ADAMA SCIENCE AND TECHNOLOGY UNIVERSITY

SCHOOL OF APPLIED NATURAL SCIENCE

DEPARTMENT OF APPLIED CHEMISTRY
CHAPTER 1
THE CHEMISTRY OF AROMATIC COMPOUNDS
Instructor :Yilkal Matebie([Link])
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Benzene and Aromaticity

 INTRODUCTION
 Aromatic refer to the class of compounds that contain
six-membered benzene-like rings.
 Kekulé’s First Structure of Benzene

 Aromatic compounds (arenes) are chemical

compounds
 contain conjugated planar ring systems
 delocalized pi electron clouds instead of
isolated alternating single and double bonds.
 Pleasing fragrances
 benzene and toluene. 2
 STRUCTURAL PROPERTIES OF BENZENE
 All its C-C bonds are the same length:
 Electron density in all six C-C bonds is identical

 Structure is planar, hexagonal

 All C–C–C bond angles are 120°

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 Each C is sp2-hybridized and has a p orbital perpendicular
to the plane of the six-membered ring

 A Resonance Picture of Bonding in Benzene

Resonance hybrid

Aromaticity: cyclic conjugated organic compounds such as 4

benzene, exhibit special stability due to resonance
delocalization of  -electrons.
 CRITERIA FOR AROMATICITY
 Aromatic a compound must meet both of the
following criteria:
1. It must have an uninterrupted cyclic cloud of π electrons.
 the molecule must be cyclic and must be planar.
2. The cloud must contain an odd number of pairs of π
electrons or 4n + 2 (n = 0, 1, 2 …) total electrons.
 Hückel’s rule: The rule states that for a planar, cyclic
compound to be aromatic, its uninterrupted p cloud
must contain (4n + 2) π electrons, where n (n = 0, 1, 2,
3…) is any whole number.

a. What is the value of n in Hückel’s rule when a

compound has nine pairs of electrons?
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b. Is such a compound aromatic?
 BENZENE
 It has 6  electrons: 4n + 2 = 6, thus n = 1
 It is aromatic: it is stable and the electrons are
delocalized.

 Compounds with 4n  electrons are NOT aromatic

 Planar, cyclic conjugated molecules with 4n  electrons
are antiaromatic
 They are much less stable than expected
 They will distort out of plane and behave like ordinary
alkenes
cyclooctatetraen
Which of the above is antiaromatic? 6

cyclobutadiene
 AROMATIC HYDROCARBONS

 Monocyclic hydrocarbons with alternating single and double

bonds are called annulenes.

cyclobutadiene
[4]-annulene benzene cyclooctatetraene
[6]-annulene [8]-annulene

 A prefix in brackets denotes the number of carbons in the

ring
 Cyclobutadiene and cyclooctatetraene are not
aromatic, because they have an even number of 
electron pairs. 7
 CYCLOBUTADIENE
 It has 4  electrons: 4n + 2 = 4, thus n = ½ (not an
integer)
 It is antiaromatic: The  electrons are localized into
two double bonds

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 CYCLOOCTATETRAENE
 It has 8  electrons: 4n + 2 = 8, thus n = 3/2 (not an
integer)
 It is nonaromatic:

Practice Problem: To be aromatic, a molecule must have

4n + 2 p electrons and must have cyclic conjugation. Is
cyclodecapentaene aromatic?

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 some other compounds and determine whether they
are aromatic

cyclopropenyl anion
cyclopropenyl cation Not aromatic
cyclopropene Aromatic
Not aromatic
sp3
 Cyclopropene not aromatic b/c it does not have an
uninterrupted ring of p orbital-bearing atoms.
 The cyclopropenyl cation has an uninterrupted ring of
p orbital-bearing atoms and the cloud contains one(an
odd number) pair of delocalized  electrons.
 The cyclopropenyl anion has an uninterrupted ring of
p orbital-bearing atoms but has an even number of 
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electron pairs
 Cyclopentadienyl anion
Cyclopentadienyl cation
cyclopentadiene aromatic
Not aromatic Not aromatic

Cyclopentadiene does not have an uninterrupted

ring of p orbital-bearing atoms.
Cyclopentadienyl cation has an even number of 
electron pairs
Cyclopentadienyl anion has an uninterrupted ring of
 orbital-bearing atoms and an odd number of 
electron pairs
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 POLYCYCLIC HYDROCARBON
 These compounds consist of fused benzene rings
and are aromatic

Anthracene

Naphthalene phenanthrene chrysene

 Naphthalene (five pairs of p electrons), phenanthrene
(seven pairs of p electrons), and chrysene (nine pairs of p
electrons) are aromatic.

