Chapter 14

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

COOH

heat
+ CaO + CaCO 3
❖ 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”
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
❖ 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
 ● 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
---------mostly halogens and alkyls

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.
 ● 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)
3. Reactions of Benzene
Br
Br2
CCl4
Br

Br2
No Reaction
CCl4
 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
H
H C H
C C
or
C C
H C H
H
The Kekulé formula for benzene

Thiele Kekulé
(1899) (1865)
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
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

p-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) p
Electron Rule
❖ Hückel’s rule is concerned with
compounds containing one planar ring in
which each atom has a p orbital as in
benzene

Aromatic:
▪ Cyclic;
▪ completely conjugated p orbitals;
▪ Planar;
▪ 4n+2
7A. How To Diagram the Relative
Energies of p Molecular Orbitals in
Monocyclic Systems Based on
Hückel’s Rule-Frost Circle

antibonding p orbitals

nonbonding p orbital

bonding p orbitals

Polygon in circle Energy levels of MOs Type of p orbital

❖ The p 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 p electrons, it would have an unpaired electron
in each of the two nonbonding orbitals. Such a system
would not be expected to be aromatic.
7B. The Annulenes
❖ Hückel’s rule predicts that annulenes
will be aromatic if their molecules have
(4n + 2) p electrons and have a planar
carbon skeleton
❖ All these (4n + 2) p, planar
annulenes are aromatic

(4n + 2) p Benzene [14]Annulene

planar annulenes: [6]Annulene (aromatic)

[18]Annulene
(aromatic)
Antiaromatic:
▪ Cyclic;
▪ completely conjugated p orbitals;
▪ Planar;
▪ 4n

All others: non-aromatic

❖ Non-planar annulenes are non-aromatic
❖ Anti-aromatic compounds sometimes change
shape, becoming non-planar to break up some of
the pi interactions

Planar structure Nonplanar structure

antiaromatic non-aromatic
Summary
❖ Rules
Aromatic Anti-Aromatic Non-Aromatic
Planar Planar Not planar
4n+2 rule 4n rule Can follow 4n or 4n+2 rules
Uninterrupted pi Uninterrupted pi X
system system
Capable of resonance Capable of resonance X
Ring has a lower π Ring has a higher π Ring has the same energy as
energy than open energy than open the open chain
chain chain

32
[18] Annulene H H
Inside protons (d 9.3)
are shielded H H
Outside protons
are deshielded
H
H H H H

(d -3.0)
H H H H
H

H H

H H
7D. Aromatic Ions

pka = 36
pka = 16
H H
H H

Why?
 H
H H

Bu Li
(a strong base)

6 p electrons
 aromatic

H strong
base H
H

sp3 sp2
H H

- H−

6 p electrons
(aromatic)
8. Other Aromatic Compounds
8A. Benzenoid Aromatic Compounds
❖ Benzenoid polycyclic aromatic hydrocarbons consist of
molecules having two or more benzene rings fused
together
8B. Nonbenzenoid Aromatic
Compounds

(Azulene)
8C. Application of Aromaticity

Stable Can not be isolated, always dimerize?

Remarkable Low pKa?

Polar Molecule?
9. Heterocyclic Aromatic
Compounds
❖ Cyclic compounds that include an element
other than carbon are called heterocyclic
compounds
❖ Aromaticity

X X = O, S N
H

X N H

−
6p e : aromatic
❖ Aromaticity
● Evidence: 1H NMR shift
 ❖ 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)

11. Spectroscopy of Aromatic
Compounds
11A. 1H NMR Spectra
❖ The ring hydrogens of benzene derivatives
absorb downfield in the region between d
6.0 and d 9.5 ppm

11B. 13C NMR Spectra

❖ The carbon atoms of benzene rings
generally absorb in the d 100–170 ppm
region of 13C NMR spectra
1H NMR Spectra
11D. Ultraviolet–Visible Spectra of
Aromatic Compounds
11E. Mass Spectra of Aromatic
Compounds