CHAPTER 6: Aromatic Hydrocarbon

Introduction to Arenes

• Arenes or aromatic hydrocarbons have at least one benzene ring.

• Benzene has molecular formula, C6H6

• All carbon atoms are sp2 hybridised and benzene has three π bonds. The electrons
are delocalised due to resonance and this π electrons delocalised system gives extra
stability to the benzene ring.

Kekule structure

• Benzene is thought to be similar to alkenes but a few evidences below suggest

otherwise (contain π electrons delocalised system).

• Benzene does not react with bromine in tetrachloromethane and acidified potassium
permanganate (VII) solution. Brown colour of Br2 / CCl4 and purple colour of KMnO4 /
H+ remains unchanged.

Resonance Structure

• There are two ways to write the structure of benzene

• These are called “resonance structures”

• However, neither of these represents the true structure of benzene since benzene
has only one structure, with all C-C bonds being equivalent

• The true structure is a hybrid of the two resonance structures; this can be
represented by drawing the  bonds as a circle

• We use the individual resonance structures when we write reaction mechanisms

involving benzene to show more clearly the bond formation and bond breaking in the
reaction

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Polar substituent:

a) An electron withdrawing group or EWG draws electrons away from a reaction

center.

Examples of electron withdrawing groups are

• halogens (F, Cl);

• nitriles CN;
• carbonyls CO;
• nitro groups NO2.

b) An electron releasing group or ERG (otherwise called electron donating groups or

EDG) releases electrons into a reaction center and as such stabilizes electron
deficient carbocations.

Examples of electron releasing groups are

• alkyl groups;
•
• alcohol groups;
• amino groups. (NH2)

Naming aromatic compounds

1) Benzene is considered as the parent and comes last in the name.

2) List substituent in alphabetical order.

3) Number ring in direction that gives lowest locate at first point of difference.

4) Simple compounds are named as substituted benzene derivatives.

2
Nomenclature of Benzene Derivatives

• If the alkyl substituent is smaller than the ring (6 or fewer carbons), the parent name
for some monosubstituted benzenes is benzene; the substituent name is added as a
prefix

CH2CH2CH3

Propylbenzene

• For other monosubstituted benzenes, the presence of the substituent results in a new
parent name

3
 O

C
H

Benzaldehyde

• If the alkyl substituent is larger than the ring (7 or more carbons), the parent name for
some monosubstituted benzenes is alkane; the substituent name is phenyl

• When two substituents are present their position may be indicated by the prefixes
ortho, meta, and para (o, m and p) or by the corresponding numerical positions

4
 O

2 2
H3C 1 C
Cl 3 CH3
1 3 H
1
2 4
Cl
Cl

1,2-Dichlorobenzene 1,3-Dimethylbenzene 4-Chlorobenzaldehyde

or or or
ortho-Dichlorobenzene meta-Dimethylbenzene para-Chlorobenzaldehyde

• Dimethyl substituted benzenes are called xylenes

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• Benzene with more than 2 substituents are named alphabetically
• -phenol and –toluene are used as the parent names rather than –benzene
OH CH3
3 1 O2N NO2
Br 4 CH3 CH3 1
2
2 6 2
1
3 3
5 5
CH3 H3C
4 4
4-Bromo-1,2-dimethylbenzene 2,5-Dimethylphenol NO2
2,4,6-trinitrotoluene

Exercise:

a) CH3 b) c) d) HO O
CH3 Br C

Br NO2

CH3

CH3

e) f) g)
NH2
Cl
O2N
OH

CH CH3
Br

CH3

6
 h) i) j)
COOH NO2 OH

OH CH3 OH

k) l) m)
OCH3 OH
O O
C6H5
HO C C OH

Br

7
4. Reactions of Arenes:

Electrophilic aromatic substitution reactions

H E

+ E Y + H Y

A) Halogenation of benzene

Aromatic rings are less reactive towards electrophiles than alkenes.

H Cl
AlCl3
+ Cl2 + HCl

Chlorine Chlorobenzene

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Mechanism:

Step 1:

AlCl3, an electron deficient compound acts as a Lewis acid accepts lone electrons pair from
one of the chlorine atom thus induces polarisation of Cl2 molecule tu form electrophile, Cl+
ion.