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EXERCISES

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 Heterocyclic Aromatic Compounds
 A heterocyclic compound is a cyclic compounds that contain
at least one atom other than carbon within their ring.
 The most common heteroatoms found in heterocyclic
compounds are N, O, and S.
 Many heterocyclic compounds are aromatic
Heterocyclic Compounds

O S
N
N
H
Pyridine Pyrrole Furan Thiophene
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ANTIAROMATICITY
 Antiaromatic if it fulfills the first criteria for
aromaticity but does not fulfill the second criteria.
 it must be a planar, cyclic compound with an
uninterrupted ring of p orbital-bearing atoms, and
the π cloud must contain an even number of pairs of
electrons.

cyclobutadiene Cyclopentadienyl cation

 Cyclobutadiene is a planar, cyclic molecule with two
pairs of electrons.
 it is antiaromatic and highly unstable.
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REACTION OF AROMATIC COMPOUNDS

• Benzene is a nucleophile then react with electrophile
(Y+).
• When an electrophile attaches itself to a benzen ring,
a carbocation intermediate is formed.
1. Electrophilic aromatic substitution reaction
2. Nucleophilic aromatic substitution reaction

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 Aromatic product is much more stable than the
nonaromatic addition product, the overall
reaction is an electrophilic substitution reaction
rather than an electrophilic addition reaction.17
AROMATIC SUBSTITUTION REACTIONS
A. Electrophilic aromatic substitution reactions:
five common electrophilic aromatic substitution
reactions:

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MECHANISM
 All of these electrophilic aromatic substitution reactions
take place by the same two-step mechanism.

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1. HALOGENATION
• The bromination or chlorination of benzene.
• Requires a Lewis acid such as ferric bromide or ferric
chloride.
• Bromination

• Chlorination

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IODINATION
 Not required Lewis acid to generate
electrophile, required oxidizing agent such as
nitric acid or hydrogen-preoxide.

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2. NITRATION

Nitronium ion formation:

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3. SULFONATION

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4. FRIEDEL-CRAFTS ALKYLATION
• Friedel–Crafts alkylation places an alkyl group on a
• benzene ring.

Mechanism
Generation of Carbocation.

Reaction of carbocation with benzene

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• One drawback to Friedel–Crafts alkylation is that

rearrangements can occur. The carbocation will
rearrange to a more stable species:

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 100% of the 2-methyl-2-phenylbutane product can be
obtained if a bulky alkyl halide is used:

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5. FRIEDEL–CRAFTS ACYLATION
• Friedel–Crafts acylation places an acyl group on a
benzene ring.
• Acyl halide or an acid anhydride can be used for Friedel–
Crafts acylation.

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MECHANISM FRIEDEL–CRAFTS ACYLATION

• An acylium ion is the electrophile required for a Friedel–
Crafts acylation reaction
• Generation of an acylium ion(electrophile).

• Reaction of benzene with acylium ion.

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EXERCISE
1. Show the mechanism for alkylation of benzene by an alkene.
2. What would be the major product of a Friedel–Crafts alkylation
reaction using the following alkyl halides?

3. Propose a mechanism for the following reaction:

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ALKYLATION OF BENZENE BY ACYLATION–REDUCTION

Friedel–crafts alkylation will not produce a good yield of

an alkylbenzene containing a straight-chain group,
because the carbocation will rearrange:

Acylium ions, however, do not rearrange:

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SYNTHESIS OF BENZALDEHYDE
 Formyl chloride can be prepared, Gatterman–Koch
formylation reaction.

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DIRECTING EFFECTS OF SUBSTITUENTS

• A substituent already present on the ring has two effects:
• Rate of electrophilic aromatic substitution?
• Regioselectivity of electrophilic aromatic substitution?
• Substituents affect the reactivity of an aromatic ring
• Some substituents activate a ring, making it more
reactive than benzene, and
• Some deactivate a ring, making it less reactive than
benzene.

