Chapter 14

Aromatic Compounds

Chapter 14
In this chapter we will consider:
❖ The structural principles that underlie
the use of the term “aromatic”
❖ The initial challenge of determining the
correct structure of benzene
❖ A rule that helps to predict what kinds
of molecules possess the special
property of aromaticity
❖ Special groups of molecules that are
also aromatic
Chapter 14
1. The Discovery of Benzene

❖ Benzene: or

❖ In 1825, Faraday isolated benzene

from a compressed illuminating gas
that had been made by pyrolyzing
whale oil

Chapter 14
❖ In 1834, a German chemist, Eilhardt
Mitscherlich, synthesized benzene by
heating benzoic acid with calcium oxide

COOH

heat
+ CaO + CaCO 3

Chapter 14
❖ In the 19th century, organic compounds
were classified as being either
aliphatic or aromatic
❖ Aliphatic
● The chemical behavior of a
compound was “fatlike”
❖ Aromatic
● The compound had a low
hydrogen-to-carbon ratio and was
“fragrant”

Chapter 14
2. Nomenclature of Benzene
Derivatives
❖ Naming monosubstituted benzenes
● In many simple compounds, benzene is
the parent name and the substituent is
simply indicated by a prefix
F Cl Br NO2

Fluorobenzene Chlorobenzene Bromobenzene Nitrobenzene

Chapter 14
● For other simple and common
compounds, the substituent and the
benzene ring taken together may form a
commonly accepted parent name

Chapter 14
❖ Naming disubstituted benzenes
● When two substituents are present,
their relative positions are indicated by
the prefixes ortho-, meta-, and para-
(abbreviated o-, m-, and p-) or by the
use of numbers

Chapter 14
 ● Other examples
CH3
NO2 Cl

COOH OH CH3

2-Nitrobenzoic acid 3-Methylphenol 4-Chlorotoluene

(o-Nitrobenzoic acid) (m-Methylphenol) (p-Chlorotoluene)
(1-Chloro-4-methyl-
benzene)

Chapter 14
 ● The dimethylbenzenes are often
called xylenes

CH3
CH3 H3C

CH3 CH3 CH3

1,2-Dimethylbenzene 1,3-Dimethylbenzene 1,4-Dimethylbenzene

(o-xylene) (m-xylene) (p-xylene)

Chapter 14
❖ Naming benzene rings with more than
two groups
● If more than two groups are present on
the benzene ring, their positions must
be indicated by the use of numbers
● The benzene ring is numbered so as to
give the lowest possible numbers to
the substituents
Cl Br
1 1
2 Cl 2 Br
6 6

5
3
5
3 1,2,4-Tribromobenzene
4
Cl 4 (not 1,3,4-Tribromobenzene)
1,2,3-Trichlorobenzene Br
Chapter 14
● When more than two substituents
are present and the substituents
are different, they are listed in
alphabetical order
Cl
1
2 F
6

3
5
4

Br
4-Bromo-1-chloro-2-fluorobenzene
Chapter 14
 ● When a substituent is one that,
together with the benzene ring
gives a new base name, that
substituent is assumed to be in
position 1 and the new parent
name is used
Cl COOH
3 1
H3C 2
4 2 6

5 1
3
5
Cl 6 OH 4 Br
3,5-Dichlorophenol 5-Bromo-2-methylbenzoic acid
Chapter 14
● When the C6H5 group is named as a
substituent, it is called a phenyl
group
● A hydrocarbon composed of one
saturated chain and one benzene
ring is usually named as a
derivative of the larger structural
unit. However, if the chain is
unsaturated, the compound may be
named as a derivative of that chain,
regardless of ring size
Chapter 14
 ● Examples

Butylbenzene Isopropylbenzene

2 4
1 3 5 7
1 3 2 4 6 8
trans-1-Phenyl-1-butene (R)-3-Phenyloctane
Chapter 14
 ● Benzyl is an alternative name for
the phenylmethyl group. It is
sometimes abbreviated Bn.

