Organic Chemistry, Second Edition
Janice Gorzynski Smith
University of Hawai’i
Chapter 17
Benzene & Aromatics
Prepared by Rabi Ann Musah
State University of New York at Albany
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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Benzene and Aromatic Compounds
Chapter 17 Topics:
• Benzene structure and properties including IR
and NMR.
• Nomenclature.
• Common aromatic compounds.
• Stability of benzene.
• Criteria for aromaticity:
• Cyclic, planar, complete conjugation, obeys
Huckel’s Rule.
• Aromatic, Anti-aromatic and Non-aromatic
Compounds
• Some aromatic compounds.
• Inscribed polygon method.
• Bonding in carbon structures (Cn). 2
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Benzene and Aromatic Compounds
Background:
• Benzene (C6H6) is the simplest aromatic hydrocarbon
(aromatic compounds are called arenes).
• Benzene has four degrees of unsaturation, making it
a highly unsaturated hydrocarbon.
• Whereas unsaturated hydrocarbons such as alkenes,
alkynes and dienes readily undergo addition
reactions, benzene does not.
Benzene and Aromatic Compounds
Background:
• Benzene does react with bromine, but only in the
presence of FeBr3 (a Lewis acid), and the reaction is a
substitution, not an addition.
• Proposed structures of benzene must account for its
high degree of unsaturation and its lack of reactivity
towards electrophilic addition.
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Benzene and Aromatic Compounds
Historical:
• August Kekulé proposed that benzene was a rapidly
equilibrating mixture of two compounds, each
containing a six-membered ring with three
alternating bonds.
• In the Kekulé description, the bond between any two
carbon atoms is sometimes a single bond and
sometimes a double bond.
• These structures are known as Kekulé structures.
Benzene and Aromatic Compounds
The Structure of Benzene:
Any structure for benzene must account for the
following facts:
1. It contains a six-membered ring and three additional
degrees of unsaturation.
2. It is planar.
3. All C—C bond lengths are equal.
The Kekulé structures satisfy the first two criteria but
not the third, because having three alternating bonds
means that benzene should have three short double
bonds alternating with three longer single bonds.
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Benzene and Aromatic Compounds
Other Information:
• Although benzene is still drawn as a six-membered ring
with alternating bonds, there is not an equilibrium
between the two different benzene structures.
• Current descriptions of benzene are based on orbital
overlap (electron delocalization) and resonance.
• In the nineteenth century, many other compounds
having properties similar to those of benzene were
isolated from natural sources. Since these compounds
possessed strong and characteristic odors, they were
called aromatic compounds. It should be noted,
however, that it is their chemical properties, and not
their odor, that make them special.
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Benzene and Aromatic Compounds
The Resonance Structure of Benzene:
• The resonance description of benzene consists of two
equivalent Lewis structures, each with three double
bonds that alternate with three single bonds.
• The true structure of benzene is a resonance hybrid of
the two Lewis structures, with the dashed lines of the
hybrid indicating the position of the bonds.
• We will use one of the two Lewis structures and not the
hybrid in drawing benzene. This will make it easier to
keep track of the electron pairs in the bonds (the
electrons).
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Benzene and Aromatic Compounds
The Structure of Benzene:
• Because each bond has two electrons, benzene has
six electrons.
Benzene and Aromatic Compounds
The Structure of Benzene:
• In benzene, the actual bond length (1.39 Å) is
intermediate between the carbon—carbon single bond
(1.53 Å) and the carbon—carbon double bond (1.34 Å).
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Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• To name a benzene ring with one substituent, name
the substituent and add the word benzene.
• Common names used for monosubstituted benzenes:
Toluene, Phenol, Aniline, Anisole
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Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• There are three different ways that two groups can be
attached to a benzene ring, so the prefixes: ortho,
meta, or para are used to designate the relative
position of the two substituents.
ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene
or or or
o-dibromobenzene m-dibromobenzene p-dibromobenzene
or 1,2-dibromobenzene or 1,3-dibromobenzene or 1,4-dibromobenzene
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Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• If the two groups on the benzene ring are different,
alphabetize the names of the substituents preceding
the word benzene.
