Aromatic compounds

The Discovery of Benzene

In 1825, Michael Faraday isolated a pure compound of boiling point 80 °C from the oily
mixture. Eilhard Mitscherlich synthesized the same compound in 1834. Like Faraday,
Mitscherlich found that the empirical formula was CH. Mitscherlich determined a
molecular weight of about 78. Since the new compound was derived from gum benzoin,
he named it benzin, now called benzene.

Many other compounds discovered in the 19 th century also had low hydrogen-to-carbon
ratios, pleasant aromas and they could be converted to benzene or related compounds.
This group of compounds was called aromatic because of their pleasant odors. Other
organic compounds without these properties were called aliphatic, meaning “fatlike.”

In 1866, Friedrich Kekulé proposed a cyclic structure for benzene with three double
bonds. Kekulé predicts two different 1,2-dichlorobenzenes, but only one is known to
exist. He suggested that a fast equilibrium interconverts the two isomers of 1,2-
dichlorobenzene.

Molecular orbital structure of benzene

All 6 carbon atoms in benzene are sp2 hybridized. The sp2 hybrid orbitals overlap with
each other and with s orbitals of the 6 hydrogen atoms forming C-C and C-H σ bonds.
Since the σ bonds result from the overlap of planar sp 2 orbitals, all carbon and hydrogen
atoms in benzene lie in the same plane. All σ bonds in benzene lie in one plane and all
bond angles are 120 °.

Also each carbon atom in benzene possesses an unhybridized p-orbital containing one
electron. These p-orbitals are perpendicular to the plane of σ bonds. The lateral overlap
of these p-orbitals produces a π molecular orbital containing 6 electrons. One half of
this π molecular orbital lies above and the other half lies below the plane of the σ
bonds.
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The Resonance Representation

Benzene is actually a resonance hybrid of the two Kekulé structures. This representation
implies that the π electrons are delocalized, with a bond order of 1.5 between adjacent
carbon atoms. The C–C bond lengths in benzene are shorter than typical single-bond
lengths, yet longer than typical double-bond lengths.

The six π electrons are delocalized; they roam freely within the doughnut-shaped clouds
that lie over and under the planar ring of carbons. So, we often inscribe a circle in the
hexagon rather than draw three localized double bonds. This representation helps us
remember there are no localized single or double bonds. We often use Kekulé structures
in drawing reaction mechanisms to show the movement of individual pairs of electrons.

Resonance Energy

The resonance energy of a compound is a measure of the extra stability of the

conjugated system compared to the corresponding number of isolated double
bonds. This can be calculated from experimental measurements. 

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The diagram shows the experimental heats of hydrogenation, ΔH h, for benzene,
cyclohexatriene, 1,3-cyclohexadiene and cyclohexene. Under appropriate conditions,
these molecules can be reduced to the same product, cyclohexane.

The ΔHh for "cyclohexatriene", a hypothetical molecule in which the double bonds are
assumed to be isolated from each other, is calculated to be 3 times the value for
cyclohexene. This value reflects the energy we could expect to be released from 3
isolated C=C. 

By comparing this value with the experimental value for benzene, we can conclude that
benzene is 152 kJ or 36 kcal/mol more stable than the hypothetical system. This is the
resonance energy for benzene. 

Aromatic, Antiaromatic and Nonaromatic Compounds

 Aromatic compounds: are those that meet the following criteria-

1. The structure must be cyclic, containing some number of conjugated π bonds.

2. Each atom in the ring must have an unhybridized p orbital.
3. The unhybridized p orbitals must overlap to form a continuous ring of parallel
orbitals. In most cases, the structure must be planar for effective overlap to
occur.
4. Delocalization of the π electrons over the ring must lower the electronic energy.

 Antiaromatic compound: is one that meets the first three criteria, but
delocalization of the π electrons over the ring increases the electronic energy.