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Relative rate of nitration

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SUBSTITUENTS AFFECT THE ORIENTATION OF A REACTION

• The substituent attached to the benzene ring determines
the location of the new substituent.

three possible disubstituted products—ortho, meta, and

para

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• Substituents can be classified into three groups

Substituent effects in electrophilic aromatic substitutions.

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ACTIVATING AND DEACTIVATING EFFECTS IN AROMATIC RINGS

• All activating groups is that they donate

electrons to the ring:
• Making the ring more electron-rich
• stabilizing the carbocation intermediate
• All deactivating groups is that they withdraw
electrons from the ring.
• Making the ring more electron- poor,
• Destabilizing the carbocation intermediate
• Electron donation or withdrawal may occur by
either an inductive effect or a resonance effect
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ORTHO AND PARA DIRECTORS
 All substituents that donate electrons by resonance are
ortho–para directors .
 Nitration of phenol.
 More resonance more stable.

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META DIRECTORS
 All substituents that cannot donate electrons into the
ring inductively or by resonance are meta directors
 Nitration of benzaldhyde

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• All activating substituents ortho and para directors.

• The weakly deactivating halogens are ortho–para

directors

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• All deactivating substituents (except the halogens) are

meta directors.

• Rank the compounds in each of the following groups in order of their

reactivity toward electrophilic aromatic substitution:
A. Nitrobenzene, phenol, toluene
B. Phenol, benzene, chlorobenzene, benzoic acid 41
C. Benzene, bromobenzene, benzaldehyde, aniline
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MULTIPLE SUBSTITUENTS EFFECTS

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 Nitration of p-tert-butyltoluene.
 Example of a steric effect.

 Nitration of m-xylene is directed ortho to one methyl

group and para to the other

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B. NUCLEOPHILIC AROMATIC SUBSTITUTION REACTIONS(SNAR )
1. REACTIONS OF ARYL HALIDES

I. Addition–elimination mechanism
 Required ortho or para highly EWG substituent to
halogen to stabilized the carboanion.
 Electron-withdrawing substituents increase the
reactivity of the benzene ring toward nucleophilic
substitution and decrease the reactivity of the benzene
ring toward electrophilic substitution
 General mechanism for nucleophilic aromatic
substitution in Addition elimintion mechanism.

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  Mechanism
Step 1: Addition stage.

Step 2: Elimination stage.

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 II. ELIMINATION–ADDITION MECHANISM
 Very strong bases such as sodium or potassium
amide react readily with aryl halides.

 Mechanism:
 Elimination stage, formation of benzyne


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 Addition phase. The product of this step is a carbanion.

 Completion of addition phase

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THE EFFECT OF SUBSTITUENTS
 o-chlorotoluene yields a mixture containing
comparable amounts of o- and m-methylaniline.

 p-chlorotoluene gives a single aryne, and this aryne

gives a mixture of m- and p-methylaniline.

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 m-chlorotoluene
 Two isomeric arynes give the three isomeric substitution
products formed from m-chlorotoluene:

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EXERCISE

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REACTIONS OF SUBSTITUTED BENZENES

• Many substituted benzenes are found in nature.
• That have physiological activity

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REACTIONS OF AROMATIC SIDE CHAINS

A. Radical Substitution of Benzylic (NBS)
N-Bromosuccinimide

B. Substitution of Alkyl Side-Chains

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C. OXIDATION OF ALKYLBENZENES
• Alkyl side chain on a benzene ring is oxidized to benzoic acid or a
substituted derivative of benzoic acid.

When two alkyl groups are present on the ring, both

are oxidized.
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• Commonly used oxidizing agents are potassium

permanganate or acidic solutions of sodium dichromate

Lacks a benzylic hydrogen 57

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• Mild oxidizing agent such as MnO2 is used, benzylic

alcohols are oxidized to aldehydes or ketones.

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4. REDUCTION OF NITRO GROUPS

• A nitro substituent reduced to an amino substituent.
• Use a metal (tin, iron, or zinc) plus an acid (HCl) or
catalytic hydrogenation can be used to carry out the
reduction.

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• Selectively reduce just one of two nitro groups.

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• Give the product of each of the following reactions:

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