reactions as given in Column-II
Column-I Column-II [IIT-JEE-2012]
H3C O O
O
(A) aq NaOH
  (P) Nucleophilic substitution

O O
CH 3MgI
(B) CH2CH2CH2Cl    CH3 (Q) Electrophilic substitution

18 O
O
18
H 2SO 4
(C) CH2CH2CH2OH   (R) Dehydration

CH2CH2CH2C(CH3)2 H 2SO 4
(D)   (S) Nucleophilic addition
OH
H3C CH3
(R) Carbanion
AH0155
34. Among P, Q, R and S, the aromatic compound(s) is / are : [JEE 2013]
Cl
AlCl3
  P

NaH
  Q

(NH 4 )2 CO3

100 115ºC
 R
OO
O
HCl
 S
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(A) P (B) Q (C) R (D) S

AH0156
35. The major product(s) of the following reaction is (are) - [JEE 2013]

OH

AqueousBr2 (3.0equivalents)
 

SO3H

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84 JEE-Chemistry 

OH OH OH OH
Br Br Br Br Br

Br Br Br Br Br
SO3H Br Br SO3H
(P) (Q) (R) (S)

(A) P (B) Q (C) R (D) S

AH0157
36. In the following reaction, the product (s) formed is (are) [JEE 2013]

OH

CHCl3
 

OH

CH3

O OH OH
OH
CHO
OHC CHO

H 3C CHCl2 H 3C CHCl2 CH3

CH3
(P) (Q) (R) (S)

(A) P (major) (B) Q (minor) (C) R (minor) (D) S (major)

AH0158
Paragraph for Question 37 and 38
P & Q are isomers of dicarboxylic acid C4H4O4. Both decolourize Br2/H2O, On heating P forms the
cyclic anhydride.
Upon treatment with dilute alkaline KMnO4, P as well as Q could produce one or more than one from
S, T and U. [JEE 2013]
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

COOH COOH COOH

H OH H OH HO H
H OH HO H H OH
COOH COOH COOH
(S) (T) (U)

E
  Aromatic Compounds 85
37. In the following reaction sequences V and W are , respectively -
H2 / Ni
Q  V

AlCl3 (anhydrous) 1.Zn Hg/ HCl

+V   
2.H PO
W
3 4

O
CH2OH
(A) O and (B) and
CH2OH
O (V) (W)
O
(V) (W)

O
HOH2C
(C) O and (D) and
CH2OH CH2OH
O (V)
(W)
(V) (W)

AH0159
38. Compounds formed from P and Q are respectively
(A) Optically active S and optically active pair (T, U)
(B) Optically inactive S and optically inactive pair (T, U)
(C) Optically active pair (T, U) and optically active S
(D) Optically inactive pair (T, U) and optically inactive S
AH0159
39. In the reaction shown below, the major product(s) formed is / are : [JEE 2014]
NH2

acetic anhydride
NH2 CH 2 Cl2
  product(s)

O
H
N CH3 NH2
O
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(A) + CH3COOH (B) H + CH3COOH

NH2 N CH3

O O O
H  
N CH3 NH3CH3COO
O
(C) H + H2O (D) H
N CH3 N CH3

O O O O
AH0160

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86 JEE-Chemistry 
40. The reactivity of compound Z with different halogens under appropriate conditions is given
below : [JEE 2014]

OH mono halo substituted derivative when X2=l2

X2
di halo substituted derivative when X2=Br2
C(CH3)3
Z tri halo substituted derivative when X2=Cl2

The observed pattern of electrop hilic substitution can be explained by -

(A) The steric effect of the halogen
(B) The steric effect of the tert-butyl group
(C) The electronic effect of the phenolic group
(D) The electronic effect of the turt-butyl group
AH0161
41. Match the four starting materials (P , Q, R, S) given in List I with the corresponding reaction scheme
(I, II, III, IV) provided in List - II and select the correct answer using the code given below in lists.
[JEE 2014]
List - I List - II
(P) H H (1) Scheme I
– +
(i) KMnO4, HO, heat (ii) H, H2O
(iii) SOCl2 (iv) NH3
? C7H6N2O3
OH

