/Arba minch university / /Organic chemistry/ /Prepared by Mitiku B , / /2023/

CHAPTER FIVE
5. AROMATIC CHEMISTRY

5.1. Introduction to Aromaticity

 Aromaticity is a property associated with the extra stability of certain types of π systems due to
the nature of the molecular orbitals. It is not restricted to substituted benzenes, 6-membered rings
or just hydrocarbons.
 The property of aromaticity is generally about a significant extra stability associated with a
resonance-delocalized structure. This extra stability moderates the reactivity of these systems
compared to alkenes and means aromatics can be considered as their own functional group.
Today, chemists use the term aromatic to refer to the class of compounds that contain benzene-
like rings.
 Benzene is the simplest aromatic compound, is a flat, symmetrical molecule with the molecular
formula C6H6. It is often represented as cyclohexatriene, a six membered carbon ring with three
double bonds. Though useful, the problem with this representation is that it gives the wrong
impression about benzenes chemical reactivity and bonding. Because benzene appears to have
three double bonds, you might expect it to react with H2, Br2, HCl, and H2O and to give the same
kinds of addition products like that of alkenes. However, this expectation is wrong. Benzene and
other aromatic compounds are much less reactive than alkenes and do not normally undergo
addition reactions.
Structure:
 Benzene has a planar, cyclic, conjugated structure and has the shape of a regular hexagon. All
bond angles are 120°, all carbon atoms are sp2-hybridized, and all carbon–carbon bond lengths
are 139 pm. Alternatively, these two forms can be combined in the resonance hybrid and the π
system represented by a circle as in the Robinson structure below. The “circle” representation
must be used carefully since it does not indicate the number of π electrons in the ring.

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Which representation is best?

 In benzene all the C-C bonds are known to be of equal length (above) so there are no C=C and
C-C. This is best represented by the resonance hybrid in the Robinson form. However, since the
key to organic chemistry is being able to understand mechanisms and drawing curly arrows to
account for the positions of the electrons, the Kekule structures give a more precise description
of the electron positions that can avoid confusion. Therefore, it is a good idea to use a Kekule
representation.

Stability:

 The aromatic character of benzene infers an inherent stability to the system. As a result,
benzene is not particularly reactive compared to alkenes.
 This stability can be expressed by the resonance energy, which for benzene is about 36 kcal
/mol.

 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.
 The diagram below shows the experimental heats of hydrogenation, DHh, for three molecules,
benzene, 1,3-cyclohexadiene and cyclohexene. These are related in that under appropriate
conditions that can all be reduced to the same product, cyclohexane.
 The DHh 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.
Reactivity: For reactions directly on the aromatic ring:
 The cyclic array of π- bonds is a region of high electron density so arenes are typically
nucleophiles (like alkenes and alkynes).

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 Unlike alkenes and alkynes (which undergo addition reactions), arenes typically undergo
substitution reactions in which a group (usually -H) is replaced and the aromatic system is
retained.

 The stability of the aromatic system favors substitution over addition that would destroy the
aromatic system.

Figure: A comparison of the heats of hydrogenation for cyclohexene, 1,3-cyclohexadiene and benzene.

NB: Benzene is 152 kJ/mol (36 kcal/mol) more stable than might be expected for “cyclohexatriene.”

5.2.General properties of aromatic compounds

Aromatic compounds have the following general properties.
(a) They have a high degree of unsaturation, but are resistant to addition reactions.
(b) They favor electrophilic substitution reactions.
(c) These compounds are unusually stable.
(d) They have a low heat of hydrogenation and low heat of combustion.
(e) They are cyclic compounds.
(f) These compounds are flat and planar.

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 Based on the properties of compounds; there are four criteria about the π system that need to be
met in order for the "special" aromatic stabilization to be observed.
1. Conjugated (there needs to one "π" orbital from each atom in the cycle, so each atom must
be either sp2 or sp hybridized)
2. Cyclic (Linear systems are not aromatic)
3. Planar (so there is good overlap / interaction between the "p" orbitals.... not always easy to
consider) Benzene is planar and has the shape of a regular hexagon. All bond angles are
120°, all carbon atoms are sp2-hybridized, and all carbon–carbon bond lengths are 139 pm.
4. The Hückel Rule.... 4n+2 π electrons (this is equivalent to an odd number of π-electrons
pairs) in the cyclic conjugated system.
 According to a theory devised in 1931 by the German physicist Erich Hückel, a molecule is
aromatic only if it has a planar, monocyclic system of conjugation and contains a total of 4n + 2
π electrons, where n is an integer (n = 0, 1, 2, 3, . . .). In other words, only molecules with 2, 6,
10, 14, 18, . . . π electrons can be aromatic.
 Molecules with 4n π electrons (4, 8, 12, 16, . . .) can’t be aromatic, even though they may be
cyclic, planar, and apparently conjugated.
 A planar, conjugated molecule with 4n π electrons are said to be anti-aromatic because
delocalization of their π electrons would lead to their destabilization.

