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. 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),

3. 4.

Chapter 2 Objectives (continued)

5. 6. 7. 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

8.

HC HC HC

CH CH CH

The structure of benzene can be represented in a variety of ways

Consider only the carbon ring that lies in a plain.

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

C
C C

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

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-

C
e-

e-

C C
e-

C
e-

C
e-

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

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.

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+ +

HSO4The proton from H2SO4 adds to HNO3 creating a Rearrangement new arrangement then occurs

Nitric acid has this spatial arrangement.

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+
The nitronium ion moves toward the benzene ring

A pair of electrons moves from the ring toward the nitronium ion 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)
Benzene
Initially, bromine does not become polarized enough to react with benzene.
as the catalyst to help the reaction. In the presence of the catalyst, bromines polarity changes from

Cl
_
+

_
_

Br
Into

Br

FeCl Fe 3Cl Cl
_

Electon density shifts

Br Br2Br
is going to react with bromine

Bromines electron density is immagined as

Cl
Br Fe Cl Cl

It spatial arrangement creates the following dipoles

+ Br+

To create

Answer SAQ 2.1, 2.2 & 2.3

The hydrogen atom is substituted by the bromine atom

Br+ ion is a strong enough electrophile to add to the benzene ring

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
OH O CH 3

Phenol

C H O

Found in seed pods of vanilla orchid Used as flavouring additive in ice cream and chocolate

An important female sex hormone Maintains female sexual characteristics Stimulates RNA synthesis and therefore promotes growth.
H2 C H2C CH 2 H2C CH CH 3 CH 3

Cholesterol Vanillin

HO

Phenol reacting with Alkali (NaOH)

OH The ring draws electron density toward it

+ OHNa NaOH

O Na+

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

Sodium phenoxide

pH ~ 6

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

H2O

Phenol reacting with sodium metal (Na(s))

+ 2Na
2

OH

Na

+ H2 (g)

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)

OH

OH Br

1
Br Br2 Br
OH Br

Br

HBr

H
OH Br

Br
Br Br

HBr 2

H
Br

OH Br

OH Br Br

3
Br Br

HBr
Br

Br

Br

OH Br

OH Br

3Br2

3HBr

phenol

bromine

Br

2,4,6-tribromophenol

Hydrogen bromide

Answer SAQs 2.4, 2.5 & 2.6

CH3

CH3 NO 2

SAQ 2.1
A. Draw and name three isomers which might be produced following electrophilic substitution of NO2+ for one hydrogen atom in methylbenzene.
NO 2

2-nitro methyl benzene

3-nitro methyl benzene
CH3

NO 2

4-nitro methyl benzene

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

CH3 O 2N NO 2

NO 2

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. B. Write a balanced equation using your suggested reactants
+
Cl C CH3 CH3

Anhydrous FeCl3 or AlCl3

Benzene + 2-chloro-2-methyl propane

CH3

+ H3C

C Cl

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