Cyclobutadiene meets the first three criteria for a continuous ring of overlapping p
orbitals, but delocalization of the π electrons increases the electronic energy.

 Nonaromatic, or aliphatic: A cyclic compound that does not have a continuous

ring of overlapping p orbitals cannot be aromatic or antiaromatic.

Hückel’s Rule

To qualify as aromatic or antiaromatic, a cyclic compound must have a continuous ring

of overlapping p orbitals, usually in a planar conformation.

Hückel’s Rule: If the number of π electrons in the cyclic system is:

 (4n+2) the system is aromatic.
 (4n) the system is antiaromatic.
n is an integer, commonly 0, 1, 2, or 3.

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 The nomenclature of benzenes
a) Monosubstituted benzenes

1. The following compounds are usually called by their historical common names,
and almost never by the systematic IUPAC names:

2. Monosubstituted benzenes are named simply by adding the name of the

substituent to “benzene.”

3. When the benzene ring is named as a substituent on another molecule, it is

called a phenyl group, Ph (or φ). The phenyl group is used in the name just like
the name of an alkyl group. A benzene ring with a methylene group is called a
benzyl group. With the exception of toluene, benzene rings with an alkyl
substituent are named as phenyl-substituted alkanes.

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 4. Aromatic hydrocarbons are sometimes called arenes. An aryl group (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 (R).

b) Disubstituted and polysubstituted benzenes

1. Many disubstituted benzenes have historical common names.

common name: m-xylene o-toluic acid p-cresol m- toluidine

IUPAC name: 1,3-dimethylbenzene 2-methylbenzoic acid 4-methylphenol 3-methylaniline

2. The relative positions of two substituents on a benzene ring can be indicated

either by numbers or by the prefixes (in italics).

 Ortho (o or 1,2): adjacent substituents

 Meta (m or 1,3): substituents separated by one carbon
 Para (p or 1,4): substituents located opposite one another

3. If the two substituents are different, they are listed in alphabetical order, each
preceded by it assigned number. The first mentioned substituent is given the 1-
position, and the ring is numbered in the direction that gives the second
substituent the lowest possible number.
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4. If one of the substituents can be incorporated into a name, then that name is
used and given the 1-position.

5. With three or more substituents on the benzene ring, numbers are used to give
the lowest possible numbers to the substituents. The substituents are listed
alphabetically in the final name.

6. If one of the substituents can be incorporated into a name, that name is used
and given the 1-position. The ring is then numbered in the direction that results
in the lowest possible numbers in the name of the compound.

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 Electrophilic aromatic substitution reactions
The cloud of π electrons above and below the plane of its ring makes benzene a
nucleophile, so it reacts with an electrophile (Y +). An electrophile becomes attached to a
ring carbon and an H+ is removed from the same ring carbon.

Electrophilic aromatic substitution reactions take place by two-step mechanism.

i. The electrophile (Y+) adds to the nucleophilic benzene ring, thereby forming a
carbocation intermediate. The structure of the carbocation intermediate can be
approximated by three resonance contributors.
ii. A base in the reaction mixture (:B) removes the proton (from the carbon that has
formed the bond with the electrophile) from the carbocation intermediate and
the electrons that held the proton move into the ring to reestablish its
aromaticity.

Why benzene undergoes electrophilic substitution reactions whereas alkenes undergo

addition reaction?

In an electrophilic addition reaction of an alkene; the nucleophilic alkene reacts with an

electrophile and forms a carbocation intermediate. In the second step of the reaction,
the carbocation reacts with a nucleophile (Z-) to form an addition product.

When an electrophile reacts with a benzene ring, a carbocation intermediate is formed.

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If benzene undergoes addition reaction, the product would no longer be aromatic. The
resonance energy of benzene would be lost. Instead, the nucleophile removes a proton
from the carbocation intermediate to regenerate the aromatic π system. Net change is
the replacement of a hydrogen atom by an electrophile.