Cl

The benzyl group Benzyl chloride

(the phenylmethyl group) (phenylmethyl chloride
or BnCl)

Chapter 14
3. Reactions of Benzene
Br
Br2
CCl4
Br

Br2
No Reaction
CCl4

Chapter 14
 OH
1. OsO4
2. NaHSO3
OH

1. OsO4
No Reaction
2. NaHSO3

Chapter 14
 OH
H+
H2O

H+
No Reaction
H2O

Chapter 14
 H2/Ni
25oC, 1 atm

H2/Ni
high temperature
and pressure

Chapter 14
❖ Benzene undergoes substitution, but
not addition
Br
Br2
(an addition)
CCl4
Br
(C6H10) (C6H10Br2)

H Br

Br2
(a substitution)
FeBr3
(a Lewis acid)
(C6H6) (C6H5Br)
Chapter 14
4. The Kekulé Structure for
Benzene
H
H C H
C C
or
C C
H C H
H
The Kekulé formula for benzene

Chapter 14
 6 6
1 Br 1 Br
5 5
and
4 2 4 2
3
Br 3
Br
These 1,2-dibromobenzenes
do not exist as isomers
6 6
1 Br 1 Br

X
5 5

4 2 4 2
3
Br 3
Br

There is no such equilibrium between

benzene ring bond isomers
Chapter 14
Br2
No Reaction

Br
Br2

Br

Chapter 14
5. The Thermodynamic Stability
of Benzene
❖ Since p bonds are formed from side-way overlap of
p orbitals, p electron clouds are above & below the
plane of the double bond

p-electrons above
and below ring

Chapter 14
Chapter 14
6. Modern Theories of the
Structure of Benzene
6A. The Resonance Explanation of the
Structure of Benzene

❖ All C C bond lengths the same (1.39 Å)

(compare with C—C single bond 1.54 Å, C=C
double bond 1.34 Å)
❖ Extra stabilization due to resonance 
aromatic
Chapter 14
❖ 3-D structure

p-electrons above
and below ring

● Planar structure
● All carbons sp2 hybridized
Chapter 14
Chapter 14
8. Other Aromatic Compounds
8A. Benzenoid Aromatic Compounds
❖ Benzenoid polycyclic aromatic hydrocarbons
consist of molecules having two or more
benzene rings fused together

Chapter 14
8B. Nonbenzenoid Aromatic
Compounds

(Azulene)

Chapter 14
Chapter 14
8C. Fullerenes

Chapter 14
9. Heterocyclic Aromatic
Compounds
❖ Cyclic compounds that include an element
other than carbon are called heterocyclic
compounds

Chapter 14
 NH2
❖ Examples of useful heterocyclic
aromatic compounds HO
HOOC H
N N
S
Serotonin H
(neurotransmitter)
O N
S O O
Penicillin COOH H
(antibiotic) N
O N
N
O
N
N H
N N
O2N
O
O S N N
Nitrofurantoin O
"Viagra"
(urinary antibacterial) O
Chapter 14
❖ Aromaticity

X X = O, S N
H

X N H

−
6p e : aromatic

Chapter 14
❖ Aromaticity
● Evidence: 1H NMR shift
H H

H H
Z Z
(2.5 ppm) (3.4 ppm)
H
Z  (ppm)  (5.5 ppm)
O 7.3 6.2
NH 6.4 6.2
H  (7.4 ppm)
S 7.1 7.0

Chapter 14
 ❖ Basicity of nitrogen-containing
heterocycles

N
Order of Basicity: > > >
N N N N
H H H
pKa of the
conjugate acid: 11.2 7 5.2 0.4

(c.f. Et3N, pKa of the conjugate acid = 9.7)

Chapter 14
❖ Basicity of nitrogen-containing
heterocycles

H H H
N N N N
+ H+
N N N N
H Imidazole H H H
(a very common base (still aromatic)
in organic synthesis)
Chapter 14
Non-basic
nitrogen

X H N H N H+ X
N N
H

5 (aromatic) (aromatic)
4
1
N H
N
3 2

H
X H N H N + X
N N H

(aromatic) (non-aromatic)
basic 6 p electrons 4 p electrons
nitrogen
Chapter 14
10. Aromatic Compounds in
Biochemistry
❖ Two amino acids necessary for protein
synthesis contain the benzene ring
O O

O O
NH3 NH3
HO
Phenylalanine Tyrosine

Chapter 14
❖ Derivatives of purine and pyrimidine
are essential parts of DNA and RNA
7
6 4
1 3
5 N 5
N N
8
2 3 6 1 2
N
4 N9 N
H

Purine Pyrimidine

Chapter 14
❖ Nicotinamide adenine dinucleotide, one
of the most important coenzymes in
biological oxidations and reductions, includes
both a pyridine derivative (nicotinamide) and
a purine derivative (adenine) in its structure

Chapter 14
 END OF CHAPTER 14 

Chapter 14