Chemistry of Aromatic

Compounds

Wolmer’s Boys’ School

CAPE Chemistry Unit 2
 By the end of this topic you
should be able to
1. State formula of benzene and discuss its structure
(delocalised electrons/ pi system, a planar molecule)
2. State the name of the mechanism that benzene and its
derivatives undergo
3. Describe the reactions of benzene:
i) nitration ii) halogenation
4. Describe the mechanisms involved in:
i) nitration ii) halogenation
5. Describe the chemical reactions of methylbenzene and
nitrobenzene
 By the end of this topic you
should be able to
6. Compare and explain the difference in reactivity of
methylbenzene vs benzene and use conditions of nitration
as an example
7. Use methylbenzene and a derivative of methylbenzene to
show how different conditions can influence the products
formed for a reaction
8. Describe the selected chemical reactions of phenol
9. Describe the formation of an azo compound
10. State uses of azo compounds
 Aromatic Compounds
Aromatic compounds

These hydrocarbons or derivatives are based on the molecule benzene

C6H6. Benzene is a planar molecule containing a ring of six carbon

atoms, each with a hydrogen atom attached.

Please note this structure is a simplification of the actual molecule. Each
carbon-carbon bond have exactly the same length, it is a hybrid between
a single bond and a double bond. There are delocalised electrons above
and below the plane of the ring.
 Reactions of Benzene and
Derivatives
The presence of the delocalised electrons makes benzene very stable.
Benzene resists addition reactions since this would cause the
delocalisation to be broken.
• Benzene does not undergo electrophilic addition

• It undergoes electrophilic substitution maintaining the

aromatic core.

• Electrophilic aromatic substitution replaces a proton on

benzene with another electrophile.
Aromatic Electrophilic
Substitution

7
 Aromatic Electrophilic
Substitution (Close up image)

E
E
H E
H :base
+ H-base
Electrophilic Substitution in
Benzene
 Nitration of Benzene
• Benzene is treated with a mixture of concentrated
nitric acid and concentrated sulphuric acid at a
temperature not exceeding 50°C. The mixture is
held at this temperature for about half an hour.
Yellow oily nitrobenzene is formed.
• The electrophile is the nitronium or nitryl cation
which forms when the nitric acid reacts with the
sulfuric acid.
 Nitration of Benzene
Mechanism
Formation of the electrophile (NO2+)
The sulfuric acid protonates nitric acid which breaks
down to form water and the nitronium ion. This happens
in situ at about 60°C. The H2SO4 serves as a catalyst.

HNO3 + H2SO4  H2NO3+ + HSO4-

NO2
H2NO3 +  HNO
H2O3+, H2SO4 (nitronium ion)
NO2+ + H2O

Overall,
Formation of electrophile
+ -
HNO3 + H2SO4 NO2 + H2O + HSO4
Nitration of Benzene (simplified)
Nitration of Benzene
Mechanism
Uses of Nitrobenzene

• Nitrobenzene is used to produce

lubricating oils such as those used in motors
and machinery.
• A small amount of nitrobenzene is used in
the manufacture of dyes, drugs, pesticides,
and synthetic rubber.
• Its is also used to mask unpleasant odours in
polishes, paints and leather dressings.
 Halogenation of Benzene
• Benzene reacts with chlorine or bromine in the
presence of a catalyst, replacing one of the
hydrogen atoms on the ring by a chlorine or
bromine atom. The reactions happen at room
temperature. The catalyst is either aluminium
chloride (or aluminium bromide if you are
reacting benzene with bromine) or iron bromide/
iron chloride.
• The catalyst is called a Friedel Crafts Catalyst
(halogen carrier).
 Halogenation of Benzene
• Benzene’s  electrons participate as a Lewis base
in reactions with Lewis acids

– Lewis acid: electron pair acceptor

– Lewis base: electron pair donor

• The product is formed by substitution of a proton,

which is replaced by a halogen
Bromination / Chlorination

H Br
Br 2, FeBr 3
+ HBr

H Cl
Cl2, FeCl3
+ HCl
 Bromination of Benzene
• Benzene’s  electrons participate as a Lewis base in
reactions with Lewis acids
• The product is formed by loss of a proton, which is
replaced by bromine
• FeBr3 is added as a catalyst to polarize the bromine
reagent

Br
FeBr3
+ Br2 + HBr
Bromination of Benzene
Mechanism
 Chlorination of Benzene
Mechanism
As a chlorine molecule approaches the benzene ring, the delocalised
electrons in the ring repel electrons in the chlorine-chlorine bond.