Step 2

Cl+ the electrophile attacks the benzene ring to form the resonance stabilised cation
intermediate which is not stable. This is because the π electron delocalised system is
destroyed.

H Cl H Cl H Cl
H H
+
+

Resonance-stabilized cation intermediate; +ve charge is delocalized onto 3 atoms of the ring

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Step 3

The intermediate loses proton, H+ to form chlorobenzene and catalyst, AlCl3

or

H Cl
Cl

H
+
AlCl3 Cl + AlCl3 + HCl
fast

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B) Nitration of benzene

H NO2
H2SO4
+ HONO2 + H2O

Nitric acid Nitrobenzene

Nitration of aromatic rings is a key step in the synthesis of explosives such as TNT
(trinitrotoluene), dyes and many pharmaceutical agents.

or

H
+
H O NO2 + H O SO3H H O NO2 + HSO4-

H H
+ +
H O NO2 H O + O N O

Nitronium ion

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H NO2 H NO2 H NO2
H H
+
+

Resonance-stabilized cation intermediate

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C) Sulfonation of benzene

H SO2OH
SO3
+ H2O
HOSO2OH (fuming)

Sulfuric Acid Benzenesulfonic acid

Sulfur trioxide, SO3, in fuming sulfuric acid is the electrophile.

_
O O O O
S S+ S+ S +
_ _
O O O O O O O O

13
OR

2H2SO4 ↔ SO3 + H3O+ + HSO4-

Or

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Step 1:

Step 2:

Step 3:

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D) Friedel-Crafts Alkylation

H C(CH3)3
AlCl3
+ (CH3)3CCl + HCl

tert-butyl chloride tert-butylbenzene

(Alkyl Halide)
2-chloro-2-methylpropane

Examples:

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Step 1 (To generate the electrophile, CH3-CH2+)

AlCl3 acts as a catalyst and halogen carrier accepts lone electron pair from Cl in CH3CH2Cl to
generate the electrophile, CH3-CH2+. It is a lewis acid by accepting lone electron pair from the
chloroethane.

Step 2 (Electrophile attacks the benzene ring)

H CH2CH3 H CH2CH3 H CH2CH3

H H
+
+

Resonance-stabilized cation intermediate

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Step 3 (Loss of proton, H+ to regain stability of the kekule structure)

H CH2CH3
CH2CH3

H
+
AlCl3 Cl + AlCl3 + HCl
fast

E) Friedel-Crafts Acylation
O

O
H CCH2CH3
AlCl3
+ CH3CH2CCl + HCl

Propanoyl chloride 1-Phenyl-1-Propanone

(acyl halide) (aryl ketone)

*The mechanism is the same with friedel-crafts alkylation

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Effect of substituents groups on the benzene ring

• Substituent groups already present in the benzene ring can influence the rate of
electrophilic substituents and orientation of the products formed.

• There are 2 types of substituent groups on the benzene ring; ACTIVATING and
DEACTIVATING.

• Activating group: result higher reactivity of the substituted benzene towards

electrophilic attack. This is because the activating group has electron donating
effect resulting higher electron density of the benzene ring thus easier to be attacked
by electrophiles.

• Deactivating groups: results lower reactivity of the substituted benzene towards

electrophilic attack. This is because the deactivating group has electron
withdrawing effect resulting lower electron density of the benzene ring thus difficult
to be attacked by electrophiles.

What makes a group either activating or deactivating?

• All activating groups donate electrons to the ring, thereby making the ring more
electron-rich, stabilizing the carbocation intermediate and lowering the activation
energy for its formation. Example: Hydroxyl (OH), alkoxyl (-OR) and amino groups
(-NH2).

• All deactivating groups withdraw electrons from the ring, thereby making the ring
more electron-poor, destabilizing the carbocation intermediate and raising the
activation energy for its formation. Example: carbonyl (-C=O), cyano (-C≡N), nitro
groups (-NO2).

A substituent already present on the ring has 2 effects:

a) Substituents affect the reactivity of the aromatic ring

• Some of the substituents activate the ring, making it more reactive than benzene.

