John E.

McMurry

www.cengage.com/chemistry/mcmurry

Chapter 15
Benzene and Aromaticity

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Learning Objectives
(15.1)
Naming aromatic compounds
(15.2)
Structure and stability of benzene
(15.3)
Aromaticity and the Hckel 4n + 2 rule
(15.4)
Aromatic ions

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Learning Objectives
(15.5)
Aromatic heterocycles: Pyridine and pyrrole
(15.6)
Polycyclic aromatic compounds
(15.7)
Spectroscopy of aromatic compounds

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Naming Aromatic Compounds

Coal and petroleum are the major sources of

simple aromatic compounds

Coal primarily comprises of large arrays of
conjoined benzene-like rings
When heated to 1000C, coal thermally breaks
down to yield coal tar
Petroleum primarily comprises alkenes and few
aromatic compounds

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Figure 15.1 - Some Aromatic

Hydrocarbons

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Naming Aromatic Compounds

Aromatic compounds possess the largest

number of nonsystematic names, of which some

are allowed by the IUPAC

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Naming Aromatic Compounds

Monosubstituted benzenes have systematic

names with benzene being the parent name

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The Phenyl Group

Arenes are alkyl-substituted benzenes
Based on the size of the alkyl substituents, they
are termed alkyl-substituted or phenyl-substituted
benzene
The term phenyl (Ph or ) is used in cases of a
substituent benzene ring in the C6H5

The term benzyl is used for the C6H5CH2 group

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Disubstituted Benzenes
Names based on the placement of substituents
Ortho (o), meta (m) , and para (p)

Provides clarity in the discussion of reactions

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Benzenes With More Than Two

Substituents
Numbers with the lowest possible values are

chosen
List substituents alphabetically with hyphenated
numbers
Common names, such as toluene can serve as
root name(as in TNT)

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Worked Example
Provide the IUPAC name for the following

compound

Solution:
The compound is 1-Ethyl-2,4-dinitrobenzene

Substituents on trisubstituted rings receive the

lowest possible numbers
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Structure and Stability of

Benzene
The reactivity of benzene is much lesser than

that of alkenes despite having six fewer

hydrogens

Benzene - C6H6

Cycloalkane - C6H12

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Heats of Hydrogenation as
Indicators of Stability
Comparison of the heats of hydrogenation

proves the stability of benzene

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Structure of Benzene
All its C-C bonds are the same length: 139 pm

between single (154 pm) and double (134

pm) bonds
Electron density in all six C-C bonds is identical
Structure is planar, hexagonal

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Structure of Benzene
Carbon atoms and p orbitals in benzene are

equivalent
Defining three localized bonds in which a
given p orbital overlaps only one neighboring p
orbital
All electrons move freely in the entire ring due
to equal overlap of all p orbitals

Resonance of benzene is another factor that

influences its rate of reactivity

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Indicating CarbonCarbon Bond

Equivalence in Benzenes
The two benzene resonance forms can be

represented by a single structure with a circle in

the center to indicate the equivalence of the
carboncarbon bonds

The ring does not indicate the number of

electrons in the ring but is a reminder of the
delocalized structure

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Molecular Orbital Description of

Benzene
The 6 p-orbitals combine to give:
Three bonding orbitals with 6 electrons
Three antibonding with no electrons
Orbitals with the same energy are degenerate

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Worked Example
Pyridine - A flat, hexagonal molecule with bond

angles of 120undergoes substitution rather

than addition and generally behaves like
benzene

Draw a picture of the orbitals of pyridine to

explain its properties

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Worked Example
Solution:

The pyridine ring is formed by the overlap of

carbon and nitrogen sp2 orbitals
Six p orbitals perpendicular to the plane of the
ring hold six electrons
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Worked Example

These six p orbitals form six molecular orbitals

that allow electrons to be delocalized over the
system of the pyridine
The lone pair of nitrogen occupies an sp2 orbital
that lies in the plane of the ring

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Aromaticity and the Hckel

4n+2 Rule
Unusually stable - Heat of hydrogenation 150

kJ/mol less negative than a hypothetical cyclic

triene
Planar hexagon - Bond angles are 120, carboncarbon bond length is 139 pm
Undergoes substitution rather than electrophilic
addition
Resonance hybrid with structure between two
line-bond structures

