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The Structure and Properties of Benzene

The Kekulé Structure. In 1866, Friedrich Kekulé proposed a cyclic structure for benzene
with three double bonds. Considering that multiple bonds had been proposed only recently
(1859), the cyclic structure with alternating single and double bonds was considered somewhat
bizarre.
The Resonance Representation. The resonance picture of benzene is a natural extension of
Kekulé’s hypothesis. In a Kekulé structure, the single bonds would be longer than the double
bonds. Spectroscopic methods have shown that the benzene ring is planar and all the bonds
are the same length (1.397 Å). Because the ring is planar and the carbon nuclei are positioned
at equal distances, the two Kekulé structures must differ only in the positioning of the pi
electrons.

Aromatic compound. A cyclic compound containing some number of conjugated double


bonds and having an unusually large resonance energy. Using benzene as the example, we will
consider how aromatic compounds differ from aliphatic compounds. Then we will discuss why
an aromatic structure confers extra stability and how we can predict aromaticity in some
interesting and unusual compounds.

The Resonance Energy of Benzene


The oscillating double bonds in the benzene ring are explained with the help of resonance
structures as per valence bond theory. All the carbon atoms in the benzene ring are sp2
hybridized. One of the two sp2 hybridized orbitals of one atom overlaps with the sp2 orbital of
adjacent carbon atom forming six C-C sigma bonds. Other left sp2 hybridized orbitals combine
with s orbital of hydrogen to form six C-H sigma bonds. Remaining unhybridized p orbitals of
carbon atoms form π bonds with adjacent carbon atoms by lateral overlap.
This explains an equal possibility for the formation of C1 –C2, C3 – C4, C5 – C6 π bonds or C2
– C3, C4 – C5, C6-C1 π bonds. The hybrid structure is represented by inserting a circle in the
ring as shown below in the figure. Hence, it explains the formation of two resonance structures
proposed by Kekule.
Aromaticity of benzene
Benzene is an aromatic compound, as the C-C bonds formed in the ring are not exactly single
or double, rather they are of intermediate length. Aromatic compounds are divided into two
categories: benzenoids (one containing benzene ring) and non-benzenoids (those not
containing benzene ring), provided they follow Huckel rule. According to Huckel rule, for a ring
to be aromatic it should have the following property:

 Planarity
 Complete delocalization of the π electrons in the ring
 Presence of (4n + 2) π electrons in the ring where n is an integer (n = 0, 1, 2, . . .)

The Unusual Reactions of Benzene


Benzene is actually much more stable than we would expect from the simple resonance-
delocalized picture. Both the Kekulé structure and the resonance-delocalized picture show that
benzene is a cyclic conjugated triene. We might expect benzene to undergo the typical
reactions of polyenes. In fact, its reactions are quite unusual. For example, an alkene
decolorizes potassium permanganate by reacting to form a glycol (Section 8-14). The purple
permanganate color disappears, and a precipitate of manganese dioxide forms. When
permanganate is added to benzene, however, no reaction occurs.

The Unusual Stability of Benzene


Benzene’s reluctance to undergo typical alkene reactions suggests that it must be unusually
stable. By comparing molar heats of hydrogenation, we can get a quantitative idea of its
stability. Benzene, cyclohexene, and the cyclohexadienes all hydrogenate to form cyclohexane.
Figure 16-2 shows how the experimentally determined heats of hydrogenation are used to
compute the resonance energies of cyclohexa-1,3-diene and benzene, based on the following
reasoning:
1. Hydrogenation of cyclohexene is exothermic by 120 kJ mol (28.6 kcal mol).
2. Hydrogenation of cyclohexa-1,4-diene is exothermic by 240 kJ mol (57.4 kcal mol), about
twice the heat of hydrogenation of cyclohexene. The resonance energy of the isolated double
bonds in cyclohexa-1,4-diene is about zero.
3. Hydrogenation of cyclohexa-1,3-diene is exothermic by 232 kJ mol (55.4 kcal mol), about 8
kJ (1.8 kcal) less than twice the value for cyclohexene. A resonance energy of 8 kJ (1.8 kcal) is
typical for a conjugated diene.
4. Hydrogenation of benzene requires higher pressures of hydrogen and a more active catalyst.
This hydrogenation is exothermic by 208 kJ mol (49.8 kcal mol), about 151 kJ (36.0 kcal) less
than 3 times the value for cyclohexene.