• If one substituent is part of a common root, name the
molecule as a derivative of that monosubstituted
benzene.
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Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
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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Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• Other common monosubstituted benzenes:
benzaldehyde, benzoic acid, acetophenone & styrene
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Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• A benzene substituent is called a phenyl group, and it
can be abbreviated in a structure as “Ph-”.
• Therefore, benzene can be represented as PhH, and
phenol would be PhOH.
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Benzene and Aromatic Compounds
Nomenclature of Benzene Derivatives:
• The benzyl group, another common substituent that
contains a benzene ring, differs from a phenyl group.
• Substituents derived from other substituted aromatic
rings are collectively known as aryl groups.
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Benzene and Aromatic Compounds
Interesting Aromatic Compounds:
• Benzene and toluene, the simplest aromatic
hydrocarbons obtained from petroleum refining, are
useful starting materials for synthetic polymers.
• Compounds containing two or more benzene rings
that share carbon—carbon bonds are called polycyclic
aromatic hydrocarbons (PAHs). Naphthalene, the
simplest PAH, is the active ingredient in mothballs.
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Benzene and Aromatic Compounds
Stability of Benzene:
• Consider the heats of hydrogenation of benzene,
1,3-cyclohexadiene and cyclohexene, all of which
give cyclohexane when treated with excess
hydrogen in the presence of a metal catalyst.
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Benzene and Aromatic Compounds
Stability of Benzene:
Figure 17.6 compares the hypothetical and observed
heats of hydrogenation for benzene.
Figure 17.6 A comparison between the observed and
hypothetical heats of hydrogenation for benzene
The difference between the hypothetical and observed
heats of hydrogenation for benzene cannot be explained
solely on the basis of resonance and conjugation. 20
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Benzene and Aromatic Compounds
Stability of Benzene:
• The low heat of hydrogenation of benzene means that benzene
is especially stable, even more so than conjugated polyenes.
This unusual stability is characteristic of aromatic compounds.
• Benzene’s unusual behavior is not limited to hydrogenation.
Benzene does not undergo addition reactions typical of other
highly unsaturated compounds, including conjugated dienes.
• Benzene does not react with Br2 to yield an addition product.
Instead, in the presence of a Lewis acid, bromine substitutes
for a hydrogen atom, yielding a product that retains the
benzene ring.
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Benzene and Aromatic Compounds
The Criteria for Aromaticity:
Four structural criteria must be satisfied for a compound
to be aromatic.
[1] A molecule must be cyclic.
To be aromatic, each p orbital must overlap with
p orbitals on adjacent atoms. 22
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Benzene and Aromatic Compounds
The Criteria for Aromaticity:
[2] A molecule must be planar.
All adjacent p orbitals must be aligned so that the
electron density can be delocalized.
Since cyclooctatetraene is non-planar, it is not
aromatic, and it undergoes addition reactions just like
those of other alkenes.
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Benzene and Aromatic Compounds
The Criteria for Aromaticity:
[3] A molecule must be completely conjugated.
Aromatic compounds must have a p orbital on every atom
and each must overlap with adjacent p orbitals.
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Benzene and Aromatic Compounds
The Criteria for Aromaticity:
[4] A molecule must satisfy Hückel’s rule, which
requires a particular number of electrons.
Hückel's rule:
Benzene is aromatic and especially stable because it
contains 6 electrons.
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Benzene and Aromatic Compounds
Cyclobutadiene is antiaromatic and especially unstable
because it contains 4 electrons.
As the number of fused rings increases, the number of
resonance structures increases. Naphthalene is a
hybrid of three resonance structures whereas
benzene is a hybrid of two.
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Benzene and Aromatic Compounds
Hückel’s Rule
Note that Hückel’s rule refers to the number of electrons,
not the number of atoms in a particular ring.
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Benzene and Aromatic Compounds
Aromatic, Antiaromatic and Nonaromatic Compounds
With regard to aromaticity, a compound can be
classified in one of three ways:
1. Aromatic: A cyclic, planar, completely conjugated
compound with 4n + 2 electrons.
2. Antiaromatic: A cyclic, planar, completely
conjugated compound with 4n electrons.