(Q) (2) Scheme II

OH
(i) Sn/HCl (ii) CH3COCl (iii) conc.H2SO4
(iv) HNO3 (v) dil.H2SO4, heat (vi) HO–
? C6H6N2O2
NO2

(R) (3) Scheme III

node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

(i) red hot iron, 873 K (ii) fuming HNO3, H2SO4, heat
(iii) H2S.NH3 (iv) NaNO2, H2SO4 (v) hydrolysis
? C6H5NO3

NO2

(S) (4) Scheme IV

CH3

E
  Aromatic Compounds 87

(i) conc. H2SO4, 60ºC

(ii) conc. HNO3, conc. H2SO4 (iii) dil. H2SO4, heat
? C6H5NO4
Code :
P Q R S
(A) 1 4 2 3
(B) 3 1 4 2
(C) 3 4 2 1
(D) 4 1 3 2
AH0162
42. The major product U in the following reactions is : [IIT 2015]
+
CH2=CH–CH 3,H radical initiator, O 2
high pressure, heat T U

H H
O O
O H3C CH3 O CH2
CH3 O CH2 O H
O H (C) O
(A) (B) (D)

AH0163
43. In the following reactions, the major product W is : [IIT 2015]
OH
NH2 , NaOH
NaNO2, HCl
0º C
V W

OH

N=N OH N=N
(A) (B)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

HO

OH
N=N
(C) N=N (D)

AH0164

E
88 JEE-Chemistry 
44. Among the following the number of reaction(s) that produce(s) benzaldehyde is : [IIT 2015]
CHCl2
CO, HCl H2O
I. II.
Anhydrous AlCl3/CuCl 100°C

CO2Me
COCl DIBAL-H
III. H2 IV. Toluene, –78°C
Pd-BaSO4 H2 O
AH0165
45. The correct statements(s) about of the following reaction sequence is(are) [IIT 2016]
(i) O2 CHCl3/NaOH
Cumene(C9H12) + P Q (major) + R (minor)
(ii) H3O
NaOH
Q S
PhCH2Br
(A) R is steam volatile
(B) Q gives dark violet coloration with 1% aqueous FeCl3 solution
(C) S gives yellow precipitate with 2, 4,-dinitrophenylhydrazine
(D) S gives dark violet coloration with 1% aqueous FeCl3 solution
AH0166
46. The product(s) of the following reaction sequence is(are) [IIT 2016]
NH2
(i) Acetic anhydride/pyridine
(ii) KBrO3 / HBr
+
(iii) H3O , heat
(iv) NaNO2 / HCl, 273-278 K
(v) Cu/HBr
Br Br Br Br
Br Br Br Br
(A) (B) (C) (D)
Br
Br Br
AH0167
47. Among the following reaction(s) which gives (give) tert-butyl benzene as the major product is(are)
[IIT 2016]
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

Br
Cl
(A) (B)
NaOC2H5 AlCl3

OH
(C) (D)
H2SO4 BF3.OEt2

AH0168

E
  Aromatic Compounds 89
48. The IUPAC name(s) of the following compound is(are) : [IIT 2017]

H3 C Cl

(A) 4-methylchlorobenzene (B) 4-chlorotoluene

(C) 1-chloro-4-methylbenzene (D) 1-methyl-4-chlorobenzene
AH0169
49. Among the following, the number of aromatic compound (s) is : [IIT 2017]

  

 

Answer 50, 51 and 52 by appropriately matching the information given in the three columns
of the following table.
Columns 1, 2 and 3 contains starting materials, reaction conditions, , and type of reactions,
respectively .
Column 1 Column 2 Column 3
(I) Toluene (i) NaOH/Br2 (P) Condensation
(II) Acetophenone (ii) Br2 / hv (Q) Carboxylation
(III) Banzaldehyde (iii)(CH3CO)2O/CH3COOK (R) Substitution
(IV) Phenol (iv) NaOH/CO2 (S) Haloform
AH0170
50. For the synthesis of benzoic acid, the only CORRECT combination is
(A) (III) (iv) (R) (B) (IV) (ii) (P) (C) (I) (iv) (Q) (D) (II) (i) (S)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

