Foundation Chemistry

FIS 0134
Chemistry 3

Aromatic Compounds
(Week 5 and 6)
PowerPoint® Slides by
Nurul Hana Minarti Omar

Last Updated:13 December 2018

 AROMATIC COMPOUNDS

Introduction to
3.1
aromatic Compounds

Arenes = aromatic compounds:

the word aromatic has nothing to do with odour.
 KEYWORDS

aromatic Kekulé structure

ortho meta para

resonance structure

Friedel-Craft acylation
electrophilic substitution

oxidation of
activating and alkylbenzene
deactivating group

substitution of
ortho-para and meta director toluene
 DISCOVERY OF BENZENE

1825 Michael Faraday

(British)

Isolated a pure compound of

boiling point 80oC

Empirical formula = CH

Named “bicarburet of hydrogen”

1834 Eilhard Mitscherlich (German)

Prepared benzene from benzoic acid

heat
C6H5CO2H + CaO  C6H6 + CaCO3

Molar mass = 78, molecular formula = C6H6

named “benzin”

benzene benzin benzoin

benjoin Luban Jawi

gum benzoin
(French) (Arabic)
1866 Friedrich August Kekulé (German)
Proposed a cyclic structure for benzene.
 AROMATIC COMPOUNDS
In earlier time, compounds are called
aromatic because of their pleasant odours.

Benzene has strong

pleasant odour.

Today, we use the word aromatic to refer to

benzene and its structural relatives.
 AROMATIC COMPOUNDS

Aromatic compound is a cyclic conjugated

molecule or ion that is stabilized by ∏ electron
delocalisation.

it is characterised by substitution reactions.

 KEKULÉ’S STRUCTURE

 Kekule was the first to formulate a

reasonable representation of benzene

H C H
C
or
C C
H C H
H

The Kekule structure suggests alternating double

and single carbon-carbon bonds
 RESONANCE STRUCTURE
Benzene is actually a resonance hybrid of the
two Kekulé structures.

equivalent to

resonance hybrid

All C–C bond length equal = 139 pm

Shorter than typical C–C (148 pm)

Longer than typical C=C (134 pm)

The six p electrons completely delocalized around the ring
 The circle represents the six p
electrons, distributed over the
six atoms of the ring!

All six C atoms and six p orbitals are equivalent

 THE CRITERIA FOR AROMATICITY

4 structural criteria must be satisfied for

compound to be aromatic
 THE CRITERIA FOR AROMATICITY

HÜckel’s Rule
* cyclic, planar and completely
conjugated compounds that
contain [4n+2] ∏ electron
(n=0,1,2…..) are said to be
aromatic

Erich HÜckel
(1896-1980)

 planar monocyclic rings with 6,10,14 and so forth

∏ electrons are aromatic
 THE CRITERIA FOR AROMATICITY

EXAMPLE OF AROMATIC COMPOUNDS

1. Aromatic compounds with a single ring

Benzene
aromatic
Benzene is aromatic because:
 contains 6∏ electrons
(obeys HÜckels Rule)
[4n+2] ∏ = [4(1) + 2]∏
 cyclic, planar and has double
= 6 ∏ electrons bond in the ring
 THE CRITERIA FOR AROMATICITY

2. Aromatic compounds with more than one ring

EXAMPLE

Aromatic

naphthalene
4n+2= 4(2)+ 2
10 ∏ electrons

* Two benzene rings joined together forms naphthalene

 AROMATIC COMPOUNDS

Nomenclature of benzene
3.2
and its derivatives

Arenes = aromatic compounds:

the word aromatic has nothing to do with odour.
 NAMING BENZENE DERIVATIVES
Many organic molecules contain a benzene
ring with one or more substituents.

Many common name are

recognized by the IUPAC system

EXAMPLE:

CH3
Common: toluene
IUPAC: methylbenzene
 MONO SUBSTITUTED BENZENE
Benzene is the parent name and the substituent
is indicated by a prefix.
F Cl Br

fluorobenzene chlorobenzene bromobenzene

NO2 CH2CH3

nitrobenzene ethylbenzene
 IUPAC rules allow some common names
to be retained.

CH3 OH NH2

toluene phenol aniline

COOH CHO

benzoic acid benzaldehyde

 DISUBSTITUTED BENZENE
Two Same Substituents
Relative position of subsituents are indicated by
prefixes ortho, meta, and para ( o–, m–, and p–)
or by the use of number.
Br
Br 1
1 Br 2
2 Br
1
2 3
4
3
Br Br
1,2–dibromobenzene 1,4–dibromobenzene
or 1,3–dibromobenzene or
o–dibromobenzene or p–dibromobenzene
m–dibromobenzene
 NO2 NO2
1
2 NO2 1
2
3
NO2

1,2–dinitrobenzene 1,3–dinitrobenzene
or or
o–dinitrobenzene m–dinitrobenzene
NO2
1
2

3
4
NO2
1,4–dinitrobenzene
or
p–dinitrobenzene
 DISUBSTITUTED BENZENE
Two Different Substituents

Select one of the substituent that give

new parent name and numbered as C1.
COOH
COOH 1
1 2
2 NO2 COOH
1
2 3
4
3
NO2
NO2
2–nitrobenzoic acid 4–nitrobenzoic acid
or 3–nitrobenzoic acid or
o–nitrobenzoic acid or p–nitrobenzoic acid
m–nitrobenzoic acid
 THREE OR MORE SUBSTITUENTS
Position of substituents must be indicated by
numbers.

The substituents are listed alphabetically when

writing the name.

Cl
Br
1 2 Br Br
3 I
4
2–bromo–1–chloro–3–iodobenzene
Br
1,2,4–tribromobenzene
C atom bearing the subtituent that define the
new parent name is numbered as C1.
OH
COOH
1
2 NO2 1
6 2
3 5 3
4 OH
HO 4
NO2
3,5–dihydroxybenzoic acid
2,4–dinitrophenol

3
Br 4 2 CH3

1 CH3
4–bromo–1,2–dimethylbenzene
 3
Br 4 2 CH3

1 CH3

4–bromo–1,2–dimethylbenzene correct

4–bromo–o–dimethylbenzene

o–, m– and p– naming system is used for

arenes with 2 substituents only!
 14.2-11
PHENYL GROUP
Benzene ring as substituent.
If alkyl substituent is larger than the ring
(more than 6 C), the compound is named as
phenyl-substituted alkane.

1 CH2
3 4 5 6 7
2 CH–CH –CH –CH –CH –CH
2 2 2 2 3

2–phenylheptane

Phenyl = C6H5– = Ph
 14.2-12

If the chain is unsaturated (have C═C or C≡C)

or contains important functional group, the
benzene ring is considered as
phenyl substituent.

1 2 3 4 2 1
CH2–C C–CH3 CH2–CH2–OH

1–phenyl–2–butene 2–phenylethanol
 14.2-13
BENZYL GROUP

CH2—

phenyl group benzyl group

CH2Br CH2OH

benzyl bromide benzyl alcohol