Chapter 14 – Aromatic Compounds - Chapter 14 is mostly descriptive and does not

include much chemistry, as the reactions of aromatic compounds are covered in chapter
15. This document provides a summary of major points of chapter 14, which we will not
spend much class time on.

Benzene – Molecular formula C6H6 was first established in 1834. Based on this
formula, benzene must have four double bonds and/or rings. However, it does not
exhibit the reactivity of typical alkenes or polyenes.

H H
CH 2 C C C C CH 2 or CH 3 C C C C CH 3

OH OH
KMnO 4

OH OH
OH H
H2SO4

H2O
H OH

Br Br
Br2

Br Br

KMnO 4 or
no reaction
H2SO4, H2O

Br2
benzene no reaction

Br2
C6H5Br + HBr a new reaction
FeBr3

There is something fundamentally different about benzene and its derivatives. They
were called aromatic compounds because of their characteristic aromas.
Several possible structures for benzene were proposed:
Kekule’ (1865)
H
H H

H H
H
This structure violates the tetravalency of carbon. The structure was later modified to:
H H
H H H H

H H H H
H H

Equlibrating isomers – This does not account for the non-alkene character of benzene.

Armstrong (1866)
H
H H

H H
H

Fourth valence directed inward.

Dewar (1867)

This is a valid structure and was synthesized by Van Tamelin et al. (1962). However, it
is not benzene and is now known as Dewar benzene.

Landenburg (1870)

This structure (prismane) was prepared by T. Katz et al. (1973) and was shown to form
benzene upon heating to 90 C.
The x-ray crystal structure of benzene shows a regular hexagonal structure (as
suggested by Kekule’). The C-C bond length is 1.40 Å, between that of a single bond
(1.54 Å) and a double bond (1.33 Å). Bond angles are all 120 (sp2-hybrid orbitals).

The fourth valence of carbon is accounted for by -bonds from p-orbitals extending
equally around the ring. This may be depicted as two equivalent resonance structures.

This is not equilibrating cyclohexatrienes. There is continuous –bonding extending

uniformly around the ring. The electrons are delocalized.

It is inconvenient to draw both resonance structures. For simplicity we write as one

resonance structure: The hexagon with the circle inside is convenient for representing
structures, but in drawing mechanisms always start from the structure with double
bonds explicitly shown and do not use the circle structure.

or

Other shorthand notations. The following are all representations of a “phenyl” group:

H H

H or = C6H5- = Ph- or Ø-

H H

Do not confuse “phenyl” with a “benzyl” group, which is phenyl-CH2:

CH 2 = Ph-CH2- or Ø-CH2- = Bn-

Example: Benzyl bromide

CH 2 Br
Nomenclature: Derivatives are named as substituted benzenes.

All positions on the ring are equivalent (there is only one isomer of a monosubstituted
benzene) so we don’t need to designate a position.

Br NO 2

bromobenzene nitrobenzene

Many monosubstituted benzenes have trivial names.

Disubstituted benzenes: There are three distinct positions for substitution on a

monosubstituted benzene and thus there are three possible isomers of any
disubstituted benzene.
For three or more substituents do not use ortho, meta, or para but only use numbers to
indicate positions.

Now let us return to the unique reactivity of benzene. The structure of benzene doesn’t
explain why it should not react like a normal alkene or polyene.

Look at some enthalpies of hydrogenation:

H2
H° = -120 kJ/mol
catalyst

2H2
H° = -232 kJ/mol
catalyst

3H2
expect H° = 3(-120 kJ/mol) = -360 kJ/mol
catalyst
actual H° = -208 kJ/mol

The difference between expected and observed of 152 kJ/mol is considered “resonance
energy”.

In contrast, cyclobutadiene and cyclooctatetraene do not exhibit this special stability and
undergo reactions typical of alkenes.

cyclobutadiene cyclooctatetraene
Why is the resonance energy of benzene so high? Look to molecular orbital theory for
an explanation.

The table below shows the  molecular orbital energies of five unsaturated systems
calculated using Hückel theory.  is the energy of an electron in an isolated p-orbital
and  is a negative value of energy. ( is the difference in energy between a p-orbital
and the bonding  molecular orbital of ethylene and is estimated at about -250 to -290
kJ/mol). Thus an orbital with energy of +  is lower in energy than an isolated p-
orbital (energy = ). An orbital with energy =  is nonbonding, orbitals lower in energy
than  are bonding, and orbitals higher in energy than  are antibonding. These
molecular orbital energies for cyclic polyunsaturated systems can be predicted using the
circle method described in sec. 14.7A of Solomons and Fryhle 10th Ed.