Examples:

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NB: The Hückel rule is strictly applicable only to monocyclic compounds, but the general concept
of aromaticity can be extended to include polycyclic aromatic compounds like naphthalene, with two
benzene-like rings fused together; anthracene, with three rings; benzo[a]pyrene, with five benzene rings.

Heterocyclic Aromatic Compounds

 Heterocycle: any cyclic compound that contains ring atom(s) other than carbon (N, O, S, P).
 Cyclic compounds that contain only carbon are called carbocycles

Pyridine pyrrole furan thiophene

The Annulenes

 Annulenes are monocyclic compounds with alternating double and single bonds.
 Annulenes are named using a number in brackets that indicates the ring size
 Benzene is [6]annulene and cyclooctatetraene is [8]annulene.

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5.3.Electrophilic Aromatic Substitution Reaction

 It is the most common aromatic reaction in which electrophile (E+) is substituted in aromatic
compounds. The electron-rich benzene ring attacks an electrophile to form a carbocation, which
rapidly loses a proton so as to regenerate the aromatic ring. As benzene contains six π-electrons, it
can act as a nucleophile and react with electrophiles in electrophilic substitution reactions. These
reactions involve the substitution of a hydrogen atom on the benzene ring for an electrophile.

 The first step is the reaction of electrophilic reagents with benzene. An electrophile accepts an
electron pair from the π system of benzene to form a carbocation.
Mechanism:

 The second step is rapidly loses of a proton, in order to restore the aromaticity of the ring and
giving the product of electrophilic aromatic substitution.
5.4. Application of electrophilic substitutions
1. Halogenation of Benzene
 Bromine is added to benzene in the presence of metallic iron (customarily a few carpet tacks) and
the reaction mixture is heated. Lewis acid like AlBr3, AlCl3, FeBr3, and FeCl3 can be used as a
catalyst in order to form strong electrophile.

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Mechanism:

Mechanism:

Step 1: The bromine–iron (III) bromide complex is the active electrophile that attacks benzene.
Two of the π electrons of benzene are used to form a bond to bromine and give cyclohexadienyl
cation intermediate.

Step 2: Loss of a proton from the cyclohexadienyl cation yields bromobenzene.

2. Sulfonation of benzene
 It is the reaction of benzene with sulfuric acid to produce benzenesulfonic acid. This is reversible,
but can be driven to completion by several techniques like by removing the water formed in the
reaction. Concentrated sulfuric acid or fuming sulfuric acid (a solution of SO3 in sulfuric acid) is
used to sulfonate aromatic rings.
 When a solution of sulfur trioxide in sulfuric acid is used as the sulfonating agent, the rate of
sulfonation is much faster and the equilibrium is displaced entirely to the side of products.

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Mechanism:
Generation of the electrophile from concentrated H2SO4

Step 1: Sulfur trioxide attacks benzene in the rate-determining step

Step 2: A proton is lost from the sp3 hybridized carbon of the intermediate to restore the
aromaticity of the ring. The hydrogen sulfate ion that abstracts the proton is formed by ionization
of sulfuric acid.

Step 3: A rapid proton transfer from the oxygen of sulfuric acid to the oxygen of
benzenesulfonate completes the process.

Sulfonation is reversible. If benzenesulfonic acid is heated in dilute acid, an H+ adds to the ring
and the sulfonic acid group comes off the ring

Exercise: Draw a stepwise reaction mechanism for the above desulfonation reaction.
3. Nitration of Benzene
 The electrophile (E+) that reacts with benzene is nitronium ion (+NO2). The concentration of
nitronium ion in nitric acid alone is too low to nitrate benzene at a convenient rate, but can be
increased by adding sulfuric acid.

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Mechanism: Generation of the electrophile by mixing concentrated H2SO4 with HNO3

Step 1: Attack of nitronium cation on the π system of the aromatic ring

Step 2: Loss of a proton from the cyclohexadienyl cation

4. Friedel–Crafts Alkylation of Benzene

 The reaction of benzene with alkyl bromides or chlorides in the presence of a Lewis acid catalyst
(such as FeBr3, FeCl3 or AlCl3) leads to the formation of alkyl benzenes.

 It was discovered by Charles Friedel and James M. Crafts in 1877. Aluminum chloride serves as a
Lewis acid catalyst to enhance the electrophilicity of the alkylating agent. With tertiary and
secondary alkyl halides, the addition of AlCl3 leads to the formation of carbocations, which then
attack the aromatic ring.