1. The halogenation of benzene

The bromination or chlorination of benzene requires a Lewis acid catalyst such as ferric
bromide or ferric chloride.

Why does the reaction of benzene with Br 2 or Cl2 require a catalyst when the reaction
of an alkene with these reagents does not require a catalyst?

Benzene’s aromaticity makes it much more stable and therefore much less reactive than
an alkene. Therefore, benzene requires a better electrophile. Donating a lone pair to the
Lewis acid weakens the Br-Br (or Cl-Cl) bond, thereby providing a better leaving group
and making Br2 (or Cl2) a better electrophile.

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 2. The nitration of benzene

The nitration of benzene with nitric acid requires sulfuric acid as a catalyst. To generate
the necessary electrophile, sulfuric acid protonates nitric acid. Protonated nitric acid
then loses water to form a nitronium ion, the electrophile required for nitration.

3. The sulfonation of benzene

Concentrated sulfuric acid is used to sulfonate aromatic rings.

4. The Friedel–Crafts acylation of benzene

Friedel–Crafts acylation places an acyl group on a benzene ring. An acyl chloride or an

acid anhydride is used as the source of the acyl group needed for a Friedel–Crafts
acylation.

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The electrophile (an acylium ion) required for the reaction is formed by the reaction of
an acyl chloride (or an acid anhydride) with AlCl 3, a Lewis acid. Oxygen and carbon share
the positive charge in the acylium ion.

5. The Friedel–Crafts alkylation of benzene

Friedel–Crafts alkylation substitutes an alkyl group for hydrogen of benzene. The

electrophile required for the reaction (a carbocation) is formed from the reaction of an
alkyl halide with AlCl3.

How some substituents on a benzene ring can be chemically changed?

Reactions of Alkyl Substituents: A bromine can be selectively substitute for a benzylic

hydrogen in a radical substitution reaction. Once a halogen has been placed in the
benzylic position, it can be replaced by a nucleophile via a nucleophilic substitution (S N2
or SN1) reaction. A wide variety of substituted benzenes can be prepared this way.

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Alkyl halides can also undergo elimination (E 2 and E1) reactions. A bulky base is used to
encourage elimination over substitution.

Substituents with double and triple bonds can be reduced by catalytic hydrogenation.

An alkyl group attached to a benzene ring can be oxidized to a carboxyl group.

Reducing a Nitro Substituent: A nitro substituent can be reduced to an amino

substituent. Catalytic hydrogenation is commonly used to carry out this reaction.

The effect of substituents on reactivity

Like benzene, substituted benzenes undergo the five electrophilic aromatic substitution
reactions. The slow step of an electrophilic aromatic substitution reaction is the addition
of an electrophile to the nucleophilic aromatic ring to form a carbocation intermediate.
A substituent that makes benzene a better nucleophile will make it more attractive to
electrophiles; a substituent that makes benzene a poorer nucleophile will make it less
attractive to electrophiles.

1. Activating, Ortho, Para-Directing Substituents

Substituents that donate electrons to the benzene ring increase benzene’s

nucleophilicity and stabilize the partially positively charged transition state, thereby
increasing the rate of electrophilic aromatic substitution; these are called activating
substituents.

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Electron Donation by Hyperconjugation: Alkyl substituents (R) stabilize carbocations by
hyperconjugation—that is, by donating electrons to an empty p orbital.

Electron Donation by Resonance: If a substituent has a lone pair on the atom directly
attached to the benzene ring, then the lone pair can be delocalized into the ring. These
substituents are said to donate electrons by resonance. Example: NH 2, OH and OR.

2. Deactivating, Meta-Directing Substituents

Substituents that withdraw electrons from the benzene ring decrease benzene’s
nucleophilicity and destabilize the transition state, thereby decreasing the rate of
electrophilic aromatic substitution; these are called deactivating substituents.