It is the slightly positive end of the chlorine molecule which acts as the
electrophile. The presence of the aluminium chloride (halogen carrier)
helps this polarisation.
Chlorination of Benzene
Mechanism
END OF LESSON 1
 Common substituent groups and their effect on EAS:

-NH2, -NHR, -NR2

-OH
-OR
-NHCOCH3
ortho/para directors
increasing reactivity

-C6H5
-R
-H
-X
-CHO, -COR
-SO3H
-COOH, -COOR
meta directors
-CN
-NR3+
-NO2
If there is more than one group on the benzene
ring:
1. The group that is more activating (higher
on “the list”) will direct the next
substitution.
2. You will get little or no substitution
between groups that are meta- to each
other.
Why do substituent groups on a benzene ring affect the
reactivity and orientation in the way they do?

 electronic effects, “pushing” or “pulling” electrons by

the substituent.

Electrons can be donated (“pushed”) or withdrawn

(“pulled”) by atoms or groups of atoms via:
Induction – due to differences in electronegativities
Resonance – delocalization via resonance
 Reactions of methylbenzene
(Toluene)
• Methylbenzene (toluene) is a benzene derivative where one of the
hydrogen on a benzene ring is replaced by a methyl group.

• Since the methyl group has a positive inductive effect, it pushes

electrons into the benzene ring and causes it to be more reactive.

• Consequently, electrophilic substitution in methylbenzene occurs

more easily than in benzene. The methyl group directs the
incoming nitronium electrophile to the ortho and para positions.
Usually a 1:1 ratio of ortho substituted and para substituted product
forms and a lower temperature is used to obtain monosubstituted
products.
 Nitration of Toluene
• Toluene reacts 25 times faster than benzene. The
methyl group is an activator.
• The product mix contains mostly ortho and para
substituted molecules.

=>
Chapter 17 28
 Nitration of Methylbenzene
Nitration of methylbenzene
It is nitrated to form a mixture of 2-nitromethylbenzene and 4-
nitromethylbenzene.
 Question
• Show the reaction between methylbenzene
and Br2. Don’t forget the Friedel Crafts
catalyst.
Electrophilic Aromatic Substitution
Reactivity & Orientation

• Bromination of a
benzene ring
containing an
electron donating
group (methyl
group) is faster
than bromination
of benzene itself.

• Substitution of
bromine at the
ortho/para
positions is
favored .
 Reduction of Nitrobenzene
• Nitrobenzene is reduced to phenylamine
(aniline) using a mixture of tin and
concentrated hydrochloric acid and heating
the mixture under reflux for half an hour.

• NaOH solution is added to liberate the

phenylamine from the tin complex.
Reduction of nitrobenzene
 How reaction conditions can
influence the product formed
• If chlorine or bromine react with boiling methylbenzene in the absence
of a catalyst but in the presence of UV light, substitution happens in
the methyl group rather than the ring.

• For example, with chlorine (bromine would be similar):

• The organic product is (chloromethyl)benzene. The brackets in the

name emphasise that the chlorine is part of the attached methyl group,
and isn't on the ring.
• One of the hydrogen atoms in the methyl group has been
replaced by a chlorine atom. However, the reaction doesn't
stop there, and all three hydrogens in the methyl group can
in turn be replaced by chlorine atoms.
• That means that you could also get
(dichloromethyl)benzene and (trichloromethyl)benzene as
the other hydrogen atoms in the methyl group are replaced
one at a time.
 How reaction conditions can
influence the product formed
(Summary)
Reactions of methylbenzene under different conditions

If the conditions involve uv light, free radical substitution occurs but if a

halogen carrier is used, the halogen atom is attached directly to the ring.
Provide the Reagents

CH2CH3

Br OH
 O CH2CH3
1) ClCCH 3, AlCl 3
2) SO3, H2SO4
3) Br 2, FeBr 3 Br OH
1) 4) H2 Pd/C
o
5) NaOH, 300 C 5,6)
+
6) H3O
O O O

2) 3) 4)

SO3H Br SO3H Br SO3H

Phenols
Phenols Ar-OH

Phenols are compounds with an –OH group

attached to an aromatic carbon. Although they
share the same functional group with alcohols,
where the –OH group is attached to an aliphatic
carbon, the chemistry of phenols is very different
from that of alcohols.
Nomenclature.
Phenols are usually named as substituted phenols. The
methylphenols are given the special name, cresols. Some other
phenols are named as hydroxy compounds.

