chemistry

AROMATIC hydrocarbons
Sakshi Vora

IIT - Roorkee

10th, 12th CBSE State Topper

7+ Years of Teaching Experience

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Aromatic
hydrocarbons
 Aromaticity -
Aromatic Compounds :-
All cyclic compounds which are unusually stabilized than its
analogous open chain compound
Rules for compound to be aromatic

Compound must:
A. Be planar : either sp or sp2
B. Be cyclic
C. Conjugated πe-
D. LARGEST CONJUGATED BOUNDARY
(4n + 2) π e-, where n≥0
Anti-Aromatic Compounds

All cyclic compounds which are highly unstable than its open chain
analogous system

Condition for Anti-aromatic compounds:

Compounds must not be

A. Be planar
B. Be cyclic
C. Be conjugated
LARGEST CONJUGATED BOUNDARY

A. Must have 4n π e-
Non-Aromatic Compounds

All cyclic compounds which are comparatively stable than their

open chain analogous system

Condition for non-aromatic compounds:

Compounds must not be
A. Aromatic
B. Non-Aromatic
Practice
Questions
The number of sp2 hybrid orbitals in a molecule of benzene is :

A. 24
B. 6
C. 18
D. 12

[Main Jan. 09, 2020 (II)]

Which compound (s) out of the following is/are not aromatic ?

A. (B), (C) and (D)

B. (C) and (D)
C. (B)
D. (A) and (C) [Main Jan. 11, 2019 (I)]
Which of the following compounds is not aromatic ?

A.

B.

C. [Main Jan. 9, 2019 (II)]

D.
Which of the following compounds will show highest dipole
moment ?

A. (I)
B. (II)
C. (III)
D. (IV)
[April 9, 2017]
Among the following, the number of aromatic compound(s) is

[Adv. 2017]
Reactions of
Aromatic
compounds
 Note
Reactions of aromatic compounds
(i) Aromatic compounds do not prefer add reaction at normal
conditions

(ii) Aromatic compounds always prefer to show substitution

reaction
Electrophilic
Aromatic
Substitution
Electrophilic aromatic substitution
Mechanism of Electrophilic Aromatic Substitution
Important
points
Important points

1. Carbocation intermediate is formed

2. Formation of sigma complex/ arenium ion is the RDS
Rate of EAS
Rate of EAS

1. Check the stability of arenium ion

2. Nucleophilicity of aromatic compound
Practice
Questions
Arrange in the order of electrophilic attack

NH2 OCH3
Identify the correct order of reactivity in electrophilic
substitution reactions of the following compounds

A. 1 > 2 > 3 > 4 [2002S]

B. 4 > 3 > 2 > 1
C. 2 > 1 > 3 > 4
D. 2 > 3 > 1 > 4
Important
reactions of
benzene
Types of Activating groups
Activating Groups

1. HIGHLY ACTIVATING

1. MODERATELY ACTIVATING

1. WEAKLY ACTIVATING
Types of Activating groups
Types of Deactivating groups
Deactivating Groups

1. HIGHLY DEACTIVATING

1. MODERATELY DEACTIVATING

1. WEAKLY DEACTIVATING
Types of Deactivating groups
Nitration of
Benzene
Nitration of benzene
Common reagents for nitration

(i) HNO3 + H2SO4

(ii) Conc HNO3

(iii) Dil HNO3

(iv) N2O5
+ - + -
(v) NO2BF4 / NO2ClO4
Mechanism of nitration
Important
points about
Nitration
Important points about nitration

1. Attacking electrophile is NO2+

2. Carbocation intermediate is formed
3. Nitric acid behaves as a base
4. Nitration is irreversible
Important points

Toluene on reaction with fuming nitric acid gives TNT

Important points

Highly activating rings on nitration give ortho, meta and para

products with meta in appreciable amounts
Alternative to direct nitration

CONVERT aniline to acetanilide by adding acetyl chloride or acetic

anhydride
Practice
Questions
[Main. 2018]
[JEE Main 2017]
Sulphonation
of benzene
Sulphonation of benzene

