Alrasheed University College

Department of Pharmacy

Aromatic Compounds
Lecture 1

Prepared by
Dr. Kutaiba Ibrahim Alzand
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
 In 1834, a German chemist, Eilhardt
Mitscherlich, synthesized benzene by
heating benzoic acid with calcium oxide

COOH

heat
+ CaO + CaCO3
 In the 19th century, organic compounds
were classified as being either aliphatic or
aromatic
 Aliphatic
● The chemical behaviour of a compound was
“fatlike”
 Aromatic
● The compound had a low hydrogen-to-
carbon ratio and was “fragrant”
 The following are a few examples of aromatic compounds,
including benzene itself.
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

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

H H H CH3
CH3 O N SO3H O

Toluene Phenol Aniline Benzene- Anisole

sulfonic acid
O O

OH
Benzoic acid Acetophenone
 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

Br
Br Br

Br Br Br

1,2-Dibromobenzene 1,3-Dibromobenzene 1,4-Dibromobenzene

(o-dibromobenzene) (m-dibromobenzene) (p-dibromobenzene)
ortho meta para
• 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)
 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)
 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
● 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
● 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
 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
● Examples

Butylbenzene Isopropylbenzene

2 4
1 3 5 7
1 3 2 4 6 8
trans-1-Phenyl-1-butene (R)-3-Phenyloctane
● 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)
Solved Problem 1.1
Provide a name for each of the following compounds.

Answer:
(a) p-tert-butylacetophenone or 4-tert-butylacetophenone.
(b) 1,4-dimethyl-2-nitrobenzene.
(c) 2-chloro-2-methyl-1-phenylpentane.
(d) benzyl ethyl ether, or ethyl phenylmethyl ether.
Practice Problem 1.1 Provide a name for each of the
following compounds.

SOLUTION TO PROBLEM

(a) 4-Bromobenzoic acid (or p-bromobenzoic acid)

(b) 2-Benzyl-1.3-cyclohexadiene
(c) 2-Chloro-2-phenylpentane
(d) Phenyl propyl ether
3. Reactions of Benzene
 When benzene is treated with bromine in the dark or with aqueous
potassium permanganate or with dilute acids, none of the expected
reactions occurs. Benzene does add hydrogen in the presence of
finely divided nickel, but only at high temperatures and under high
pressures:
• Benzene does react with bromine but only in the presence of a
Lewis acid catalyst such as ferric bromide. Most surprisingly,
however, it reacts not by addition but by substitution—benzene
substitution.

• When benzene reacts with bromine, only one monobromobenzene

is formed. That is, only one compound with the formula C6H5Br
is found among the products.
• Similarly, when benzene is chlorinated, only one
monochlorobenzene results.
Practice Problem 1.2
Listed below are four compounds that have the molecular formula
C6H6. Which of these compounds would yield only one
monosubstitution product, if, for example, one hydrogen were
replaced by bromine?

Answer
Compounds (a) and (b) would yield only one monosubstitution
product.
3. Reactions of Benzene

Br
Br2
CCl4
Br

Br2
No Reaction
CCl4
 OH
1. OsO4
2. NaHSO3
OH

1. OsO4
No Reaction
2. NaHSO3
 +
OH
H
H2O

H+
No Reaction
H2O
 H2/Ni
25oC, 1 atm

H2/Ni
high temperature
and pressure
 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)
4. The Kekulé Structure for Benzene
 In 1865, August Kekulé, the originator of the structural theory,
proposed the first definite structure for benzene, a structure that
is still used today.
 Kekulé suggested that the carbon atoms of benzene are in a
ring, that they are bonded to each other by alternating
single and double bonds, and that one hydrogen atom is
attached to each carbon atom.
H
H C H
C C
or
C C
H C H
H
The Kekulé formula for benzene
 6 6
1 Br 1 Br
5 5 These 1,2-dibromobenzenes
and
4 4
do not exist as isomers
2 2
3
Br 3
Br

 Only one 1,2-dibromobenzene has ever been found, however.