• Some of the substituents deactivate the ring, making it less reactive than benzene

• In aromatic nitration, -OH substituent makes the ring 1000 times more reactive than
benzene, while an –NO2 substituent makes the ring more than 10 million times less
reactive

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b) Substituents affect the orientation of the reaction

• The three possible disubstituted product –ortho, meta, and –para are usually not
formed in equal amount

• The nature of the substituent present on the benzene ring determines the position of
the second substitution

Ortho-para directing Meta-directing

Activating -NH2, -NHR, -NR2, -OH, -OR –
C6H5, -R,
-NHCOR, -OCOR
Deactivating (-F, -Cl, -Br, -I) -NO2, -COOH, -CN, -COOR, -CHO, -
COR, -SO3H,
-COCl, -CONH2, -CX3

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Disubstitution Reactions on Benzene Ring

Example:

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EXERCISE:

Beginning with benzene, suggest a synthetic sequence for the preparation of

4-chlorobenzene:

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When there is competition between ortho-para and meta directing groups, ortho-para
directing groups win out.

Example:
OH
OH
OH
a)
Br
Br2
+
FeBr3

NO2
NO2
NO2
Br

b)
OH OH

NO2 NO2

SO3

H2SO4

SO3H

CH3 CH3
c)
Br

Br2

AlCl3

SO3H SO3H

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Naming Tri & Tetra-substituted Benzene

- If one of the substituents imparts a special name, then the compound is named as a
derivative of the parent molecule.

- If none of the substituent imparts a special name, the substituents are numbered to give the
smallest sets of numbers and listed in alphabetical order before the ending benzene.

Example:
CH3
OH NO2 NH2
1 NO2
Br 1 Br 4 1
6 2 Cl Cl
2 2
5 6
6 3

3 3
5 5 6 5 3
4 2
4 1
Br 4
Cl
Br CH2CH3 Cl

4-chloro-2-nitrotoluene 2,4,6-tribromophenol 2-bromo-1-ethyl-4-nitrobenzene 2,4,6-trichloroaniline

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Reactivity

• Benzene (like alkene) has the nucleophilic character of the π system.

• Benzenes (unlike alkenes – which undergo addition reactions) typically undergo

electrophilic substitution reactions in which a group (usually H) is replaced and the
aromatic system is retained.

1. Oxidation of alkylbenzene (side chain oxidation)

• Alkylbenzene is oxidized to benzoic acid using oxidising agents such as acidified

potassium manganate (VII), warm and acidified sodium dichromate (VI), warm. The
benzene ring remains intact.

• In order for alkylbenzene to be oxidised, it must posses 1 benzylic hydrogen

(hydrogen atom bonded to C atom which is bonded directly to benzene ring).
CH3

H3C C CH3

[O]
No reaction

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2. Halogenation of alkylbenzene (Free radical substitution of alkylbenzene)

• Involving halogens such as Cl2 / Br2 in the presence of an ultraviolet light or high
temperature.

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3. Addition reaction under certain condition:

a) Catalytic Hydrogenation

• Elevated heat and pressure is required.

• Possible catalysts: Pt, Pd, Ni, Ru, Rh.

• Reduction cannot be stopped at an intermediate stage.

CH3 CH3

3 H2, 1000 psi

Ru, 100°C
CH3 CH3

b) Chlorination of Benzene

• Addition to the benzene ring may occur with high heat and pressure (or light).

• The first Cl2 addition is difficult, but the next 2 moles add rapidly.

• The product, benzene hexachloride, is an insecticide sold commercially as Lindane

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Uses and effects of aromatic compounds

HO
HO

O O

O ibuprofen
vanillin (painkiller drugs)
(in vanilla flavour)

HO

O
O

BHA
OH
(Food antioxidant)
Aspirin

HO

NH

HO

OH
Adrenaline
(hormone)

benzopyrene

dibenzanthracene

• Similar to benzene, benzopyrene and dibenzanthracene are known as carcinogens-

chemical that cause cancer. These compounds are formed from heating of organic
materials at high temperature. They are present in tobacco smoke, automobile
exhaust and in burned and heavily browned foods.

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Exercises

a) Write structural formulae of compounds A → K

b) State reagent X and reaction conditions

c) Name the reaction and write the mechanism for the formation of E from B

d) Draw the structure of electrophile W

2. Propose a synthesis of each of the following substances from benzene:

a) o-bromotoluene

b) m-chlorobenzoic acid

c) p-benzenedibenzoic acid

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