A2 Chemistry

Chapter 2
Chapter 2 Objectives

Properties of Phenol

Delocalisation of Benzene

Phenol + NaOH

Nitration of Benzene

Phenol + Na(s)

Halogenation of Benzene

Phenol + Br2

SAQ 2.1

SAQ 2.3

SAQ 2.6

A2: Arenes
Chapter 2 Objectives (1-8)
1.
2.

3.
4.

Show understanding of the concept of delocalisation of

electrons as used in a model of benzene
Describe electrophilic substitution of arenes with concentrated
nitric acid in the presence of concentrated sulphuric acid, a
halogen in the presence of a halogen carrier, and a
halogenoalkane such as chloromethane in the presence of a
halogen carrier (Friedel-Crafts reaction).
Describe the mechanism of electrophilic substitution in
arenes, using the mononitration of benzene as an example
Understand that reactions of arenes, such as those in point 2
above, are used by industry during the synthesis of
commercially important materials, for example explosives,
pharmaceuticals and dyes (from nitration), and polymers such
as polystyrene (from alkylation),

Chapter 2 Objectives
(continued)
5.
6.
7.
8.

Explain the relative resistance to bromination of benzene,

compared with cyclohexene, in terms of delocalisation of the
benzene ring.
Describe the reactions of phenol with bases and sodium to form
salts and with bromine to form 2,4,6-tribromophenol
Explain the relative ease of bromination of phenol, compared with
benzene, in terms of activation of the benzene ring
State the uses of phenols in antiseptics and disinfectants

HC

CH

HC

CH
HC

Consider only
the carbon ring
that lies in a
plain.

The structure of benzene

can be represented in a
variety of ways

CH

C
C

Add the bonds noticing they

are adding perpendicular to the
plain of the ring, then taking away the lower lobes for clarity

If you imagine
the lobes
being large
enough to
overlap, the
image
changes to:

Again for clarity, the electron clouds

above and below the plain of the ring
have been reduced in size , the
green being above the plain of
the ring and pink below.
e-

e-

C
e-

C
e-

C
e-

Three electrons are added to each cloud area.

Because of the overlapping orbitals, they are able to
move over the entire perimeter of the ring.
This is known as delocalisation.

Because of the
delocalisation, a
benzene ring
does not attract
electrophiles with
the same force as
aliphatic double
bond molecules.

Replay
slides

Electrophilic Substitution of Arenes

Example 1: A mixture of concentrated nitric acid
(HNO3) and concentrated sulphuric acid (H2SO4)
The sulphuric acid catalyst provides protons

H2SO4 (l)

H+ +

HSO4-

Nitric acid has this

spatial
arrangement.

The proton from H2SO4

adds to HNO3 creating a
Rearrangement
new arrangement
then occurs

HNO3
This is the
electrophile
which will add
molecules with
NO2+
double bonds.
Nitronium ion
To replay the sequence, right click on the screen and select previous.

Loss of H2O occurs

Substitution on the benzene ring continues as illustrated

benzene

nitronium ion

NO2+

A pair of electrons
moves from the
ring toward the
nitronium ion

The nitronium ion

moves toward the
benzene ring

giving the
intermediate
Loss of H+
occurs finally
giving nitro
benzene

To replay the sequence, right click on the screen and select previous.

Electrophilic Substitution of Arenes

Example 2: A halogen (X2) in the presence of a
Iron (III) chloride arrives
halogen carrier. (Br2 with FeCl3)
as the catalyst to help
the reaction.

Benzene
Initially, bromine
does not become
polarized enough to
react with benzene.

In the presence of
the catalyst,
bromines polarity
changes from

Br

Br

Br Br2Br
is going to
react with
bromine

Fe
FeCl3Cl
Cl

Cl
Br

Fe
Cl

Cl

Electon
density
shifts

Into
Bromines
electron density
is immagined
as

Cl

+ Br+

It spatial
arrangement
creates the
following
dipoles

To
create

Answer SAQ 2.1, 2.2 & 2.3

Br+ ion is a strong enough

electrophile to add to the benzene
ring

The hydrogen
atom is
substituted by
the bromine
atom

Br+
Br
H

+ HBr
Cl
+

Br FeCl
Fe 3 Cl
Cl

The catalyst is regenerated

To replay the sequence, click

Phenols and their properties

OH

Phenol occurs widely in

nature but the effects differ
remarkably.

OH

Estradiol

HO

An important female sex

hormone
Maintains female sexual
characteristics
Stimulates RNA synthesis and
therefore promotes growth.

Phenol

OH
O
CH3

Found in seed pods of vanilla

orchid
Used as flavouring additive in ice
cream and chocolate

C
H

H2
C
H2C

Vanillin

Cholesterol

CH2
H2C

CH3
CH
CH3

HO

Phenol reacting with Alkali (NaOH)

OH
The ring
draws
electron
density
toward it

This weakens
the O-H bond
allowing it
dissociate more
easily than
other alcohols.
It is therefore
slightly acidic.

pH ~ 6

O- Na+

+
Na
NaOH
OH-

Sodium phenoxide
An alkali will
react with
phenol in the
expected way
producing a salt
and water.

H2O

Phenol reacting with sodium metal (Na(s))

OH

2Na

Na(s) reacts similarly with all alcohols

but phenol is somewhat more reactive.
Because density is drawn into the ring
the hydrogen comes off more readily (H+)
Reduction: gain of electrons

Sodium metal and

hydrogen ions undergo
oxidation and reduction.

Na(s) + 2H+(aq)
Oxidation: loss of electrons

Na+(aq) + H2(g)

Na

+ H2 (g)

OH

OH
Br

Br

Br2 Br

HBr

Br

OH

OH

Br

Br

Br
Br

Br

HBr 2

H
Br

OH

OH
Br

Br

Br

3
Br

HBr

Br

Br

Br

Br

OH

OH
Br

phenol

Br

3Br2

bromine

Br

2,4,6-tribromophenol

Answer SAQs 2.4, 2.5 & 2.6

3HBr

Hydrogen
bromide

CH3

CH3

SAQ 2.1
A. Draw and name three
isomers which might be
produced following
electrophilic substitution of
NO2+ for one hydrogen
atom in methylbenzene.

NO2

NO2

2-nitro methyl benzene

3-nitro methyl benzene

CH3

NO2

4-nitro methyl benzene

B. TNT has the systematic

name 1-methyl-2,4,6trinitrobenzene. Draw the
structural formula of TNT

CH3
O2N

NO2

NO2

2,4,6-trinitro methyl benzene

SAQ 2.3
A. Suggest a suitable halogen
carrier to use in the
reaction of benzene with
chloromethane.
B. Suggest suitable reactants
which might lead to the
formation of the following
compound in the presence
of a halogen carrier.

Anhydrous FeCl3 or AlCl3

Benzene + 2-chloro-2-methyl propane

CH3

+ H3C

CH3

Cl

B. Write a balanced equation

using your suggested
reactants

CH3

Cl

C
CH3
CH3

CH3
CH3
CH3

SAQ 2.6
Br

A. How does bromine in

aqueous solution become
sufficiently polar to achieve
electrophilic substitution

Br

Br

Fe
FeCl3 Br
Br

Bromine has a
symmetrical electron
density arrangement

In the presence of
FeBr3, the electron
density shape
changes