6 6
5
1 Br
X 5
1 Br
There is no such equilibrium
between benzene ring bond
4 4
Br isomers
2 2
3 Br 3

 We now know that this proposal was also incorrect and that
no such equilibrium exists.
• The tendency of benzene to react by substitution rather than
addition gave rise to another concept of aromaticity.
• For a compound to be called aromatic meant, experimentally,
that it gave substitution reactions rather than addition reactions
even though it was highly unsaturated.
• Cyclooctatetraene reacts with bromine by addition, it adds
hydrogen readily, it is oxidized by solutions of potassium
permanganate, and thus it is clearly not aromatic.
5. The Thermodynamic Stability of Benzene
 Since  bonds are formed from side-way overlap
of  orbitals,  electron clouds are above & below
the plane of the double bond

-electrons above
and below ring
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
 3-D structure

-electrons above
and below ring

● Planar structure
● All carbons sp2 hybridized
6B. The Molecular Orbital Explanation
of the Structure of Benzene
7. Hückel’s Rule: The (4n + 2)  Electron Rule
 Hückel’s rule is concerned with compounds containing
one planar ring in which each atom has a  orbital
as in benzene.
 Planar monocyclic rings containing (4n + 2)  electrons,
where n = 0, 1, 2, 3, and so on (i.e., rings containing 2, 6,
10, 14 . . . etc.  electrons), have closed shells of
delocalized electrons like benzene and have substantial
resonance energies.
 Hückel’s rule states that planar monocyclic rings with 2, 6,
10, 14 . . . delocalized electrons should be aromatic
7A. How To Diagram the Relative Energies of 
Molecular Orbitals in Monocyclic Systems
Based on Hückel’s Rule

antibonding  orbitals

nonbonding  orbital

bonding  orbitals

Polygon in circle Energy levels of MOs Type of  orbital

 The  molecular orbitals that cyclooctatetraene would have
if it were planar. Notice that, unlike benzene, this molecule
is predicted to have two nonbonding orbitals, and because
it has eight  electrons, it would have an unpaired electron
in each of the two nonbonding orbitals. Such a system
would not be expected to be aromatic.
 The bonds of cyclooctatetraene are known to be
alternately long and short; X-ray studies indicate
that they are 1.48 and 1.34 Å, respectively, and
that the molecule has a tub-like shape
7B. The Annulenes
 Hückel’s rule predicts that annulenes will be aromatic
if their molecules have (4n + 2)  electrons and have
a planar carbon skeleton.
 Consider the [14], [16], [18], [20], [22], and
[24]annulenes as examples.
 Of these, as Hückel’s rule predicts, the [14], [18],
and [22]annulenes (4n + 2 when n = 3, 4, 5,
respectively) have been found to be aromatic.
 The [16]annulene and the [24]annulene are not
aromatic; they are antiaromatic. They are 4n
compounds, not 4n + 2 compounds:
 The [16]annulene and the [24]annulene are not
aromatic; they are antiaromatic. They are 4n
compounds, not 4n + 2 compounds:
 All these (4n + 2) , planar
annulenes are aromatic

(4n + 2)  Benzene [14]Annulene

planar annulenes: [6]Annulene (aromatic)

[18]Annulene
(aromatic)
 Non-planar (4n + 2)  annulenes are
non-aromatic
 (4n)  non-planar annulenes are antiaromatic

Cyclobutadiene [8]Annulene [16]Annulene

[4]Annulene
Solved Problem 1.2
Using the polygon-and-circle method to outline the molecular
orbitals of cyclobutadiene, explain why cyclobutadiene is not
aromatic.
Strategy and Answer: We inscribe a square inside a circle with
one corner at the bottom.

