Chapter 14

Aromatic Compounds
Benzene – a remarkable compound
Discovered by Faraday 1825
Formula C6H6
Highly unsaturated, but remarkably
stable
Whole new class of benzene derivatives –
called
aromatic compounds
BENZENE : Resonance description
Later spectroscopic evidence showed all bond
lengths in benzene to be equal and intermediate
between single and double bond lengths (1.39 Å).
Resonance instead considers such molecules to be
an intermediate or average (called a resonance
hybrid) between several structures that differ only
in the placement of the valence electrons
Benzene-orbitals
.It was also found that benzene was a flat (planar) molecule
Characteristics of aromatic compounds
1. A delocalized conjugated π system, most
commonly an arrangement of alternating single
and double bonds : Conjugated
2. Coplanar structure, with all the contributing
atoms in the same plane
3. Contributing atoms arranged in one or more
rings
4. A number of π delocalized electrons that is, 4n
+ 2 number of π electrons, where n=0, 1, 2, 3,
and so on. This is known as Hückel's Rule.
 Huckel’s Rule: The 4n+2 Rule

Planar monocyclic rings with a continuous system of p

orbitalsand 4n + 2p electrons are aromatic(n = 0, 1, 2,
3 etc)
Aromatic means substantial resonance stabilization
Benzene is aromatic:
planar
Cyclic
orbital at every carbon 6 p electrons (n=1)
Benzene has 3 bonding and 3 antibonding orbitals
All the bonding orbitals are full and there are no
electrons in antibonding orbitals; benzene has a closed
shell of delocalized electrons and is very stable
 Aromatic compounds

+
O + CH
-

N n=0 n=1
n=1 n=1
n=1 n=1

Non Aromatic compounds

+
-
CH
Nomenclature of Aromatic Compounds
1. Monosubstituted Benzenes
a. IUPAC name
CH2CH3 Cl CH2
C(CH3)3 NO2

t-Butylbenzene Ethylbenzene Nitrobenzene Chlorobenzene Benzyl group

b. Common name
CH3 H HO
CH2 Cl CH=CH2 OH C O C O H2N

Benzyl chloride Toluene Styrene Phenol Benzaldehyde Benzoic acid Aniline

 Disubstituted Benzenes .2
All disubstituted benzenes, can give rise to three possible isomers. The
differentiate between the isomers, the relative positions of the substituents
are designated by number or, more commonly, by the prefixes ortho (o: 1,2),
meta (m:1,3) or para (p:1,4).
Br
Br
Br
Br

Br
Br
1,2-Dibromobenzene 1,3-Dibromobenzene 1,4-Dibromobenzene
o-Dibromobenzene m-Dibromobenzene p-Dibromobenzene

When the substituents are different, they are listed in alphabetical order
F
O 2N
C2H5
Cl

Br
I
1-Chloro-2-ethylbenzene 1-Bromo-3-nitrobenzene 1-Fluoro-4-iodobenzene
o-Chloroethylbenzene m-Bromonitrobenzene p-Fluoroiodobenzene
 If one of the substituents is part of a parent
compound, then the disubstituted benzene is
named as a derivative of the parent compound.
O 2N COOH
OH
Cl

Br
H3C
2-Chlorophenol 4-Nitrotoluene 3-Bromobenzoic acid
o-Chlorophenol p-Nitrotoluene m-Bromobenzoic acid

Certain disubstituted benzenes are referred to by their common

names.
CH3
CH3 H3C
CH3

CH3
CH3
o-Xylene m-Xylene p-Xylene
Reactions of Benzene
 Even though benzene is highly unsaturated, it does
not
 undergo any of the regular reactions of alkenes
 Reactions of Benzene
 Benzene can be induced to react with bromine if a
Lewis acid catalyst is present
 The reaction is a substitution and not an addition!

Benzene produces only one monobrominatedcompound

All 6 carbon-hydrogen bonds are equivalent in benzene
Specific Electrophilic Aromatic :
Substitution Reactions
X
X2 , FeX3
Halogenation
+ HX (X=Cl, Br)

R
RCl, AlCl 3
Alkylation + HCl

NO 2
HONO 2 , H2SO 4

Nitration
+ H2O

SO 3H
SO 3 , H2SO 4
Sulfonation
 Side-Chain Reactions of Aromatic
Compounds
a. Halogenation of an Alkyl Side Chain
CH3 CH2Br
Br2

UV light
+ HBr

Toluene Benzyl Bromide

b. Oxidation of an Alkyl Side Chain

CH3 COOH
KMnO 4

Toluene Benzoic acid

CH 2CH 3 COOH
KMnO 4
+ CO 2 + H2O

Benzoic acid
 Disubstituted Benzenes : Orientation
Orientation Effects of Substituents in
Electrophilic Aromatic Substitution :
Meta directors Ortho , para directors
-NO2 -OH, -OR
-SO3H -NH2, -NHR, -NR2
-COOH, -COOR -C6H5
-CHO, -COR -CH3, -R (alkyl)
-CN -F, -Cl, -Br, -I
OH
OH
OH
NO 2
nitration
+
NO 2
o-Nitrophenol p-Nitrophenol
NO 2 53 47
NO 2
nitration

NO 2