Lesson Five

Aromatic Compounds

Aromatic compounds are defined as benzene and compounds that are similar to
benzene in chemical behavior. Benzene is the simplest aromatic compound with a general
formula C was first isolated by Michael Faraday in 1825 from oily residues that had
accumulated in London gas pipelines. Although benzene and many other aromatic compounds
are extracted from foul smelling coal tar, they have a fragrant odor, hence the term (aromatic).

The structure of benzene

The carbon-to-hydrogen ratio in benzene, C 6H6 Suggests a highly unsaturated

structure and therefore expected to be very reactive. On the contrary, it appeared to be
remarkably stable. It does not undergo typical addition reactions of alkenes or alkynes
(unstaturated compounds). For instance, it neither decolorize dilute potassium permanganate
(the Beyer test for unsaturation) nor did it add bromine readily as one would expect alkenes or
alkynes to do. Instead, benzene reacts mainly by substitution. For example, when benzene is
treated with bromine in presence of ferric bromide as a catalyst, it gives bromo benzene and
hydrogen bromide.

FeBr3
C6H6 + Br2 C6H5Br + HBr

Only one monobromo benzene was isolated and no other isomer are obtained. This
fact indicated to the German chemist Keukule that each hydrogen atom of benzene must be
equivalent to every other hydrogen. In 1865 he proposed a structure for benzene that was in
accord with its chemical behaviour. He suggested that the six carbon atoms are located at the
corners of a regular hexagon, with one hydrogen attached to each carbon atom. To give each
carbon atom a valence of 4, he proposed that single and double bonds alternate around the
ring (conjugated system of double bonds). This is a highly unsaturated system and to explain
the benzene’s negative tests for unsaturation kekulé suggested that the single and double
bonds exchange position around the ring so rapidly that the typical addition reactions of
alkenes cannot take place.
H H
H H H H

H H H H
H H

Kekules resonance forms of benzene

The two resonance forms differ only in the position of electron and not in the position of
the atoms. Benzene does not alternate between the above two resonance structures nor are
some benzene molecules of one form and the rest of the other, rather, the true structure of
benzene is an average of the two forms and is called the resonance hybrid. The resonance
hybrid has six identical carbon-carbon bonds, all intermediate in length between a carbon-
carbon double and single bond.

Delocalized p1 cloud

Symbols of Resonance hybrid for Benzene

H H

H H

H H

Molecular orbitals of the Resonance hybrid.

Aromaticity

Aromatic compounds are compounds that resemble benzene in chemical behaviour.

They have a significant amount of resonance energy and tendency towards substitution rather
than addition reaction.

To be classified as aromatic, a compounds must be:

1. Cyclic and planar.

2. Each atom of the aromatic ring must have a p orbital. These p orbitals must be parallel so
that continuous overlap is possible around the ring.

3. The cyclic clouds of parallel orbitals must contain

4n + 2 pi electrons (where n is an integer 0,1,2,3 ).

This requirement is usually referred to as “Huckle rule” this rule specifies that not only
continuous ring formation

pi electrons is important for aromaticity, but also, the number of must be a total of 2,6,10,14 If
we apply these aromaticity rules to the benzene ring which is cyclic and planar and has a p
orbital on each atom of the ring (each carbon is involved in a double bond and thus must have
a p orbital). There are three double bonds and pi electrons in accordance with Huckle Rule
where n equal to 1 (integer).
 

Since benzene meets all the three requirements for aromaticity it is aromatic.

Cyclooctatetraene

Cyclooctatetraene is not aromatic.

This molecule is cyclic with a p orbital on each atom of the ring. The Huckel rule is not satisfied
since there are eight pi electrons

Since n is equal o 1.5 which is not an integer the molecule of cycleoctatetraene is not aromatic.

Naphthalene

It is cyclic with a p orbital on each ring carbon. The total number of pi electrons is 10 which is
consistent with Huckle Rule where n = 2

4n+2 = 10          4n = 8               n  =  2

So Naphthalene is aromatic.

Cycloprpenyl cation

1. It is cyclic.

2. Each carbon of the ring hasp orbital.

3. It is consistent with Huckel rule where n = o which is an integer.

4n+2=2

4n=o   n=o

So, it is aromatic.

Cyclopentadienyl Cation and Anion

                                                                                            
1.Cyclic                                                                 1. Cyclic

2.   Each carbon has p orbital                                  2.  Each carbon has p orbital   

3.Inconsistent                                                         3.  Follows Huckel Rule

Huckle rule

4n+2=4                                                                4n+2=6                                

4n=2  and   n=O.5                                                            n=1

Not aromatic                                                                  Aromatic

Tetralin

Tetrahydronaphthalene called tetralin contains two ring, one aromatic and one aliphatic

a b

Ring a is aromatic      Ring b is aliphatic

Nomenclature of Aromatic compounds

a.      Monosubstituted benzenes.

They are named as derivatives of benzene.

Cl OCH3 NO2
CH2CH3

                                                                     

     Chlorobenzene  Ethylbenzene      Methoxybenzene       Nitrobenzene

Common names usually early in origin and have been used for some benzene derivatives are
now widely accepted and used.

CH CH2
CH3 CHO COOH

                                           

    Styrene        Toluene              Benzaldehyde        Benzoic acid

 OH NH2

                                                  

                        Phenol                                                       Aniline

B. Positional Isomerism in Benzene Derivatives

CH3 CH3 CH3

CH3

CH3
CH3

1,2-Dimethyl benzene             1,3-Dimethyl benzene         1,4-Dimethyl benzene

             Ortho(o-Xylene)                meta (m-xylene)            para (p-xylene)

Polysubstituted Benzenes

When more than two groups are on a benzene ring, their position must be numbered.
Ortho, meta and para designations are not acceptable. If one of the groups in associated with a
common name, the molecule will benamed as a derivative of the mono-substituted compounds
starting from the group designated in the common name.

Br
CH3
Cl

Br NH2
                                           I

3-amino-5-bromotoluene                        1-Bromo-2-chloro-3-iodobenzene

         or 3-methyl-6-bromoaniline

Aromatic Compounds Designated By Prefixes

In some cases, the substituents on aromatic ring are too complex to name easily by
prefix and the aromatic ring is named with a prefix. The terms phenyl and benzyl are commonly
used.
 CH2
C 6H 5 (Ph) C6H5CH2 (Bz)
                                     

Phenyl group                                   Benzyl group

1 2 3 CH3 CH3
4
CH3 CH2 CH C CH2 CH3 CH2 Cl
H
C C CH3

Cl        

3-m-chlorophenyl-4-methylhexane                            2-Chloro-3-phenyl-2-pentene

Fused ring Aromatics

Fused-ring aromatic compounds are derivatives of benzene in which carbons is shared

between benzene rings

Naphthalene            Anthracene                 phenanthrene                         Benzopyrene

Anthracene is found in coal and forms the basic structure of the steroids. Benzopyrene
poses a threat to health.