We see that cyclobutadiene, according to this model, would have

an unpaired electron in each of its two nonbonding molecular
orbitals. We would, therefore, not expect cyclobutadiene to be
aromatic.
7D. Aromatic Ions
pka = 36
pka = 16
H H
H H

Cyclopentadiene Cycloheptatriene
 H
H H

Bu Li
(a strong base)

6  electrons
 aromatic

H strong
base H
H

sp3 sp2
H H

- H+

8  electrons
(antiaromatic)
H H

- H

6  electrons
(aromatic)
Solved Problem 1.3
Apply the polygon-and-circle method to explain why the
cyclopentadienyl anion is aromatic.
Strategy and Answer: We inscribe a pentagon inside a
circle with one corner at the bottom and find that the
energy levels of the molecular orbitals are such that three
molecular orbitals are bonding and two are antibonding:

Cyclopentadienyl anion has six p electrons, which is a

Hückel number, and they fill all the bonding orbitals. There
are no unpaired electrons and no electrons in antibonding
orbitals. This is what we would expect of an aromatic ion.
Practice Problem 1.4 Apply the polygon-and-circle
method to cyclopentadienyl cation and explain whether it
would be aromatic or not.
Practice Problem 1.5 Apply the polygon-and-circle method to the
cycloheptatrienyl anion and cation and explain whether each would be
aromatic or not.
7E. Aromatic, Antiaromatic, and
Nonaromatic Compounds
 An aromatic compound has its  electrons
delocalized over the entire ring and it is stabilized
by the -electron delocalization.
 One way to evaluate whether a cyclic compound
is stabilized by delocalization of  electrons
through its ring is to compare it with an open-
chain compound having the same number of 
electrons
 To use this approach we do the following:
1. We take as our model a linear chain of sp2-hybridized
atoms having the same number of p electrons as our
cyclic compound.
2. Then we imagine removing a hydrogen atom from each
end of the chain and joining the ends to form a ring.

 Based on sound calculations or experiments

● If the ring has lower -electron energy, then the ring is
aromatic
● If the ring and the chain have the same -electron
energy, then the ring is nonaromatic
● If the ring has greater -electron energy than the open
chain, then the ring is antiaromatic
 Cyclobutadiene
-electron
+ H2
energy increases

1,3-Butadiene Cyclobutadiene
4  electrons 4  electrons
(antiaromatic)

 Benzene
-electron
+ H2
energy decreases

1,3,5-Hexatriene Benzene
6  electrons 6  electrons
(aromatic)
 Cyclopentadienyl Anion

 Cyclooctatetraene
Solved Problem 1.4
Calculations indicate that the p-electron energy decreases for the
hypothetical transformation from the allyl cation to the
cyclopropenyl cation below. What does this indicate about the
possible aromaticity of the cyclopropenyl cation

Strategy and Answer: Because the p-electron energy of the

cyclic cation is less than that of the allyl cation, we can conclude
that the cyclopropenyl cation would be aromatic.
Practice Problem 1.8
The cyclopentadienyl cation is apparently antiaromatic.
Explain what this means in terms of the p-electron
energies of a cyclic and an open-chain compound.

Answer
The fact that the cyclopentadienyl cation is antiaromatic
means that the following hypothetical transformation would
occur with an increase in π-electron energy.
8. Other Aromatic Compounds
8A. Benzenoid Aromatic Compounds
 Benzenoid polycyclic aromatic hydrocarbons
consist of molecules having two or more benzene
rings fused together
8 1 8 9 1
2 2
Naphthalene 7 7 Anthracene
C10H8 3 3
C14H10
6 6
5 4 5 10 4

6 9 8

5 7 10 7

4
8 6
3
Phenanthrene 1 Pyrene
C14H10 C16H10
2 9 2 5
1 10 3 4
8B. Nonbenzenoid Aromatic
Compounds

(Azulene)
8C. Fullerenes
9. Heterocyclic Aromatic
Compounds
 Cyclic compounds that include an element
other than carbon are called heterocyclic
compounds
4 4 3 4 3 4 3
5 3
5 2 5 2 5 2

6 2
N1 O1 S1
N
1 H
Pyridine Pyrrole Furan Thiophene
(electronically
related to
benzene) (electronically related to
cyclopentadienyl anion)
 Aromaticity

X X = O, S N
H

X N H

6 e: aromatic
  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)

 Basicity of nitrogen-containing
heterocycles
H
+ H+
N N N H
H H
H H
(loss of aromaticity)

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)
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  electrons 4  electrons
nitrogen