AROMATIC COMPOUNDS

Recapitulation:

Hydrocarbons, these are any classes of organic chemical compounds that are composed of the
elements carbon (C) and hydrogen (H) only.

Hydrocarbons can be classified as aliphatic and aromatic compounds.

Aliphatic hydrocarbons are divided into three main groups according to the types of bonds they
contain: alkanes, alkenes, and alkynes. Alkanes have only single bonds, alkenes contain a
carbon-carbon double bond, and alkynes contain a carbon-carbon triple bond. These groups can
either be acyclic or cyclic compounds.

CH3
H3C
2,4–hex-di-ene 1,3-cyclo-hex-di-ene

Aromatic compounds are chemical compounds that consist of conjugated planar ring systems
accompanied by delocalized pi-electron clouds in place of individual alternating double and
single bonds.

These compounds have low H/C ratio, possess strong and characteristic odor and therefore called
aromatic compounds. It is their chemical properties that made the special compounds but not
their odor.

Benzene (C6H6) is the simplest aromatic hydrocarbon. It was isolated by Michael Faraday from
the oily residue remaining in the illuminating gas line in London (1825). It has been recognized
as an unusual compound by possessing four degrees of unsaturation, making it a highly
unsaturated compound.

(2C + 2 + N – X – H)/2

(12 + 2 + 0 – 0 – 6)/2 = 4

Unsaturated compounds (alkenes and alkynes) readily undergo addition reaction, benzene does
not. For example, bromine adds to cyclohexene to form a dibromide but benzene is inert under
similar condition and would rather undergo electrophilic substitution reaction.

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 Electrophilic addition reaction of cyclohexene

Electrophilic substitution reaction of Benzene

In 1866, August Kekule proposed structures for benzene. In his structure, the bond between any
two carbon atoms is sometimes a single bond and sometimes a double bond. In kekule model,
benzene was thought to be a rapidly equilibrating mixture of two compounds

Although benzene is still drawn as a six-membered ring with three alternating pie bond, in
reality, there is no equilibrium between these two different kinds of benzene molecules. Instead,
current descriptions of benzene are based on resonance and electron delocalization due to orbital
overlap.
Because each π bond has two electrons, benzene has six π electrons

Resonance structure of Benzene

Building the orbital model

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Benzene is built from hydrogen atoms (1s1) and carbon atoms (1s22s22px12py1).

Each carbon atom has to join to three other atoms (one hydrogen and two carbons) and doesn't
have enough unpaired electrons to form the required number of bonds, so it needs to promote
one of the 2s2 pair into the empty 2pz orbital.

Promotion of an electron

There is only a small energy gap between the 2s and 2p orbitals, and an electron is promoted
from the 2s to the empty 2p to give 4 unpaired electrons. The carbon atom is now said to be in
an excited state.

The new orbitals formed are called sp2 hybrids, because they are made by an s orbital and two p
orbitals reorganizing themselves. The three sp2 hybrid orbitals arrange themselves as far apart as
possible - which is at 120° to each other in a plane. The remaining p orbital is at right angles to
them. Each carbon also has a p-orbital with one electron that extends above and below the plane
of the molecule. The six adjacent p-orbitals overlap, delocalizing the six electrons over the six
atoms of the ring, because each p-orbital has two lobes (one above and one below the plane of
the ring) the overlap of the p-orbital creates two doughnut of electrons density where the six pie
electrons are located.

 Benzene’s six πelectrons make it electron rich and so it readily react with
electrophiles

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 https://www.youtube.com/watch?v=OmRzPTxyKis
https://www.chemguide.co.uk/basicorg/bonding/benzene2.html

Benzene ring won’t readily undergo addition reaction (except under a very rigorous condition)
because of its stability due to the resonance and delocalization of pie electrons. That is, the pie
bonds cannot be broken easily. Furthermore the presence of pie electrons in the ring makes it
electron rich.

Nomenclature of Benzene derivatives

Many organic molecules contain a benzene ring with one or more substituents, so we must learn
to name them. Some of these derivatives have both UPAC (International Union of Pure and
Applied Chemistry) and common names.

Monosubstituted Benzene (Benzene ring with one substituent):

To name a benzene ring with one substituent, name the substituent and add the word benzene.
Carbon substituents are named as alkyl groups.

CH 2 CH 3 Cl Br NO 2

Ethylbenzene Chlorobenzene Bromobenzene Nitrobenzene

The phenyl group

Remember that you get a methyl group, CH3, by removing a hydrogen from methane, CH4.

You get a phenyl group, C6H5, by removing a hydrogen from a benzene ring, C6H6. Like a
methyl or an ethyl group, a phenyl group is always attached to something else.

Phenylethene

This is an ethene molecule with a phenyl group attached. Ethene is a two carbon chain with a
carbon-carbon double bond. Phenylethene is therefore:

CH=CH 2

The old name for phenylethene is styrene

Phenylethanone (acetophenone)

This is a slightly awkward name - take it to pieces. It consists of a two carbon chain with no
carbon-carbon double bond. The one ending shows that it is a ketone, and so has a C=O group

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somewhere in the middle. Attached to the carbon chain is a phenyl group. Putting that together
gives:

CH3

CH3
O

O
Name this?

For other compounds, the substituents and the benzene ring taken together may form a new
parent name. Methylbenzene is usually called toluene, hydroxylbenzene is called phenol,
aminobenzene is called aniline and methyoxybenzene is called anisole.

For example:

CH3 OH NH2 H3 CO

Toluene Phenol Aniline Anisole

Other examples of monosubstituted derivatives

COOH
CH 2Cl SO 3H

Benzoic acid
Benzyl chloride or benzene carboxylic acid Benzene sulfonic acid

Disubstituted Benzene derivatives

There are three different ways that two groups can be attached to a benzene ring. A prefix ortho
(o), meta (m) or para (p) can be used to designate the relative position of the two substituents.

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 Br Br
Br
Br

Br
o-dibromobenzene m-dibromobenzene p-dibromobenzene
or or or
Br
1,2-dibromobenzene 1,3-dibromobenzene 1,4-dibromobenzene

If the two groups on the benzene ring are different, alphabetize the names of the substituents
preceding the word benzene. If one of the substituents is part of a common root, name the
molecule as a derivative of that monosubstituted benzene. For examples:

CH3

Br O 2N

Cl

F Br
o-bromochlorobenzene m-fluoronitrobenzene p-bromotoluene

Polysubstituted Benzene Derivatives

When there are two or more substituents on a benzenes ring. These are steps to take:

1. Number to give the lowest possible number to the substituents around the ring.

2. Alphabetize the substituent names.

3. When the substituents are part of the common roots, name the molecule as a derivative of
that monosubstituted benzene. The carbon that carries the common root is located at C1.

Examples of naming polysubstituted benzene

H2N

Cl 1
1 CH 2CH 3
2
2 5
4 3
Cl C3H7
3 4 Cl

4-chloro-1-ethyl-2-propylbenzene 2,5-dicholoroaniline

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Problem 1 - Write the structural formulae for each of the following:

1. 3-nitrobenzoic acid
2. o-bromotoluene
3. o-dibromobenzene
4. m-dinitrobenzene
5. 3,5-dinitrophenol
6. p-nitroaniline
7. Isobuthylbenzene
8. 4-chloro-1,2-diethylbenzene

Problem 2 – Give the IUPAC name for each compound

1. PhCH(CH3)2

C2H5
2.

OH

3.

CH3

H3C
Br
4.

Cl