Aromatic Hydrocarbons Complete Lecture

Aliphatic and

aromatic
hydrocarbons
Aromatic
Compounds

 Originated from word “Aroma” means pleasant smell

 Some variation do exist
 Functional group –C=C-
 Low hydrogen content
 Chemical reactions different from alkenes
 Undergo substitution reactions as compared to addition reaction
 Basic structural unit of aromatic compounds is benzene
 Highly stable compounds
 Stability is referred as aromaticity.
The Criteria for Aromaticity
 A molecule must be cyclic.
 To be aromatic, each p orbital must overlap with p orbitals on

adjacent atoms.
 A molecule must be planar.
 A molecule must be completely conjugated.
4
 A molecule must satisfy Hückel’s rule
Hückel's rule:
5
6
 As the number of fused rings increases, the number of resonance
structures increases. Naphthalene is a hybrid of three resonance
structures whereas benzene is a hybrid of two.
Examples of Aromatic Rings

Benzene
• Isolated in 1825 by Michael H
Faraday who determined C:H
ratio to be 1:1. C H
• Synthesized in 1834 by H C C
Eilhard Mitscherlich who
determined molecular C C
formula to be C6H6. H C H
• Structure was proposed in H
1866 by Friedrich Kekulé,
Unusual behavior of Benzene
 Alkene + KMnO4  diol (addition)
Benzene + KMnO4  no reaction.
 Alkene + Br2/CCl4  dibromide (addition)
Benzene + Br2/CCl4  no reaction.
Unusual Stability
Structure of benzene
1. Six membered ring and each carbon is sp2 hybridized
2. Each carbon has unhybridized p orbital perpendicular to
the ring which overlaps around the ring.
3. 𝜋 electrons are not confined to a specific carbon and are
represented as a cloud above and below the benzene ring
4. All c-c bond length are equal
5. Structure is planar
August Kekulé proposed that benzene was a rapidly equilibrating mixture of
two compounds, each containing a six-membered ring with three alternating 
bonds. i.e. the bond between any two carbon atoms is sometimes a single bond
and sometimes a double bond.
• The resonance description of benzene consists of two equivalent Lewis
structures, each with three double bonds that alternate with three single
bonds.
• The true structure of benzene is a resonance hybrid of the two Lewis
structures, with the dashed lines of the hybrid indicating the position of the 
bonds.
• We will use one of the two Lewis structures and not the hybrid in drawing
benzene. This will make it easier to keep track of the electron pairs in the 
bonds (the  electrons).
Reactivity of Aromatic
compounds/ Benzene
• Benzene does not undergo electrophilic addition

• It undergoes electrophilic aromatic substitution maintaining
the aromatic core
• Electrophilic aromatic substitution replaces a proton on
benzene with another electrophile
1. Bromination / Chlorination
H Br
Br2, FeBr3
+ HBr
H Cl
Cl2, FeCl3
+ HCl
Bromination Mechanism
2. Nitration
NO2
HNO3, H2SO4
+ H2O
Formation of electrophile
+ -
HNO3 + H2SO4 NO2 + H2O + HSO4
Nitration Mechanism
3. Sulfonation
fuming sulfuric acid
H SO3H
SO3, H2SO4
O
S
O O H OSO3H
SO3H
OSO3H
H
4. Friedel-Crafts Acylation
Mechanism
Step 1
O
O
+ -
C   C
Cl AlCl3 R C O AlCl4
R R
acylium ion
Step 2
O
O
C
C R
H Cl AlCl3
OR O O
C C C
R R R
H H H
O
C
R + HCl
5. Friedel-Crafts Alkylation
Mechanism
CH3 CH3
CH3 C Cl AlCl3 CH3 C AlCl4
CH3 CH3
t-butyl carbocation
CH3 (CH3)3C (CH3)3C (CH3)3C

CH3 C
H
CH3
resonance stabilized intermediate
Cl AlCl3
(CH3)3C
+ HCl
(+ AlCl 3)
Product possibility
1st
2nd
Carbocations Rearrangement
H
CH3CH2CH2CH2 Cl AlCl3 CH3CH2CHCH2
o
1
hydride shift
CH3CH2CHCH3
2o
Electrophilic Aromatic Substitution of
Substituted Benzenes
Substituent
Ortho
Meta
Para
• Effect of substituent
1. The rate of the reaction
2. The orientation
Directing Effects
EDG EWG
electron donating groups electron withdrawing groups

activate ring deactivate ring
atom attached is atom attached is

usually sp3 usually sp2 or sp
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Aliphatic and

 Originated from word “Aroma” means pleasant smell

 To be aromatic, each p orbital must overlap with p orbitals on

 A molecule must be completely conjugated.

Examples of Aromatic Rings

• Benzene does not undergo electrophilic addition

CH3 (CH3)3C (CH3)3C (CH3)3C

electron donating groups electron withdrawing groups

atom attached is atom attached is

Ortho/para directors Meta directors

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