AH0171
51. The only CORRECT combination in which the reaction proceeds through radical mechanism is
(A) (I) (ii) (R) (B) (II) (iii) (R) (C) (III) (ii) (P) (D) (IV) (i) (Q)
AH0171
52. The only CORRECT combination that gives two different carboxylic acids is
(A) (IV) (iii) (Q) (B) (III) (iii) (P) (C) (II) (iv) (R) (D) (I) (i) (S)
AH0171

E
90 JEE-Chemistry 
53. The major product of the following reaction is :
OH
i) NaNO2, HCl, 0°C
ii) aq. NaOH

NH2
–
O Na+ OH OH
N=N OH
(A) (B) (C) (D)
N2Cl N=N Cl

AH0172
Paragraph for 54 & 55
The reaction of compound P with CH3MgBr (excess) in (C2H5)2O followed by addition of H2O gives
Q, The compound Q on treatment with H2SO4 at 0ºC gives R. The reaction of R with CH3COCl in
the presence of anhydrous AlCl3 in CH2Cl2 followed by treatment with H2O produces compounds S.
[Et it compounds P is ethyl group] [IIT 2017]

54. The reactions, Q to R and R to S, are -

(A) Dehydration and Friedel -Crafts acylation
(B) Friedel-Crafts alkylation, dehydration and Friedel-Crafts acylation
(C) Aromatic sulfonation and Friedel-Crafts acylation
(D) Friedel-Crafts alkylation and Fridel-Crafts acylation
AH0173
55. The product S is -

HO3S
(H3C)3C O CH3 H3COC
(H3C)3C H3C CH3
(A) (B)

COCH3
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

H3C CH3
COCH3 (H3C)3C
(H3C)3C CH3
(C) (D)

COCH3

AH0173

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  Aromatic Compounds 91
56. The reaction(s) leading to the formation of 1,3,5-trimethylbenzene is (are) [IIT 2018]
O heated iron tube
Conc. H2 SO4
(A) (B) Me H
873 K


O
1) Br2, NaOH CHO
2) H3O+
(C) 3) sodalime,  (D) Zn/Hg, HCl
OHC CHO
O O
AH0174
Paragraph "X"
Treatment of benzene with CO/HCl in the presence of anhydrous AlCl3/CuCl followed by reaction with
Ac2O/NaOAc gives compound X as the major product. Compound X upon reaction with
Br2/Na2CO3, followed by heating at 473 K with moist KOH furnishes Y as the major product. Reaction
of X with H2/Pd-C, followed by H3PO4 treatment gives Z as the major product. [IIT 2018]
(There are two questions based on PARAGRAPH "X", the question given below is one of them)
57. The compound Y is :-
OH Br
COBr Br COBr
(A) (B) (C) (D)
HO O Br
AH0175
Paragraph "X"
Treatment of benzene with CO/HCl in the presence of anhydrous AlCl3/CuCl followed by reaction with
Ac2O/NaOAc gives compound X as the major product. Compound X upon reaction with Br2/Na2CO3,
followed by heating at 473 K with moist KOH furnishes Y as the major product. Reaction of X with
H2/Pd-C, followed by H3PO4 treatment gives Z as the major product.
(There are two question based on PARAGARAPH "X", the question given below is one of them)
58. The compound Z is :-
OH

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

O O O
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

AH0175
59. Aniline reacts with mixed acid (conc. HNO3 and conc. H2SO4) at 288 K to give P (51%), Q (47%)
and R (2%). The major product(s) the following reaction sequence is (are) :- [IIT 2018]

1) Ac2O, pyridine 1) Sn/HCl

2) Br2, CH3CO2H 2) Br2/H2O (excess)
R S major product(s)
3) H3O+ 3) NaNO 2, HCl/273-278K
4) NaNO2, HCl/273-278K 4) H3PO2
5) EtOH, 

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92 JEE-Chemistry 

Br Br Br Br
Br Br
(A) (B) (C) (D)
Br Br Br Br Br Br
Br Br Br
AH0176
60. In the following reaction sequence, the amount of D (in g) formed from 10 moles of acetophenone is____.
[IIT 2018]
–1
(Atomic weight in g mol : H = 1, C = 12, N = 14, O = 16, Br = 80. The yield (%) corresponding
to the product in each step is given in the parenthesis)
O

