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Chapter 16: Aromatic Compounds

I. Structures of Benzene (16-1, 16-2)

Benzene was discovered in 1825 by Michael Faraday.

A. Proposed Structure of Benzene (Kekule Structure, 1865)

B. Resonance Structures of Benzene

Resonance accounts for the fact that all bonds are identical. The real
structure is a hybrid of the two resonance structures.

C. MO Picture: Benzene (Cyclic system)

There is a delocalized bond that extends over all six atoms of the
ring:

In benzene this creates a cyclic system.

All molecules that have resonance have delocalized systems.

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II. Special Properties of Benzene

1. Reactivity:

CASE ONE:

CASE TWO:

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2. Benzene is unusually stable (low H of hydrogenation)

III. Resonance Picture for Aromatics

A. What are annulenes?

o Annulenes are cyclic hydrocarbons with alternating double and

single carbon-carbon bonds

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C. MO of Benzene (6 pi electrons)

This electron configuration is sometimes referred to as a closed

bonding shell. (no unpaired electrons)

D. The MO Picture of Cyclobutadiene (4 pi electrons)

Although it is possible to write resonance structures for

cyclobutadiene, experimental evidence indicates that it is very
unstable.

This arrangement is not a closed bonding shell.

MO theory correctly predicts that cyclobutadiene should be very

reactive, and therefore unstable.

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E. Polygon Rule:

In general for an annulene, the MO energy diagram can be predicted

by drawing the relevant polygon shape on its apex, and drawing MO's
are each vertex.

IV. Aromaticity and Huckels Rules

The term aromatic refers to compounds with special properties similar

to that of benzene.

Initially, it was believed that the alternating -bonds in the ring

(alternating -bonds is called conjugation) caused its special
properties.

However, scientists synthesized some larger cyclic compounds with

conjugated double bonds and some of them were found to react like
normal alkenes, and were not aromatic. Hence, a new explanation had
to be made to define aromaticity.

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A. Huckels Rules:

A compound will be aromatic if it has all the following properties:

1. Planar and cyclic;

2. Cyclic system (-bond, lone-pair or empty p-orbital an every

atom of ring);

3. 4n+2 electrons in the cyclic system (2, 6, 10, 14, 18, etc).

Three cases are seen:

1. Aromatic compounds are more stable than their open chain

counterparts.

on-aromatic

3. Anti-aromatic

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B. Ions and Huckels Rule:

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V. Nomenclature of Aromatic Compounds

1. Monosubstituted benzenes are named as substituent benzene.

2. Common names of special monosubstituted benzenes (MEMORIZE).

These are also used in the IUPAC system

3. Use ortho (1,2); meta (1,3); or para (1,4) to indicate the relative
positions of substitute nts on disubstituted benzenes. For groups
that are part of the special benzenes (see part 2 above), the special
group is at position 1.

4. Use the lowest numbers possible to indicate the positions of

substituents on benzenes with three or more substituents. However,
the special groups (from part 2 above) are always placed at position 1

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5. The benzene ring can be named as a phenyl group when attached to

complicated chains

6. There are several polycyclic aromatics with common names

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