3. Nonaromatic: A compound that lacks one (or more)
of the following requirements for aromaticity: being
cyclic, planar, and completely conjugated.
A completely conjugated, monocyclic hydrocarbon is
called an annulene (not necessarily aromatic). 28
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Benzene and Aromatic Compounds
Aromatic, Antiaromatic and Nonaromatic Compounds
Note the relationship between each compound type and a similar
open-chained molecule having the same number of electrons.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Two or more six-membered rings with alternating
double and single bonds can be fused together to
form polycyclic aromatic hydrocarbons (PAHs).
• There are two different ways to join three rings
together, forming anthracene and phenanthrene.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Completely conjugated rings larger than benzene are
also aromatic if they are planar and have 4n + 2
electrons.
• An annulene is a monocyclic hydrocarbon with
alternating double and single bonds.
• To name an annulene, indicate the number of atoms in
the ring in brackets and add the word annulene.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• [10]-Annulene has 10 electrons, which satisfies
Hückel's rule, but a planar molecule would place the
two H atoms inside the ring too close to each other.
Thus, the ring puckers to relieve this strain.
• Since [10]-annulene is not planar, the 10 electrons
can’t delocalize over the entire ring and it is not
aromatic.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Heterocycles containing oxygen, nitrogen or sulfur, can
also be aromatic.
• With heteroatoms, one must determine whether the
lone pair is localized on the heteroatom or part of the
delocalized system.
• An example of an aromatic
heterocycle is pyridine.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Pyrrole is an aromatic heterocycle that contains a
five-membered ring with two bonds and one
nitrogen atom.
• Pyrrole has a p orbital on every ring atom that
overlaps, so it is completely conjugated.
• Pyrrole has six electrons—four from the bonds
and two from the lone pair (obeys Huckel’s Rule).
• It is aromatic since it is cyclic, planar, completely
conjugated, and has 4n + 2 electrons.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Imidazole is an aromatic heterocycle with two N
atoms, one which is similar to the N atom of pyridine,
and the other which is similar to the N atom of pyrrole.
It is a component of histidine
and histamine.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
Both negatively and positively charged ions can be
aromatic if they possess all the necessary elements.
One can draw five equivalent resonance structures for the 36
cyclopentadienyl anion.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Having the “right” number of electrons is necessary for
a species to be unusually stable by virtue of aromaticity.
• Thus, although five resonance structures can also be
drawn for the cyclopentadienyl cation and radical, only
the cyclopentadienyl anion has 6 electrons, a number
that satisfies Hückel’s rule.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Cyclopentadiene is more acidic than many
hydrocarbons because its conjugate base is aromatic.
• The pKa of cyclopentadiene is 15, much lower (acidic)
than the pKa of any C—H bond discussed thus far.
• The cyclopentadienyl anion is both aromatic and
resonance stabilized, so it is a very stable base.
• Cyclopentadiene itself is not aromatic because it is not
fully conjugated.
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Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• The tropylium cation is a planer carbocation with
three double bonds and a positive charge contained
in a seven-membered ring.
• Because the tropylium cation has three bonds and
no other nonbonded electron pairs, it contains six
electrons, thereby satisfying Hückel’s rule.
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Benzene and Aromatic Compounds
The Basis of Hückel’s Rule:
• Why does the number of electrons determine
whether a compound is aromatic?
• The basis of aromaticity can be better understood by
considering orbitals and bonding.
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Benzene and Aromatic Compounds
Molecular Orbitals:
• We have used “valence bond theory” to explain how
bonds between atoms are formed.
• Valence bond theory is inadequate for describing
systems with many adjacent p orbitals that overlap,
as is the case in aromatic compounds.
• Molecular orbital (MO) theory permits a better
explanation of bonding in aromatic systems.
• MO theory describes bonds as the mathematical
combination of atomic orbitals that form a new set
of orbitals called molecular orbitals (MOs).
• A molecular orbital occupies a region of space in a
molecule where electrons are likely to be found.
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Benzene and Aromatic Compounds
Molecular Orbitals:
• When forming molecular orbitals from atomic
orbitals, keep in mind that a set of n atomic orbitals
forms n molecular orbitals.
