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 Hückel 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 1000°C, 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 Φ) 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 Carbon–Carbon 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
carbon–carbon 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 120°undergoes 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 σ 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 Hückel
4n+2 Rule
▪ Unusually stable - Heat of hydrogenation 150
kJ/mol less negative than a hypothetical cyclic
triene
▪ Planar hexagon - Bond angles are 120°,
carbon-carbon 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 Hückel 4n + 2 Rule
▪ Developed by Erich Hückel 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 Hückel 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 Hückel 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 C–H bond results in a carbocation
▪ Removing the hydrogen with one electron (H·)
from the C–H bond results in a carbon radical
▪ Removing the hydrogen without any electrons
(H+) from the C–H 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
carbon–carbon 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 Hückel 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 (Hückel
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 Hückel number)

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Spectroscopy of Aromatic
Compounds
▪ Infrared Spectroscopy
▪ C–H stretching absorption is seen at 3030 cm–1
▪ Usually of low intensity
▪ A series of peaks are present between 1450 and
1600 cm–1
▪ Caused by the complex molecular motions of the
ring

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Infrared Spectroscopy of Aromatic
compounds
▪ 2000-1665 cm-1 (weak bands known as
"overtones")
▪ 900-675 cm-1 (out-of-plane or "oop" bands)

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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 δ
▪ 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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H-NMR of Annulene

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Nuclear Magnetic Resonance
Spectroscopy
▪ Aromatic protons appear as two doublets at 7.04
and 7.37 δ
▪ Benzylic methyl protons appear as a sharp
singlet at 2.26 δ

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13CNMR of Aromatic
Compounds
▪ Carbons in aromatic ring absorb between 110
and 140 δ
▪ Shift is distinct from alkane carbons but in same
range as alkene carbons

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13CNMR of Aromatic
Compounds
▪ 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 Hückel 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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