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Mechanism:

 The electrophile required for the reaction (a carbocation) is formed from the reaction of an alkyl
halide with AlCl3. Alkyl chlorides, alkyl bromides, and alkyl iodides can all be used. Vinylic
halides and aryl halides cannot be used because their carbocations are too unstable to be formed.

 Tertiary and Secondary alkyl halides react by a similar mechanism involving attack on benzene by
tertiary and secondary carbocation. Methyl and ethyl halides do not form carbocations when treated
with aluminum chloride, but do alkylate benzene under Friedel–Crafts conditions.
Step 1: Once generated by the reaction of alkyl chloride and aluminum chloride, alkyl
carbocation attacks the π electrons of benzene, and a carbon-carbon bond is formed.

Step 2: Loss of a proton from the cyclohexadienyl cation intermediate yields alkyl benzene as
shown above.
Limitation of Friedel–Crafts alkylation

Rearrangement

 One drawback to Friedel–Crafts alkylation is that rearrangements can occur, especially when
primary alkyl halides are used. For example, Friedel–Crafts alkylation of benzene with n-butyl
chloride (a primary alkyl halide) yields only sec-butylbenzene.

Example 2. Isobutyl chloride (a primary alkyl halide) yields only tert-butylbenzene as a major
product.

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 A hydride migration that will accompanies ionization of the carbon–chlorine bond to form stable
tert-butyl cation.

5. Friedel–Crafts Acylation of Benzene

 An acyl chloride or an acid anhydride is used as the source of the acyl group needed for a Friedel–
Crafts acylation instead of alkyl halides and yields acylbenzenes.
The electrophile is an acyl cation (also referred to as an acylium ion).

 Acyl cations formed by coordination of an acyl chloride with aluminum chloride, followed by
cleavage of the carbon–chlorine bond.

 Acyl chlorides are readily available. They are prepared from carboxylic acids by reaction with
thionyl chloride.

Mechanism:
Step 1: The acyl cation attacks benzene. A pair of π electrons of benzene is used to form a
covalent bond to the carbon of the acyl cation.

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Step 2: Aromaticity of the ring is restored when it loses a proton to give the acylbenzene.

6. The Clemmensen Reduction:

 Synthesis of Alkylbenzenes by Acylation–Reduction Reaction

O H H
H O 1. AlCl3 Zn(Hg)
+ R R
R Cl 2. H2O aq. HCl
O O H H
H 1. AlCl3
CH2CH3
Zn(Hg)
Example: 1. + H3CH2C Cl 2. H2O
CH2CH3
aq. HCl
O H H
C C
2. CH3 Zn(Hg), conc. HCl CH3

Acetophenone 1-Ethylbenzene

5.5.Effect of substituent on the ring

Directing Effects of Substituents
 A substituent on the ring can also affect the orientation that the incoming group takes when it
replaces a hydrogen atom on the ring. Substituents fall into two general classes:
A. Ortho–para directors predominantly direct the incoming group to a position ortho or para to
itself.

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B. Meta directors predominantly direct the incoming group to a position meta to itself.

 Relative rates of electrophilic aromatic substitution

5.5.1. Substituents can be arranged into three major categories:

1. Activating and ortho, para-directing: These substituents stabilize the cyclohexadienyl
cation formed in the rate-determining step. The most strongly activating members of this
group are bonded to the ring by a nitrogen or oxygen atom that bears an unshared pair of
electrons.
2. Deactivating and ortho, para-directing: The halogens are the most prominent members of
this class. They withdraw electron density from all the ring positions by an inductive effect,
making halobenzenes less reactive than benzene. Lone-pair electron donation stabilizes the
cyclohexadienyl cations corresponding to attack at the ortho and para positions more than
those formed by attack at the meta positions, giving rise to the observed regioselectivity.
3. Deactivating and meta-directing: These substituents are strongly electron withdrawing and
destabilize carbocations. They include –CF3, -C=OR, -CN, -NO2 and related species. All the
ring positions are deactivated, but since the meta positions are deactivated less than the ortho
and para, meta substitution is favored.

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Example
 Nitration of chlorobenzene afford ortho and para-substitution product as a major product.

Cl Cl
Cl Cl
H2SO4 NO2
+ HNO3 + +
NO2
35% 64 % NO2 1%

 Nitration of nitrobenzene gives about 93% m-dinitrobenzene, 6% o-dinitrobenzene, and 1% p-

dinitrobenzene.
NO2 NO2
NO2 NO2
H2SO4 NO2
+ HNO3 + +
NO2
6% 1% NO2 93%

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