Failures of the Resonance Picture


For many years, chemists assumed that benzene’s large resonance energy resulted from
having two identical, stable resonance structures. They thought that other hydrocarbons with
analogous conjugated systems of alternating single and double bonds would show similar
stability. These cyclic hydrocarbons with alternating single and double bonds are called
annulenes. For example, benzene is the six-membered annulene, so it can be named
[6]annulene. Cyclobutadiene is [4]annulene, cyclooctatetraene is [8]annulene, and larger
annulenes are named similarly.
The Molecular Orbitals of Benzene
Benzene has a planar ring of six carbon atoms, each with an unhybridizedporbital that overlaps
with the porbitals of its neighbors to form a continuous sp2 ring of orbitals above and below the
plane of the carbon atoms. Six pi electrons are contained in this ring of overlapping p orbitals.
The six overlapping p orbitals create a cyclic system of molecular orbitals. Cyclic systems of
molecular orbitals differ from linear systems such as buta-1,3-diene and the allyl system. A two-
dimensional cyclic system requires two-dimensional MOs, with the possibility of two distinct
MOs having the same energy. We can still follow the same principles in developing a molecular
orbital representation for benzene, however.
1. There are six atomic p orbitals that overlap to form the benzene pi system. Therefore,
there must be six molecular orbitals.
2. The lowest-energy molecular orbital is entirely bonding, with constructive overlap
between all pairs of adjacent p orbitals. There are no vertical nodes in this lowest-lying
MO.
3. The number of nodes increases as the MOs increase in energy.
4. The MOs should be evenly divided between bonding and antibonding MOs, with the
possibility of nonbonding MOs in some cases.
5. We expect that a stable system will have filled bonding MOs and empty antibonding
MOs.
Nomenclature of Benzene Derivatives
Benzene derivatives have been isolated and used as industrial reagents for well over 100 years.
Many of their names are rooted in the historical traditions of chemistry. The following
compounds are usually called by their historical common names, and almost never by the
systematic IUPAC names:

Disubstituted benzenes are named using the prefixes ortho-, meta-, and para- to specify the
substitution patterns. These terms are abbreviated o-, m-, and p-. Numbers can also be used to
specify the substitution in disubstituted benzenes.

When the benzene ring is named as a substituent on another molecule, it is called a phenyl
group. The phenyl group is used in the name just like the name of an alkyl group, and it is often
abbreviated Ph (or ) in drawing a complex structure.
The seven-carbon unit consisting of a benzene ring and a methylene (------CH2------) group is
often named as a benzyl group. Be careful not to confuse the benzyl group (seven carbons) with
the phenyl group (six carbons).

Aromatic hydrocarbons are sometimes called arenes. An aryl group, abbreviated Ar, is the
aromatic group that remains after the removal of a hydrogen atom from an aromatic ring. The
phenyl group, Ph, is the simplest aryl group. The generic aryl group (Ar) is the aromatic relative
of the generic alkyl group, which we symbolize by R.

Physical Properties of Benzene and Derivatives


Benzene derivatives tend to be more symmetrical than similar aliphatic compounds, so
they pack better into crystals and have higher melting points. For example, benzene melts at 6
°C, while hexane melts at Similarly, paradisubstituted benzenes are more symmetrical than the
ortho and meta isomers, and they pack better into crystals and have higher melting points.
The relative boiling points of many benzene derivatives are related to their dipole
moments. For example, the dichlorobenzenes have boiling points that follow their dipole
moments. Symmetrical p-dichlorobenzene has zero dipole moment and the lowest boiling point.
m-Dichlorobenzene has a small dipole moment and a slightly higher boiling point. o-
Dichlorobenzene has the largest dipole moment and the highest boiling point. Even though p-
dichlorobenzene has the lowest boiling point, it has the highest melting point of the
dichlorobenzenes becauseit packs best into a crystal.

Benzene and other aromatic hydrocarbons are slightly denser than the nonaromatic analogues,
but they are still less dense than water. The halogenated benzenes are denser than water.
Aromatic hydrocarbons and halogenated aromatics are generally insoluble in water, although
some derivatives with strongly polar functional groups (phenol, benzoic acid, etc.) are
moderately soluble in water.

