Chapter 15

Benzene and Aromatic Compounds

15.1 Background
15.2 Structure of benzene
15.3 Nomenclature of benzene derivatives
15.4 Spectroscopic properties
15.5 Interesting aromatic compounds
15.6 Benzene’s unusual stability
15.7 The criteria for aromaticity – Huckel’s rule
15.8 Examples of aromatic compounds
15.9 What is the basis of Huckel’s rule?
15.10 The inscribed polygon method for predicting aromaticity
15.11 Buckminsterfullerene – Is it aromatic?
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15.1 Background
Benzene (C6H6)
the simplest aromatic hydrocarbon (or arene).
Reactivity of Benzene
1. Whereas unsaturated hydrocarbons (alkenes, alkynes, and
dienes) readily undergo addition reactions, benzene does not.

2. Benzene undergoes substitution, rather than addition,

in the presence of Lewis acid.

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15.1 Background
Structure of Benzene (C6H6)
Four degrees of unsaturation, highly unsaturated hydrocarbon
Kekulé Description

benzene was a rapidly equilibrating mixture of two compounds

Current View of Structure of Benzene

There is no equilibrium between the two different kinds
of benzene molecules.
Current descriptions of benzene are based on resonance
and electron delocalization due to orbital overlap.
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15.2 The Structure of Benzene
Any structure for benzene must account for the
following facts:
• It contains a six-membered ring and three additional degrees
of unsaturation.
• It is planar.
• All bond lengths are equal.

The Kekulé Structure

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15.2 The Structure of Benzene
Resonance

Bond Distance

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15.2 The Structure of Benzene
Hybridization and Orbitals

Electron Density in Benzene

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15.3 Nomenclature of Benzene Derivatives
15.3A Monosubstituted Benzenes
Name the substituent and add the word benzene.

Many monosubstituted benzenes have common names.

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15.3 Nomenclature of Benzene Derivatives
15.3B Disubstituted Benzenes
- Consider the relative positions of the substituents!!
- ortho, meta, or para—can be used to designate the relative
position of the two substituents.

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15.3 Nomenclature of Benzene Derivatives
15.3B Disubstituted Benzenes
When two groups on the benzene ring are different,
- Consider the relative positions of the substituents
- Consider the priority of the substituents based on alphabet.

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15.3 Nomenclature of Benzene Derivatives
15.3C Polysubstituted Benzenes
For three or more substituents on a benzene ring:
1. Number to give the lowest possible numbers around the ring.
2. Alphabetize the substituent names.
3. When substituents are part of common roots, name the molecule
as a derivative of that monosubstituted benzene. The substituent
that comprises the common root is located at C1.

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15.3 Nomenclature of Benzene Derivatives
15.3D Naming Aromatic Rings as Substituents
A benzene substituent is called a phenyl group

The benzyl group

Aryl groups:
Substituents derived from other substituted aromatic rings
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15.4 Spectroscopic Properties

NMR spectroscopy can be used to determine the substitution patterns in

disubstituted benzenes!!

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15.5 Interesting Aromatic Compounds
BTX (benzene, toluene, xylene)

Polycyclic Aromatic Hydrocarbons (PAHs)

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15.5 Interesting Aromatic Compounds
Helocenes and Twistoflex

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15.6 Benzene’s Unusual Stability
Heats of Hydrogenation

Resonance Energy of Benzene

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15.6 Benzene’s Unusual Stability
Reactivity of Benzene

rt High P and T

Reaction of Benzene with Bromine

Benzene does not undergo addition reactions with bromine,

but it yields an addition product.
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15.7 The Criteria for Aromaticity – Huckel’s Rule
Four structural criteria for aromatic compounds :
1. A molecule must be cyclic.

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15.7 The Criteria for Aromaticity – Huckel’s Rule
Four structural criteria for aromatic compounds :
2. A molecule must be planar.

Reaction of Cyclooctatetraene with Bromine:

Addition Reaction

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15.7 The Criteria for Aromaticity – Huckel’s Rule
Four structural criteria for aromatic compounds :
3. A molecule must be completely conjugated.

4. A molecule must contain a particular number of π-electrons.

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15.7 The Criteria for Aromaticity – Huckel’s Rule
Four structural criteria for aromatic compounds :
4. A molecule must contain a particular number of π-electrons.

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15.8 Examples of Aromatic Compounds
15.8A Aromatic Compounds with a Single Ring
Annulene

[10]-Annulene: aromatic??

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15.8 Examples of Aromatic Compounds
15.8B Aromatic Compounds with More than One Ring

Resonance Structure of Naphthalene

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15.8 Examples of Aromatic Compounds
15.8C Aromatic Heterocycles
Pyridine

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15.8 Examples of Aromatic Compounds
15.8C Aromatic Heterocycles
Pyrrole
Pyrrole has six π electrons
—four from the bonds and two from the lone pair
pyrrole  Aromatic compound

Pyridine vs Pyrrole

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15.8 Examples of Aromatic Compounds
15.8C Aromatic Heterocycles
Histamine

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15.8 Examples of Aromatic Compounds
15.8D Charged Aromatic Compounds
Cyclopentadienyl Anion

Similar to Pyrrole!!

Cyclopentadienyl Compounds

Preparation of Cyclopentadienyl Anion

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15.8 Examples of Aromatic Compounds
15.8D Charged Aromatic Compounds
Tropylium Cation

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15.9 What is the Basis of Huckel’s Rule?
Why does the number of π electrons determine whether a
compound is aromatic?

The basis of aromaticity can be better understood

by considering orbitals and bonding.

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15.9 What is the Basis of Huckel’s Rule?
15.9A Bonding and Antibonding Orbitals
Valence Bond Theory:
Inadequate for describing systems with delocalized p orbitals in
the compounds, such as aromatic compounds

Molecular Orbital Theory:

Permits a better explanation of bonding in aromatic systems

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15.9 What is the Basis of Huckel’s Rule?
15.9A Bonding and Antibonding Orbitals

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15.9 What is the Basis of Huckel’s Rule?
15.9B MOs Formed When More Than Two p Orbitals Combine

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15.10 The Inscribed Polygon Method
How to Predict Aromaticity

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15.10 The Inscribed Polygon Method
How to Predict Aromaticity

This method works for all monocyclic completely conjugated systems

regardless of ring size.
The inscribed polygon method is consistent with Hückel's rule—there is
always one lowest energy bonding MO that can hold two electrons and the
other bonding MOs come in degenerate pairs that can hold a total of four
electrons. 33
15.10 The Inscribed Polygon Method
How to Predict Aromaticity
This method works for all monocyclic completely conjugated systems
regardless of ring size.

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15.10 The Inscribed Polygon Method
MO Patterns for Cyclic, Completely Conjugated Systems

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15.10 The Inscribed Polygon Method

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15.11 Buckminsterfullerene-Is It Aromatic?
The two most common elemental forms of carbon

Their physical characteristics are very different because their molecular

structures are very different.

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15.11 Buckminsterfullerene-Is It Aromatic?
Buckminsterfullerene

Is it aromatic? Nope
1. Not satisfy Huckel’s rule (not planar)
2. Addition reaction with E+

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