NaOBr NH3, Br2/KOH Br2(3 equiv)

A B C D
H3O+ (60%) (50%) (50%) AcOH (100%)
AH0177
61. Scheme 1 and 2 describe the conversion of P to Q and R to S, respectively. Scheme 3 describes the
synthesis of T from Q and S. The total number of Br atoms in a molecule of T is ________
Scheme 1 : [IIT 2019]

(i) Br2 (excess), H2O

NH2 (ii) NaNO 2, HCl, 273 K
(iii) CuCN/KCN
+
Q
(iv) H3 O , (major)
(v) SOCl2, pyridine
P

Scheme 2 :
(i) Oleum
(ii) NaOH, 
+
S
(iii) H (major)
R (iv) Br2, CS2 273 K

Scheme 3 :
(i) NaOH
S T
(ii) Q (major)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

AH0178
62. Choose the correct option(s) that give(s) an aromatic compound as the major product.
[IIT 2019]
H3C i) alc.KOH
ii) NaNH2
UV, 500K Br 
iii) red hot iron tube,873 K

(1) + Cl 2 (excess)   (2)
Br
Br
NaOEt NaOMe
(3)   (4) 
AH0179

E
  Aromatic Compounds 93
63. Choose the correct option(s) for the following reaction sequence [IIT 2019]

CHO
i)Hg2 , dil.H2SO4 Zn Hg
ii)AgNO3 , NH 4OH
i)SOCl2 pyridine conc. HCl

 Q 
iii)Zn Hg, conc. HCl
ii) AlCl 3
R  S
MeO
Consider Q, R and S as major products

OH

CO2H

(1) MeO MeO

Q S

CO2H
(2) MeO MeO
O
Q R

(3) MeO MeO

O
R S

(4) MeO MeO

O
R S
AH0180
64. Answer the following by appropriately matching the lists based on the information given in
the paragraph
List-I includess starting materials and reagents of selected chemical reactions. List-II gives structures of
compounds that may be formed as intermediate products and/or final products from the reactions of
List-I [IIT 2019]
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

List-I List-II
i) DlBAL-H
CN CHO
(I) O ii) dil, HCl (P)
iii) NaBH4
CO2H
O iv) conc. H2SO4

i) O3 OH
(II) ii) Zn, H2O (Q) OH
CO2H iii) NaBH4
iv) conc. H2SO4

E
94 JEE-Chemistry 

Cl i) KCN
(III) ii) H3O,+  (R) O
CO2CH3 iii) LiAlH 4
iv) conc. H2SO4

CO 2Me OH
i) LiAlH4
(IV) CO2Me (S)
ii) conc. H2 SO4 CO2H

CO2H
(T)
CO2H

(U) O

O
Which of the following options has correct combination considering List-I and List-II?
(1) (III), (S), (R) (2) (IV), (Q), (R)
(3) (III), (T), (U) (4) (IV), (Q), (U)
AH0181
65. Answer the following by appropriately matching the lists based on the information given in
the paragraph
List-I includess starting materials and reagents of selected chemical reactions. List-II gives structures of
compounds that may be formed as intermediate products and/or final products from the reactions of
List-I [IIT 2019]
List-I List-II
i) DlBAL-H
CN CHO
(I) O ii) dil, HCl (P)
iii) NaBH4
CO2H
O iv) conc. H2SO4

i) O3 OH
(II) ii) Zn, H2O (Q) OH
CO2H iii) NaBH4
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

iv) conc. H2SO4

Cl i) KCN
+
(III) ii) H3O ,  (R) O
CO2CH3 iii) LiAlH4
iv) conc. H2SO4

CO 2Me OH
i) LiAlH4
(IV) CO2Me (S)
ii) conc. H2 SO4 CO2H

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  Aromatic Compounds 95

CO2H
(T)
CO2H

(U) O

O
Which of the following options has correct combination considering List-I and List-II?
(1) (I), (Q), (T), (U) (2) (II), (P), (S), (U)
(3) (II), (P), (S), (T) (4) (I), (S), (Q), (R)
AH0182
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