Other Properties of Benzene

1. Benzene is immiscible in water but soluble in organic solvents.


2. It is a colourless liquid and has an aromatic odour.
3. It has a density of 0.87g cm-3. It is lighter than water.
4. Benzene has a moderate boiling point and a high melting point. (Boiling point: 80.5°C,
Melting point: 5.5°C)
5. Benzene shows resonance.
6. It is highly inflammable and burns with a sooty flame.
Uses of Benzene
Benzene is used in various industrial processes such as in the manufacture of lubricants,
plastics, rubbers, dyes, synthetic fibres, etc. However, it has non-industrial uses too which are
limited due to the reason benzene is toxic and carcinogenic. The different uses of Benzene are
mentioned below.

 Benzene is used in the preparation of phenol. It is also used to prepare aniline used in
dyes and in dodecylbenzene used for the detergents.
 In early times, benzene was used in degreasing of metal.
 It is used for manufacturing of nylon fibres.
 The main use of benzene is that it is used in the manufacture of other chemicals such as
ethylbenzene, cyclohexane, cumene, nitrobenzene, alkylbenzene, etc.
Reactions of Aromatic Compounds

Bromination of Benzene
Bromination follows the same general mechanism for the electrophilic aromatic
substitution (EAS). Bromine itself is not electrophilic enough to react with benzene. But the
addition of a strong Lewis acid (electron pair acceptor), such as FeBr3, catalyses the reaction,
and leads to the substitution product. The bromine molecule reacts with FeBr3 by donating a
pair of its electrons to the Lewis acid, which creates a more polar Br-Br bond, and thus a more
reactive electrophile. Benzene will now attack this electrophile to generate the sigma complex.

Chlorination of Benzene
The chlorination proceeds analogously to the bromination except this time the Lewis acid
catalyst used is AlCl3.

Iodination of Benzene
The iodination procedure requires an acidic oxidizing agent, such as nitric acid
Nitration of Benzene
Benzene will react with hot concentrated nitric acid to produce nitrobenzene

Sulfunation of Benzene
Benzene will react with sulfur trioxide, and in the presence of an acid, aryl sulfonic acids
are produced

Friedel-Crafts Alkylation
Carbocations are electrophiles, and can therefore be useful reagents for forming new C-
C bonds in EAS processes. Friedel and Crafts demonstrated that benzene would react with
alkyl halides in the presence of a Lewis acid (e.g. AlCl3) to produce alkyl benzenes.

The Friedel-Crafts Acylation


An acyl group is a substituent which contains an alkyl group bound to a carbonyl group.
Catalytic Hydrogenation
The addition of hydrogen to benzene occurs at elevated temperatures and pressures, and
requires a catalyst

Birch Reduction
The use of sodium (or lithium) in a mixture of alcohol and liquid ammonia

Nucleophilic Aromatic Substitution


Normally electrophilic aromatic substitution is the type of reaction mechanism we
associate most commonly with benzene derivatives. However, it is also possible for
nucleophiles to displace halide ions (i.e. good leaving groups) from aryl halides if there are
strong electron withdrawing groups bound to the ring (and especially if they are located ortho
and para to the halide)
The Benzyne Mechanism (Elimination Addition Mechanism).

The Clemmensen Reduction


We can use the acylation procedure to produce alkyl benzenes that otherwise cannot
be prepared directly by alkylation. All that is required is the reduction of the acyl carbonyl group
to a CH2.

Reactions of the Side Chains in Benzene Derivatives

Permanganate Oxidation
An aromatic ring imparts extra stability to the carbon atoms directly bonded to it.
Therefore when an alkyl benzene is oxidized with permanganate, the product is the carboxylate
salt of di-benzoic acid.
Side Chain Halogenation
Alkyl benzenes undergo free radical halogenation very easily at the benzylic position,
since the required intermediate radical is a benzylic radical, and is therefore resonance
stabilized.

Reactions of Phenols
Phenols behave very similarly to aliphatic alcohols (Ch 11), with the exceptions that (a)
they form more stable phenoxide ions (vs. alkoxide ions), and (b) they do not undergo either
acid catalyzed reactions or back side attack (e.g. no reaction with HBr)
. The aromatic ring in phenol also gives rise to some unique phenol reactions.
Oxidation of Phenols to Quinones
Oxidation of normal alcohols gives either carbonyl products (aldehydes/ketones) or
carboxylic acids. However, oxidation of phenols gives conjugated 1,4-diketone products, which
are called quinones.
SUMMARY OF REACTIONS