Electron Withdrawal by Resonance: If a substituent is attached to the benzene ring by

an atom that is doubly or triply bonded to a more electronegative atom, then the
electrons of the ring can be delocalized onto the substituent; these substituents are said
to withdraw electrons by resonance. Example: C=O, C≡N and SO3H.

3. Halogen Substituents: Deactivating, but Ortho, Para-Directing

We can explain this unusual combination of properties by considering that

a) Inductive withdrawal: The carbon–halogen bond is strongly polarized, with the

carbon atom at the positive end of the dipole. This polarization draws electron
density away from the benzene ring, making it less reactive toward electrophilic
substitution.

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 b) Resonance donation: If an electrophile reacts at the ortho or para position, the
positive charge of the complex is shared by the carbon atom bearing the
halogen. The nonbonding electrons of the halogen can further delocalize the
charge onto the halogen, giving a halonium ion structure. This resonance
stabilization allows a halogen to be π-donating, even though it is σ-withdrawing.

Reaction at the meta position gives intermediate which is not stabilized by the halonium
ion structure.

Table: Directing Effects of Substituents

π donors σ donors Halogens Carbonyls Other

-NH2 Alkyl -F -COR -SO3H
-OH Aryl -Cl -COOH -CN
-OR -Br -COOR -NO2
-NHCOCH3 -I
ortho, para-directing meta-directing

Activating Deactivating

The ortho-para ratio

On the basis of probability, more of the ortho product is expected because two ortho
positions are available to the incoming electrophile but only one para position is
available. The ortho positions, however, are sterically hindered by the substituent on
the ring, whereas the para position is not. Consequently, the para isomer will be formed
preferentially if either the substituent on the ring or the incoming electrophile is large.

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Why a substituent directs an incoming electrophile to a particular position?

When a substituted benzene undergoes an electrophilic aromatic substitution reaction,

three different carbocation intermediates can be formed: ortho, meta, and para -
substituted carbocation. The relative stabilities of the three carbocations enable us to
determine the preferred pathway of the reaction because the more stable the
carbocation, the more stable the transition state for its formation will be, and therefore
the more rapidly it will be formed.

All substituents that donate electrons are ortho–para directors: When the substituent is
one that can donate electrons by resonance, the carbocations formed by putting the
incoming electrophile on the ortho and para positions have a fourth resonance
contributor. This is an especially stable resonance contributor because it is the only one
whose atoms all have complete octets. It is obtained only by directing an incoming
substituent to the ortho and para positions.

All substituents that cannot donate electrons are meta directors: Substituents with a
positive charge or a partial positive charge on the atom attached to the benzene ring will
withdraw electrons from the benzene ring. For all of these substituents, the resonance
contributors are the least stable because they have a positive charge on each of two
adjacent atoms, so the most stable carbocation is formed when the incoming
electrophile is directed to the meta position.

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Effects of Multiple Substituents on Electrophilic Aromatic Substitution

1. If both substituents direct the incoming substituent to the same position, the
product of the reaction is easily predicted.

2. Notice that three positions are activated in the next reaction, but the new
substituent ends up primarily on only two of the three. Steric hindrance makes
the position between the substituents less accessible, so only a very small
amount of the third product will be formed.

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 3. If the two substituents direct the new substituent to different positions, then a
strongly activating substituent will win out over a weakly activating substituent
or a deactivating substituent.

-OH, -OR, -NR2 > -R, -X > -COR, -SO3H, -NO2

4. If the two substituents have similar activating properties, neither will dominate
and a mixture of products will be obtained.

Addition Reactions of Benzene Derivatives

a) Chlorination: Aromatic compounds may undergo addition if forcing conditions

are used.

The addition of chlorine to benzene, believed to involve a free-radical mechanism, is

normally impossible to stop at an intermediate stage. The first addition destroys the
ring’s aromaticity and the next 2 moles of Cl2 add very rapidly.

b) Catalytic Hydrogenation of Aromatic Rings: Catalytic hydrogenation of benzene

to cyclohexane takes place at elevated temperatures and pressures.

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