OH OH CH3 OH
OH COOH

Br

phenol m-bromophenol o-cresol salicylic acid

OH OH COOH
OH
OH

OH
OH OH

catechol resorcinol hydroquinone p-hydroxybenzoic acid

physical properties
phenols are polar and can hydrogen bond
phenols are water insoluble
phenols are stronger acids than water and
will dissolve in 5% NaOH
phenols are weaker acids than carbonic acid and
do not dissolve in 5% NaHCO3
Intramolecular hydrogen bonding is possible in some
ortho-substituted phenols. This intramolecular hydrogen
bonding reduces water solubility and increases volatility.
Thus, o-nitrophenol is steam distillable while the
isomeric p-nitrophenol is not.
OH
O
H
O
N
O NO2

o-nitrophenol p-nitrophenol
bp 100oC at 100 mm bp decomposes
0.2 g / 100 mL water 1.69 g / 100 mL water
volatile with steam non-volatile with steam
phenols, syntheses:
1. From diazonium salts

N2 OH
H2O,H+

2. Alkali fusion of sulfonates

SO3 Na NaOH,H2O ONa OH

H+

300o
as acids:
with active metals:
OH ONa
Na
+ H2(g)

sodium phenoxide
with bases:
CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF

OH ONa

+ NaOH + H2O

SA SB WB WA
 CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF

OH ONa

+ NaOH + H2O

SA SB WB WA
water insoluble water soluble

OH

+ NaHCO3 NR phenol < H2CO3

We use the ionization of acids in water to measure acid
strength (Ka):
HBase + H2O H3O+ + Base-

Ka = [H3O+ ][ Base ] / [ HBase]

ROH Ka ~ 10-16 - 10-18

ArOH Ka ~ 10-10

Why are phenols more acidic than alcohols?

 ROH + H2O H3O+ + RO-

ArOH + H2O H3O+ + ArO-

OH OH O O O O O

Resonance stabilization of the phenoxide

ion, lowers the PE of the products of the
ionization, decreases the ΔH, shifts the equil
farther to the right, makes phenol more
acidic than an alcohol
effect of substituent groups on acid strength?

OH O

G + H2O G + H3O

Electron withdrawing groups will decrease the negative

charge in the phenoxide, lowering the PE, decreasing the ΔH,
shifting the equil farther to the right, stronger acid.
Electron donating groups will increase the negative charge
in the phenoxide, increasing the PE, increasing the ΔH,
shifting the equilibrium to the left, weaker acid.
Number the following acids in decreasing order of acid
strength (let # 1 = most acidic, etc.)

OH OH OH OH OH

NO2 CH3 Br

3 5 1 4 2
SO3H COOH OH CH2OH

1 2 3 4
2. ester formation (similar to alcohols)

OH
CH3 O H+ O
+ CH3CH2C CH3CH2C + H2O
OH O

H3C

O
OH H3C C
COOH O
+ (CH3CO)2O COOH

salicyclic acid aspirin

 O
analgesic
H3C C anti-inflamatory
O
antipyrretic
COOH anticoagulant

Reye's syndrome
aspirin not to be used by children
with high fevers!

OH

aspirin substitute
Tylenol

H3C C NH Kidney damage!

O

acetaminophen
4. Electrophilic Aromatic Substitution
The –OH group is a powerful activating group in EAS
and an ortho/para director.
a) nitration

OH OH
HNO3 O2N NO2
polynitration!
NO2

OH OH OH
dilute HNO3 NO2
+

NO2
 b) halogenation

OH OH
Br2 (aq.) Br Br no catalyst required
use polar solvent

Br
polyhalogenation!
OH OH OH
Br2, CCl4 Br
+
non-polar solvent
Br
d) Friedel-Crafts alkylation.

OH OH
CH3 AlCl3
+ H3C C CH3
Cl
H3C C CH3
CH3
e) Friedel-Crafts acylation

OH OH
O AlCl3
+ CH3CH2CH2C
Cl

Do not confuse FC acylation with esterification:

OH
O
O
+ CH3CH2CH2C O
Cl
g) coupling with diazonium salts
(EAS where a H is substituted with a benzenediazonium ion
which is a weak electrophile)

OH N2 Cl OH
CH3 CH3
+

benzenediazonium N
chloride N

an azo dye
Azo Compounds
Phenylamine reacts with sodium
nitrite under acidic conditions to
form the benzenediazonium ion
Uses and Importance of Azo dyes
 Are you able to
1. State formula of benzene and discuss its structure
(delocalised electrons/ pi system, a planar molecule)
2. State the name of the mechanism that benzene and its
derivatives undergo
3. Describe the reactions of benzene:
i) nitration ii) halogenation
4. Describe the mechanisms involved in:
i) nitration ii) halogenation
5. Describe the chemical reactions of methylbenzene and
nitrobenzene
 Are you able to
6. Compare and explain the difference in reactivity of
methylbenzene vs benzene and use conditions of nitration
as an example
7. Use methylbenzene and a derivative of methylbenzene to
show how different conditions can influence the products
formed for a reaction
8. Describe the selected chemical reactions of phenol
9. Describe the formation of an azo compound
10. State uses of azo compounds