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The Hckel 4n + 2 Rule

Developed by Erich Hckel in 1931
States that a molecule can be aromatic only if:
It has a planar, monocyclic system of conjugation
It contains a total of 4n + 2 molecules

n = 0,1,2,3

4n electrons are considered antiaromatic

Cyclobutadiene possesses four electrons and

is antiaromatic

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The Hckel 4n + 2 Rule

It reacts readily and exhibits none of the

properties corresponding to aromaticity
It dimerizes by a Diels-Alder reaction at 78 C

Benzene possesses six electrons (4n + 2 = 6

when n = 1) and is aromatic

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The Hckel 4n + 2 Rule

Cyclooctatetraene possesses eight molecules

and is not aromatic

Comprises four double bonds

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Aromatic Stability and the

Molecular Orbital Theory
Calculation of energy levels of molecular orbitals

for cyclic conjugated molecules shows that there

is always a single lowest-lying MO above which
MOs come in degenerate pairs

Lowest lying molecular orbital is filled by a pair of

electrons and higher orbitals are filled by two
pairs of electrons

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Figure 15.5 - Energy Levels of the

Six Benzene Molecular Orbitals

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Worked Example
To be aromatic, a molecule must have 4n + 2

electrons and must have a planar, monocyclic

system of conjugation

Explain why cyclodecapentaene has resisted all

attempts at synthesis though it has fulfilled only
one of the above criteria

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Worked Example
Solution:

Cyclodecapentaene possesses 4n + 2 (n = 2)
but is not flat
If cyclodecapentaene were flat, the starred
hydrogen atoms would crowd each other across
the ring

To avoid this interaction, the ring system is distorted

from planarity
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Aromatic Ions
The 4n + 2 rule applies to ions as well as neutral

substances

Both the cyclopentadienyl anion and the

cycloheptatrienyl cation are aromatic

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Aromatic Ions
When one hydrogen is removed from the

saturated CH2 in an aromatic ion, rehybridization

of the carbon from sp3 to sp2 would result in a
fully conjugated product with a p orbital on every
product
Methods to remove the hydrogen molecule

Removing the hydrogen with both electrons (H:)

from the CH bond results in a carbocation
Removing the hydrogen with one electron (H)
from the CH bond results in a carbon radical
Removing the hydrogen without any electrons
(H+) from the CH bond results in a carbanion
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Figure 15.6 - Cyclopentadienyl Anion

and Cycloheptatrienyl Cation

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Aromaticity of Cyclopentadienyl
Anion
Disadvantages of the four--electron

cyclopentadienyl cation and the five-cyclopentadienyl radical

Highly reactive
Difficult to prepare
Not stable enough for aromatic systems

Advantages of using the six--electron

cyclopentadienyl cation

Easily prepared
Extremely stable
pKa =16
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Figure 15.7 - The Aromatic Cyclopentadienyl

Anion and the Aromatic Cycloheptatrienyl Cation

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Worked Example
Cyclooctatetraene readily reacts with potassium

metal to form the stable cyclooctatetraene

dianion, C8H82

Explain why this reaction occurs so easily

Determine the geometry for the
cyclooctatetraene dianion

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Worked Example
Solution:
When cyclooctatetrene accepts two electrons, it
becomes a (4n + 2) electron aromatic ion
Cyclooctatetraenyl dianion is planar with a
carboncarbon bond angle of 135, that of a
regular octagon

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Aromatic Heterocycles: Pyridine

and Pyrrole
Heterocycle: Cyclic compound that comprises

atoms of two or more elements in its ring

Carbon along with nitrogen, oxygen, or sulfur

Aromatic compounds can have elements other

than carbon in the ring

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Pyridine
Six-membered heterocycle with a nitrogen atom

in its ring
electron structure resembles benzene (6
electrons)
The nitrogen lone pair electrons are not part of
the aromatic system (perpendicular orbital)
Pyridine is a relatively weak base compared to
normal amines but protonation does not affect
aromaticity

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Pyridine and Pyrimidine

The structure of pyridine is quite similar to that

of benzene

All five sp2-hybridized ions possess a p orbital

perpendicular with one to the plane of the ring
Each p orbital comprises one electron
The nitrogen atom is also sp2-hybridized and
possesses one electron in a p orbital