__  - 2 __ - 2
__ - 1.80
__ - 1.62

__ - 1.25

__ -  __ __ - 

__ - 0.62
__ - 0.45

_ _

 + 0.45
 + 0.62

 +    + 

 + 1.25

 + 1.62
  + 1.80
 + 2  + 2

ethene 1,3-butadiene 1,3,5-hexatriene cyclobutadiene benzene

The total  electron energy is equal to the number of electrons in each occupied
molecular orbital times the energy of that orbital, summed over all occupied molecular
orbitals. Thus the  electron energy of ethene (ethylene) is 2( + ) = 2 + 2.
Calculated electron energies can be used to estimate “resonance energy” and to
rationalize the special stability and instability of certain systems. Note at a glance from
the above table that cyclobutadiene has two unpaired electrons in nonbonding orbitals.
For the other molecules, all electrons are paired and are in bonding orbitals.
Cyclooctatetraene like cyclobutadiene has unpaired electrons in nonbonding orbitals.

In reality cyclooctatetraene is not planar because the planar structure would be very
unstable. It has alternating short (double) and long (single) bonds in a puckered
structure.

Huckel’s 4n + 2 rule: Fully conjugated planar cyclic systems with (4n + 2)  electrons (n
= any integer) are especially stable relative to their acyclic analogs. Such compounds
are called aromatic. Systems having 4n  electrons are especially unstable relative to
their acyclic analogs and are called antiaromatic.

Annulenes – a general term for monocyclic compounds that can be represented with
alternating single and double bonds.

4 e-s
not aromatic 6 e-s 8 e-s
aromatic not aromatic

Some larger aromatic annulenes are the following:

14  e-s 18  e-s

Polycyclic aromatic hydrocarbons

Biaryls – two aromatic rings linked by a single bond.

biphenyl
Condensed benzenoid systems.

Many examples are known. Like benzene, these are all aromatic. Each of these can
be viewed as one cyclic conjugated system by basically ignoring the “bridging” bonds.
For naphthalene, this is better represented by the resonance structure on the right.
Unlike the two resonance structures of benzene, these two structures are not
equivalent. Anthracene and phenanthrene are both shown in the resonance structure
that best illustrates the continuous cyclic  system.

azulene

Azulene is a nonbenzenoid aromatic compound having 10 -electrons.

Some cyclic conjugated ions are also aromatic:

Graphite consists of stacked sheets of condensed benzene rings. The distance

between sheets is about 3.4 Å. Graphite is soft because the sheets can slide over each
other readily. (Diamond is very different, as each carbon atom is sp3 hybridized and is
bonded to four other carbon atoms by single bonds.)

The third and most recently discovered allotrope of carbon is the fullerenes. The name
comes from their similarity to the geodesic domes of the architect Buckminister Fuller.
Fullerenes, like graphite, consist of an array of fused benzene rings. The most common
fullerene has the molecular formula C60 and has the shape of a soccer ball. All 60
carbons are equivalent, are sp2 hybridized and are bonded to three other carbon atoms.

Carbon nanotubes are all carbon tubes with structures related to the fullerenes. They
consist of a tube-shaped network of fused benzene rings with half of a fullerene at each
end. Carbon nanotubes are 100-times as strong as steel and have potential practical
applications that are still being developed.
Heterocyclic aromatic compounds.

Cyclic compounds that contain elements other than carbon as one or more of the ring
atoms are called heterocyclic compounds. The most common ring “heteroatoms” are
nitrogen and oxygen. The structures shown below are all aromatic “heterocycles”.

Each ring atom can have only one p-orbital oriented perpendicular to the plane of the
ring as part of the cyclic  system. If a ring heteroatom has a double bond to an
adjacent atom, as in the nitrogen atom of pyridine, the p-orbital that is part of the 
system is part of that bond. Any lone electron pair on that atom is orthogonal and not
part of the ring  system. The lone pair is thus not included in the electron count for
determining aromaticity. If a ring heteroatom has only single bonds to adjacent atoms,
as in the nitrogen of pyrrole and the oxygen of furan, one of the lone electron pairs on
the heteroatom is in a p-orbital that is part of the  system. One electron pair of the
heteroatom is thus included in the electron count for determining aromaticity. Thus
pyridine, pyrrole, and furan are all cyclic conjugated systems with 6  electrons.
Purine is the ring system of the “bases” adenine and guanine found in DNA and RNA.
The nitrogen atom at position 9 has a lone electron pair that is part of the cyclic 
system.