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96 JEE-Chemistry 

AROMATIC COMPOUNDS _ ANSWER KEY

EXERCISE # O-I
1 Ans. (B) 2 Ans. (C) 3 Ans. (C) 4 Ans. (C) 5 Ans. (C)
6 Ans. (B) 7 Ans. (D) 8 Ans. (B) 9 Ans. (B) 10 Ans. (D)
11 Ans. (C) 12 Ans. (A) 13 Ans. (B) 14 Ans. (A) 15 Ans. (B)
16 Ans. (B) 17 Ans. (D) 18 Ans. (B) 19 Ans. (B) 20 Ans. (A)
21 Ans. (A) 22 Ans. (B) 23 Ans. (A) 24 Ans. (C) 25 Ans. (B)
26 Ans. (B) 27 Ans. (B) 28 Ans. (D) 29 Ans. (C) 30 Ans. (D)
31 Ans. (D) 32 Ans. (A) 33 Ans. (D) 34 Ans. (C) 35 Ans. (C)
36 Ans. (A) 37 Ans. (A) 38 Ans. (B) 39 Ans. (C) 40 Ans. (A)
41 Ans. (D) 42 Ans. (C) 43 Ans. (A)
EXERCISE # O-II
1 Ans. (A,B,C,D) 2 Ans. (A,B,D) 3 Ans. (B,D) 4 Ans. (B,C,D)
5 Ans. (A,B,C) 6 Ans. (B,D) 7 Ans. (C,D) 8 Ans. (C,D)
9 Ans. (B,C) 10 Ans. (B,C,D) 11 Ans. (A,B) 12 Ans. (A,B,C,D)
13 Ans. (A,B,C) 14 Ans. (A,C) 15 Ans. (A,B,D) 16 Ans. (B,C,D)
17 Ans. (A,B,C) 18 Ans. (A,B,C) 19 Ans. (A,B,C,D) 20 Ans. (C)
21 Ans. (B) 22 Ans. (A) 23 Ans. (A,C,D) 24 Ans. (B,C)
25 Ans. (A,B,D) 26 Ans. (A) 27 Ans. (A) 28 Ans. (A)
29 Ans. (B) 30 Ans. (A) 31 Ans. (A)-Q, (B)-P,R,S, (C)-R,S, (D)-
P,Q,R,S
32 Ans. (A)-P, S ; (B)- P, R ; (C)-Q, S ; (D)-P, R
33 Ans. (A)Q,R,S ; (B)P,R,S ; (C)R,S ; (D)Q,R,S
34 Ans. (A)  R, T ; (B)  R, S ; (C)  Q, S ; (D)  P, R
EXERCISE # S-I
O¯ O
NO2 N
F OCH3
1 Ans. F

NH–NH2 CF3 OCH2CH3 SCH2–C6H5

NO2 NO2 NO2
2 Ans. (i) (ii) (iii) (iv)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

NO2
NO2 OCH 3 NO2 NO2
Cl Br
Br
3 Ans. (i) (ii)
CH2 OCH3
Br Br CH3S
Br OC2H5
4 Ans.
O2N Br O N Br
2

E
  Aromatic Compounds 97

Solution for No. 8 & 9

O
C—H
O
P = Q = CH3–C–H R = Ph–CH = CH–CHO

O
CH3 C–OH
CH = O
S = T = U=
CH = O

V = W = HC  CH

EXERCISE # (MAINS)
1 Ans. (1) 2 Ans. (2) 3 Ans. (4) 4 Ans. (2)
5 Ans. (3) 6 Ans. (1)

 
NH 2 N 2Cl CN

NaNO2/HCl CuCN/KCN
Sol. + N2
0–5ºC 
CH 3 CH3 CH3
D E
Formation of D is example of Diazotisation
Formation of E from D is example of Sandmayer's Reaction

7 Ans. (2)

O Cl O H
CH3 COOH C C
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

KMnO 4 H2 Pd
Sol. 
Oxidation
 SOCl2
  
BaSO

4
(Rosenmund
reduction )
(Toluene)