Pyrimidine comprises two nitrogen atoms in a

six-membered, unsaturated ring

The sp2-hybridized nitrogen atoms share an

electron each to the aromatic system
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Figure 15.8 - Pyridine and

Pyrimidine

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Figure 15.9 - Pyrrole and

Imidazole

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Rings of Pyrimidine and

Imidazole
Significant in biological chemistry
Pyrimidine is the parent ring system present in

cytosine, thymine, and uracil

Histidine contains an aromatic imidazole ring

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Worked Example
Draw an orbital picture of Furan to show how the

molecule is aromatic

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Worked Example
Solution:

Furan is an oxygen analog of pyrrole

It possesses 6 electrons on a cyclic,
conjugated system; it is aromatic
Oxygen contributes two lone-pair electron from a
p orbital perpendicular to the plane of the ring
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Polycyclic Aromatic Compounds

While the Hckel rule is relevant only to

monocyclic compounds, the concept of

aromaticity can also be applied to polycyclic
aromatic compounds

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Naphthalene Orbitals
Three resonance forms and delocalized

electrons

Naphthalene and other polycyclic aromatic

hydrocarbons possess certain chemical

properties that correspond to aromaticity

Heat of hydrogenation in naphthalene is

approximately 250 kJ/mol
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Aromaticity of Naphthalene
Naphthalene possesses a cyclic, conjugated

electron system

p orbital overlap is present along the ten-carbon

periphery of the molecule and across the central
bond

Aromaticity is due to the electron delocalization

caused by the presence of ten electrons (Hckel
number)

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Heterocyclic Analogs of
Naphthelene
Quinolone, isoquinolone, and purine have

pyridine-like nitrogens that share one electron

Indole and purine have pyrrole-like nitrogens
that share two electrons

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Worked Example
Azulene, a beautiful blue hydrocarbon, is an

isomer of naphthalene

Determine whether it is an aromatic

Draw a second resonance form of azulene in
addition to the form shown below

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Worked Example
Solution:

Azulene is an aromatic because it has a

conjugated cyclic electron system containing
ten electrons (a Hckel number)

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Spectroscopy of Aromatic
Compounds
Infrared Spectroscopy
CH stretching absorption is seen at 3030 cm 1

Usually of low intensity

A series of peaks are present between 1450 and

1600 cm1

Caused by the complex molecular motions of the

ring

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Ultraviolet Spectroscopy
Presence of a

conjugated system
makes ultraviolet
spectroscopy possible

Intense absorption
occurs near 205 nm
Less intense absorption
occurs between 255 nm
and 275 nm

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Nuclear Magnetic Resonance

Spectroscopy
The aromatic ring shields hydrogens
Absorption occurs between 6.5 and 8.5
The ring current is responsible for the difference

in chemical shift between aromatic and vinylic

protons

Ring current is the magnetic field caused by the

circulation of delocalized electrons when the
aromatic ring is perpendicular to a strong
magnetic field

The effective magnetic field is greater than the

applied field
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Figure 15.13 - The Origin of

Aromatic Ring Current

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Nuclear Magnetic Resonance

Spectroscopy
Aromatic protons appear as two doublets at

7.04 and 7.37

Benzylic methyl protons appear as a sharp
singlet at 2.26

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C NMR of Aromatic
Compounds
13

Carbons in aromatic ring absorb between 110

and 140
Shift is distinct from alkane carbons but in same
range as alkene carbons

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C NMR of Aromatic
Compounds
13

The mode of substitution influences the

formation of two, three, or four resonances in

the proton-decoupled 13C NMR spectrum

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Figure 15.16 - The Proton-Decoupled 13C

NMR Spectra of the Three Isomers of
Dichlorobenzene

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Summary
The term aromatic refers to the class of

compounds that are structurally similar to

benzene
Apart from IUPAC terms, disubstituted benzenes
are also called ortho, meta, or para derivatives

The C6H5 unit is called a phenyl group

The C6H5CH2 unit is called a benzyl group

The Hckel rule states that in order to be

aromatic, a molecule must possess 4n + 2

electrons, where InI = 0,1,2,3, and so on
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Summary
Planar, cyclic, conjugated molecules with other

numbers of electrons are antiaromatic

Pyridine and pyrimidine are six-membered,
nitrogen containing, aromatic heterocycles

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