Aromatic Compounds

Aromatic compounds are unusually STABLE and have important chemical and synthetic uses. In fact, nucleic
acids and amino acids that make up every cell rely heavily on the use aromatic compounds. But, what makes a
compound aromatic? A short list of rules, discovered by Eric Huckel in the 1930’s, lists the properties of
aromatic compounds.
The Huckel aromaticity rules are:

1. Molecule is cyclic
2. Have one p orbial per atom of the ring
3. Be planar, in an sp2 hybridized orbital, over every atom of the ring
4. Have a closed loop of 4n+2 pi-bond electrons, where n is equal to any integer (0,1,2,3,…)
But like most natural phenomenon, there exists a rule exactly the opposite. Molecules that have an unusual
INSTABILITY to them are anti-aromatic compounds. They have similar rules to aromaticity, including:
1. Molecule is cyclic
2. Have one p orbial per atom of the ring
3. Be planar, in an sp2 hybridized orbital, over every atom of the ring
4. But, anti-aromatic compounds have a closed loop of 4n pi-bond electrons.
Below are the pi-orbital diagrams of benzene, the most identifiable aromatic compound. Each of the three
double bonds contributes 2 pi-electrons over 6 atoms, for a total of 4*1+2=6 electrons, in a ring, in a pi-orbital
that is planar. Therefore it is aromatic. In contrast, hexatriene meets all of these criteria as well, but is not in a
closed ring. Hexatriene is therefore non-aromatic. Finally, cyclobutadiene is the most identifiable anti-
aromatic compound which is different only in that it has 4*1=4 pi-electrons, in a ring, in a pi-orbital that is

planar.

Heterocyclic Aromatic Compounds

The diversity of compounds relies on using atoms other than carbon, however. What about when atoms with
lone pairs of electrons are involved? A good rule of thumb is that if the atom is already participating in the pi-
bond forming in the ring, then the lone pair of electrons are perpendicular to the ring and therefore are NOT
participating to aromaticity. A good example of this is pyrimidine, where both nitrogens are already
contributing to the pi-bond ring and therefore, the lone pairs of electrons are not accessible.
However, there are many molecules where lone pair DO participate to aromaticity. Below are several
examples. Take furan for example; oxygen has two lone pairs of electrons. One of them is in a geometry
parallel to the pi-bond system. Therefore, these electrons DO participate in the pi-bond system and add 2
electrons the pi-bond count resulting in 4*1+2=6 electrons, therefore furan is aromatic. Imidiazole is molecule
that has two nitrogen atoms; one nitrogen participating in pi-bonding and not contributing lone pairs, while the
other is not participating in pi-bonding but contributes electrons the pi-bond count. The 4*1+2=6 electron
count for imidazole renders it aromatic.

Aromatic Hydrocarbon Ions

Sometimes, carbocations and carbanions are produced in chemical reactions. If these species are created in a
cyclic conjugated system, it is possible that they can contribute to the formation of a Huckel aromatic
compound, which gives the molecule added stability and special reactivity.
For example, cyclopentadiene is not aromatic because of the sp3 hybridized carbon at position 5 on the
ring. However, in the presence of strong base, cyclopentadiene can be deprotonated and cyclopentadienyl
anion is generated. The lone pair of electrons assumes a sp2 hybridized orbital, making the molecule planar,
adding 2 more electrons to the ring to give 4n+2 pi-electrons and creating the 5th pi orbital necessary to
complete Huckel’s Rule and results in an aromatic ion.
Another example is formation of a carbocation, a common intermediate in substitution and elimination
reactions. Deprotonation of cycloheptatriene, a non-aromatic compound, at the sp3 hybridized position creates
a sp2 hybridized orbital and, although this carbon’s pi-bond orbital is empty (a carbocation), it completes the
7th pi orbital necessary to complete the ring and maintains a 4n+2 electron count. This carbocation, called
tropylium ion, is now aromatic.
Difference Between Benzenoid and Non Benzenoid

The key difference between benzenoid and non benzenoid compounds is that benzenoid
compounds contain at least one benzene ring in the molecule whereas non
benzenoid compounds have no benzene rings.

An aromatic compound is a cyclic, planar molecule with a ring of resonance bonds. These
structures are more stable than normal ring structures. Both benzenoid and non benzenoid
compounds are aromatic compounds. Therefore, all aromatic compounds are not
necessarily benzenoid compounds.

CONTENTS

1. Overview and Key Difference

2. What is Benzenoid
3. What is Non Benzenoid
4. Similarities Between Benzenoid and Non Benzenoid
5. Side by Side Comparison – Benzenoid vs Non Benzenoid in Tabular Form
6. Summary

What is Benzenoid
Benzenoid compounds are molecules that have at least one benzene ring in its chemical
structure. A benzene ring is a cyclic structure having six carbon atoms as the ring members.
It has three pi bonds (double bonds) and three sigma bonds arranged in an alternative
pattern. Therefore, we call this pattern a conjugated pi system.

Figure 01: Toluene – Benzenoid Compound

 Since the molecule has double bonds due to benzene ring, the molecule is an unsaturated
compound with extra stability provided by the conjugated pi system.

What is Non Benzenoid?

Non benzenoid compounds are aromatic molecules that do not have benzene rings in its
chemical structure. Although a benzene ring is absent, these molecules have a conjugated
pi system. The ring structures of these compounds have around 5-7 carbon atoms.

Figure 02: Azulene – A Non Benzenoid Compound

The aromatic nature arises due to the presence of conjugated pi system. This conjugated pi
system provides the molecule with extra stability. Some common examples include
azulenes, Oxaazulanones, Pentafulvene, Tropones & Tropolones, etc.

What are the Similarities Between Benzenoid and Non

Benzenoid?
 Both are cyclic structures
 Benzenoid and Non Benzenoid are aromatic compounds with conjugated pi systems
 Both Benzenoid and Non Benzenoid exhibit an extra stability

What is the Difference Between Benzenoid and Non

Benzenoid?
Although both benzenoid and non benzenoid compounds are aromatic compounds, they
have few differences between them. The difference is the presence of a benzene ring in
these two compounds. In benzenoid compounds there are benzene rings present that gives
cause to its name whereas a benzene ring is absent in non benzenoid compounds. These
structural differences definitely affect the chemical properties and reactivity of these
compounds.

Summary – Benzenoid vs Non Benzenoid

Both benzenoid and non benzenoid compounds are aromatic structures having a
conjugated pi system. Therefore, both these structures show extra stability. The difference
between benzenoid and non benzenoid compounds is that benzenoid compounds contain
at least one benzene ring in the molecule whereas non benzenoid compounds have no
benzene rings.