1. It is a reversible process
2. Can use conc sulphuric acid or oleum
Mechanism of sulphonation
Important
points
Important points about sulphonation
NOTE -

(i) Attacking electrophile is SO3

(ii) Carbocation (arenium ion) intermediate

(iii) No change of Poly Sulphonation

(iv) Reversible process and desulphonation can be carried out

Practice
Questions
Predict the product of the following reaction

H+ , Δ
Predict the product of the following reaction

D+ , Δ
For a long time ?
Halogenation
of benzene
Halogenation of benzene
Reagents used for halogenation
(a) X2 or X2 / lewis Acid (AlCl3 , BF3, BCl3, SbCl5 etc)
(b) Interhalogen compound
I - Cl , Br - Cl , I - Br etc
Mechanism of halogenation
Important
points
Important points about halogenation

● Use of lewis acid is must to increase the electrophilic character,

however an activated ring does not require the use of lewis acid
● Attacking electrophile is X+ (X+ FeX-4)
● Carbocation (Arenium Ion)
Important points about halogenation

● Iodination of benzene is reversible where as chlorination and

bromination is irreversible
● Poly halogenation will not occur.
Practice
Questions
Predict the product of the following reaction

+ Cl2 ⟶ ?
 Predict the product of the following reaction

Fe
+ Cl2 ⟶ ?

Cl2 / h𝝂

?
Important
points
Note -
If - SO3H / - COOH is present at ortho and para position of
highly activated group then it undergoes desulphonation /
decarboxylation during reaction with Br2 / H2O
Practice
Questions
Predict the product

Br2 / H2O ?
Predict the product of the following reaction

Br2/CS2

Br2/H2O
Predict the product of the following reaction

CS2
+ Br2

H2O
+ Br2
Friedel Craft
Alkylation
Friedel craft alkylation
Reagents used for Friedel craft alkylation

(i) R - X , lewis Acid ( AlCl3 / BF3 / FeCl3 …. )

(ii) R - OH, H+
(iii) Alkene , H+
Mechanism of FC alkylation
Important
points
Important points

● Attacking electrophile is R+
● Carbocation intermediate
● Rearrangement is possible
● Formation of arenium Ion is r.d.s
Practice
Questions
Predict the product of the reaction

+ AlCl3
Predict the product of the reaction

CH3Cl + Cl2/AlCl3
Predict the product

Cl

+ AlCl3
Important
points
Important points

Highly deactivated rings never show Friedel craft alkylation

Highly activated rings never show Friedel Craft Alkylation
Practice
Questions
predict the product of the reaction

AlCl3
+ CH3Cl
predict the product of the reaction

AlCl3
+ CH3Cl
[JEE Main 2020]
predict the product

Cl anhyd
Cl
AlCl3
The major product U in the following reactions is

[Adv. 2015]
Friedel Craft
Acylation
FC Acylation
Reagents used for FC Acylation
Mechanism of FC Acylation
Important
points
Important points

● Electrophile is acyl carbocation

● No rearrangement is possible
● Highly activated and highly deactivated rings do not show
friedel craft acylation
Predict the product of the reaction
Practice
Questions
Among the following, reaction(s) which gives (give) tert-butyl
benzene as the major product is (are)

A.

B.
[Adv. 2016]

C.

D.
Among P, Q, R and S, the aromatic compound(s) is/ are

[Adv. 2013 - I]

A. P
B. R
C. Q
D. S
Nucleophilic
Aromatic
substitution
Introduction
+ NaOH ⟶ ?
SN2 Ar
Mechanism of SN2 Ar
Important points of SN2 Ar
1. Carbanion intermediate is formed
2. It is a bimolecular reaction
3. First step, formation of M complex is RDS
Practice
Questions
Compare the rate of reaction
Predict the product of the reaction

+ NaOH ⟶ ?
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Bratin Mondal Top Results Amaiya singhal
100 %ile 100 %ile
 11th / 9, 10

12th / Drop

SAKSHI SAKSHI