8 Ans. (3) 9. Ans.(4) 10. Ans.(2) 11. Ans.(4)

12. Ans.(1) 13. Ans.(3) 14. Ans.(4) 15. Ans. (4)
16. Ans. (1) 17. Ans. (3) 18. Ans. (2) 19. Ans. (3)
20. Ans. (2) 21. Ans. (1) 22. Ans. (4) 23. Ans. (2)
24. Ans. (1) 25. Ans.(4) 26. Ans. (Bonus) 27. Ans. (3)
28. Ans. (3) 29. Ans. (2) 30. Ans. (3) 31. Ans. (1)

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98 JEE-Chemistry 
32. Ans. (4) 33. Ans. (1) 34. Ans.(3) 35. Ans. (1)
36. Ans. (1) 37. Ans. (4)
38. Ans. (1)
O
NH2 NH–C–CH3
O O O
CH3–C–O–C–CH3
 + Me–C–OH
Sol.
CH3 CH3
(A) Br2/ACOH

O
NH–C–CH3
Br

CH3
39. Ans. (2)
Cl
Cl Cl Cl
anhyd. AlCl
3
anhydrous + Cl2 
Sol. (a) + No reaction (b) dark Cl Cl
AlCl 3
Cl
(electrophilic substitution)
AlCl3 3 AlCl –CH2–CH=CH2
(c) + CH2=CH–Cl No reaction (d) + CH2=CH–CH2–Cl 

40. Ans. (3)

Sol. NH2 OH COOH

Cl Cl Cl

O = C – OH O = C – O– Na+
NaHCO3
+ H2CO3  H2O + CO2
Cl Cl

Fraction-A
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

OH O –Na+

NaOH

Cl Cl

Fraction-B

NH2

Cl

Fraction-C
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  Aromatic Compounds 99
41. Ans. (1)
Sol.
H3 C – –
N + Cl NN SO3 Na+
H3C

Me
–
N N=N SO3 Na+
Me
(Methyl orange)
It is an acid base indicator
42 Ans. (13)

Sol. (H–C C–H) Red Hot

Cu-tube
(A)
Lowest m.wt. alkyne CH 3 – Cl (1eq)
Anhydrous
AlCl3
H
H
C H

Total 13 atom are present in same plane (7 carbon & 6 hydrogen atoms. )
EXERCISE # (ADVANCE)
1 Ans. (D) 2 Ans. (A) 3 Ans. (A,B) 4 Ans. (C)
5 Ans. (D) 6 Ans. (C) 7 Ans. (C) 8 Ans. (A)
9 Ans. (A,C) 10 Ans. (C) 11 Ans. (B) 12 Ans. (A,C)
13 Ans. (D) 14 Ans. (C) 15 Ans. (B) 16 Ans. (D)
17 Ans. (C) 18 Ans. (C) 19 Ans. (D) 20 Ans. (D)
21 Ans. (B) 22 Ans. (C) 23 Ans. (C) 24 Ans. (B)
25 Ans. (B) 26 Ans. (C) 27 Ans. (D) 28 Ans. (A,B,C)
29 Ans. (C) 30 Ans. (A)
31 Ans. (A)R, S, T ; (B)T ; (C)P, Q ; (D)R 32 Ans. (C)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aromatic Compound\Eng\02_Ex.p65

33 Ans. (A)(R,S,T) ; (B)(P, S) ; (C)(R, S) ; (D)(Q, R)

34 Ans. (A,B,C,D) 35 Ans. (B) 36 Ans. (B,D) 37 Ans. (A)
38 Ans. (B) 39 Ans. (A) 40 Ans. (A,B,C) 41 Ans. (C)
42 Ans. (C) 43 Ans. (A) 44 Ans. (4) 45. Ans. (B,C)
46. Ans. (B) 47. Ans. (B,C,D) 48. Ans. (B,C) 49. Ans. (5)
50. Ans. (D) 51. Ans. (A) 52. Ans. (B) 53. Ans. (C)
54. Ans. (B) 55. Ans. (D) 56. Ans.(A,B,D) 57. Ans.(C)
58. Ans.(A) 59. Ans.(D) 60. Ans.(495) 61. Ans. (4.00)
62. Ans. (2,4) 63. Ans. (2,4) 64. Ans. (2) 65. Ans. (2)