• If two atomic orbitals combine, two molecular
orbitals are formed.
• Recall that aromaticity is based on p orbital overlap.
• Also note that the two lobes of each p orbital are
opposite in phase, with a node of electron density at
the nucleus.
• When two p orbitals combine, two molecular
orbitals should form.
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Benzene and Aromatic Compounds
Molecular Orbitals:
• The combination of two p orbitals can be
constructive: with like phases reinforcing, or
destructive: with opposite phases cancelling.
• When two p orbitals of similar phase overlap side-by-
side, a bonding molecular orbital results.
• When two p orbitals of opposite phase overlap side-43
by-side, a * antibonding orbital results.
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Benzene and Aromatic Compounds
Molecular Orbitals:
• The * antibonding MO is higher in energy because
a destabilizing node results, which pushes nuclei
apart when orbitals of opposite phase combine.
Figure 17.8 Combination of
two p orbitals to form π and π*
molecular orbitals
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Benzene and Aromatic Compounds
Molecular Orbitals of Benzene:
• The molecular orbital description of benzene is much
more complex than the two MOs formed in Figure 17.8.
• Since each of the six carbon atoms of benzene has a p
orbital, six atomic p orbitals combine to form six
molecular orbitals as shown in Figure 17.9.
The six MOs are labeled 1- 6, with 1 being the
lowest energy and 6 being the highest.
• The most important features of the six benzene MOs
are as follows:
The larger the number of bonding interactions, the
lower in energy the MO.
The larger the number of nodes, the higher in energy
the MO. 45
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Benzene and Aromatic Compounds
Molecular Orbitals of Benzene:
• A greater number of bonding interactions gives a lower
MO energy.
• A greater number of nodes, gives a higher MO energy.
• Three of the MOs are lower in energy than the starting
p orbitals, and are bonding MOs, whereas three of the
MOs are higher in energy than the starting p orbitals,
and are antibonding MOs.
• The two pairs of MOs with the same energy are called
degenerate orbitals.
• The highest energy orbital that contains electrons is
called the highest occupied molecular orbital (HOMO).
• The lowest energy orbital that does not contain
electrons is called the lowest unoccupied molecular
orbital (LUMO). 46
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Benzene and Aromatic Compounds
Molecular Orbitals of Benzene:
In benzene, each of the six carbon atoms has a p orbital,
so, six atomic p orbitals combine to form six MOs.
Figure 17.9 The six molecular orbitals of benzene
To fill the MOs, the
six electrons are
added, two to an
orbital. The six
electrons
completely fill the
bonding MOs,
leaving the anti-
bonding MOs
empty. All bonding
MOs (and HOMOs)
are completely
filled in aromatic
compounds. No
electrons occupy
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antibonding MOs.
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Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity
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Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity
• This method works for all monocyclic completely
conjugated systems regardless of ring size.
• The total number of MOs always equals the number of
vertices of the polygon.
• This method is consistent with Hückel's 4n + 2 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.
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Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity
Figure 17.10 Using the inscribed polygon method
for five- and seven-membered rings
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Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity
··
+ + ··
··
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Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity
• For the compound to be aromatic, these MOs must be
completely filled with electrons, so the “magic
numbers” for aromaticity fit Hückel’s 4n + 2 rule.
Figure 17.11 MO patterns for cyclic, completely conjugated systems
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Benzene and Aromatic Compounds
Buckminsterfullerene: Is it Aromatic?
• The two most common elemental forms of carbon are
diamond and graphite. Their physical characteristics
are very different because their molecular structures
are very different.
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Benzene and Aromatic Compounds
Buckminsterfullerene: Is it Aromatic?
• Buckminsterfullerene (C60) is a third elemental form of
carbon.
• Buckminsterfullerene is completely conjugated, but it
is not aromatic since it is not planar.
• It undergoes addition reactions with electrophiles in
much the same way as ordinary alkenes.
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Organic Chemistry, Second Edition
Janice Gorzynski Smith
University of Hawai’i
End Chapter 17
Prepared by Rabi Ann Musah
State University of New York at Albany
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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