Week 2/Lecture 1:

Aromaticity
Weekly objectives

1. Draw benzene and understand its structure and unique stability

2. Identify aromatic compounds and heterocycles and apply Hückel’s rule
3. Identify the structure of phenols and anilines
4. Draw the resonance structures of phenol
5. Connect reactivity and pKa of phenols and anilines to resonance
 Original sample of benzene isolated
by Faraday.
Pre-workshop activity recap
• Isolated in 1825 by Michael Faraday, from distillation of
“illuminating gas” residue, was an unknown material with
the empirical formula C6H6

A number of possible structures for benzene were proposed

in the following years

all are C6H6

Claus Dewar Ladenburg

1867 1867 1869
Benzene – alternating single and double bonds?
In 1865, Kekulé proposed a structure with three C−C single bonds and 3 C−C double bonds.
Benzene – trouble with the model.
In 1865, Kekulé proposed a structure with three C−C single bonds and 3 C−C double bonds.
• BUT Kekulé’s structure does not fit the thermochemical evidence from hydrogenation studies.

H2

ΔH° = −120 kJ mol -1

(experimental)

three double bonds!

Benzene is
H2 more stable
than predicted
ΔH° = −360 kJ mol -1 for a simple
(prediction) triene!
ΔH° = −208 kJ mol -1
(experimental)
Benzene – more trouble with the model.
In 1865, Kekulé proposed a structure with three C−C single bonds and 3 C−C double bonds.
• NOR does Kekulé’s structure explain how benzene reacts.

Br
Br2
Br

Br
Br2 HBr
Benzene – Resonance structures
• In 1899, the proposal was refined with a model in which each bond is intermediate between
single and double.

HC CH

or HC CH

HC CH

This is the resonance hybrid (a mix of the two other structures).

The dotted lines mean “half a bond”
Benzene – a modern model
This model can be refined further by considering orbital hybridisation to provide an
explanation of benzene’s properties.
• Not isolated alkenes, but a cloud of electrons in a delocalised p-system.
Determining aromaticity
Benzene is not the only molecule to have stability due to such delocalisation. Molecules of this
type we call aromatic. Hückel’s rules determine if a compound is aromatic:
1. Is the molecule a planar ring system with conjugated p electrons?
2. Does the number of p electrons = (4n + 2), where n is an integer? Note. The rule can be used
with all molecules. Neutral,
If Yes to both it is aromatic! positive or negative.

Note. Analyse
each ring
separately.
Hetero-aromatic compounds
6 π-electrons

sp2 electron pair not

N pyridine N involved in aromaticity.
Why?

O furan NH pyrrole

6 π-electrons 6 π-electrons

O N H
sp2 electron pair not
involved in aromaticity.
 Pairs
ACTIVITY 1: Determining aromaticity
Determine whether the molecule is aromatic.

10 mins.

H 3C CH3 N
N

N N N
H H H
ACTIVITY 1: Discussion and feedback

10 π electrons 8 π electrons 6 π electrons

∴ n=2 (integer) ∴ n=1.5 (not an integer) ∴ n=1 (integer)
∴ aromatic ∴ not aromatic but not conjugated
∴ not aromatic

H 3C CH3 N
N

N N N
H H H

Answers for the following materials are explained on the following slides.
Bromination of Benzene

Br
Br2
Br

Br
Br2 HBr

Why does the bromination of benzene proceed differently?

Bromination of Benzene

Br
Br2
Br
Bromination of Benzene

Br
HBr
Br Br
Summary

Today we have:
• discussed the discovery of benzene.
• Introduced Hückel’s rules for determining if a molecule is aromatic.
Week 2/Lecture 2:
Phenols and anilines
Weekly objectives

1. Draw benzene and understand its structure and unique stability

2. Identify aromatic compounds and heterocycles and apply Hückel’s rule
3. Identify the structure of phenols and anilines
4. Draw the resonance structures of phenol
5. Connect reactivity and pKa of phenols and anilines to resonance
Phenol
Phenols are commonly occurring materials with many uses.

OH

phenol

OH
O
H 3CO CH3
N
OH H
CH3
resorcinol HO
(Antibacterial used in acne treatment) capsaicin
Phenol
Phenol’s are strong acids. Phenol is about ~106 times more acidic than ethanol!

OH O
[A ][H ]
Ka =
[AH]
H 2O H 3O
= 1.02 X10-10
pK a = 9.99
AH A H

[A ][H ]
H 3C OH H 3C O Ka =
H 2O H 3O [AH]
= 1.3 X10-16
AH A H
pK a = 15.9
Phenol
Consider the resonance stabilisation of the phenoxide anion.

O O O O

δ
O

δ δ

Resonance hybrid structure

The negative charge has been

stabilised by spreading it around.
Resonance structures
Resonance is a model used commonly to explain the structure and reactivity of molecules
where a single Lewis structure is inadequate.
Consider the following example

H 3C H 3C H 3C
I O18 O18 O18 O18
I and CH3
C C C C
H 3C O16 H 3C O16 H 3C O16 H 3C O16

Instead a mixture is observed.

O O Notes on resonance
C C
H 3C O H 3C O 1) These are structures related through resonance
(resonance structures)
1/2
O 2) They are hypothetical.
or 3) Neither is real, a mix (the resonance hybrid)
C
H 3C O can be useful to explain reactivity.
1/2
Resonance structures
When must we consider resonance structures?
Below is a common case that will come across a few times in CHM1022.

A A O O
B B i.e. C C
C C C C

1. Atom A has a lone pair (can be

an anion or neutral).
This is a resonance arrow.
2. Atoms B and C are connected
• One line with an arrow at each end.
via a double bond.
 Pairs
ACTIVITY 2: Acidity of phenol derivatives.

In your group you need to:

5 mins.
1. Decide whether phenol 1 or its derivative 2 is more acidic. Explain why.
2. Give an explanation of this answer using resonance structures.

OH OH

N
O O

1 2
 Pairs
ACTIVITY 2: Discussion and feedback

5 mins.
a) b) OH O O
OH

C C
N N N
O O O O O O
pK a = 9.99 pK a = 7.15
We can draw a resonance structure, where
the phenoxide negative charge is
delocalised onto the electron-withdrawing
nitro group.
Aniline
Anilines are common in the dyeing industry and have properties explainable by resonance

NH2

• Badische Anilin und Soda Fabrik (BASF)

• Largest chemical manufacturing company in the
world.
• 120 000 employee’s worldwide.
• 4.7 billion euro revenue in 2018
Aniline
is a weak base. Aniline is ~106 times less basic than cyclohexylamine!

NH 2 NH 3
[B ][OH ]
Kb =
[B]
H 2O OH
= 4.5 X10-10
pKb = 9.36
B B OH

NH 2 NH 3
[B ][OH ]
Kb =
[B]
H 2O OH
= 4.5 X10-4
pKb = 3.34
B B OH
Aniline
Consider the resonance structures of aniline.

NH2 NH2 NH2 NH2

δ
NH2

δ δ

Resonance hybrid structure

 Pairs
ACTIVITY 3: Basicity of aniline derivatives

In your group you need to:

5 mins.
1. Decide whether aniline 1 or the derivative 2 is more basic. Explain why.
2. Give an explanation of this answer using resonance structures.

NH2 NH2

H 3C
O O

1 2
 Pairs
ACTIVITY 3: Discussion and feedback
NH2 NH2
a) b)

H 3C
O O
Most basic. Least basic.
N lone pair is withdrawn
by ester.

NH2 NH2 NH2 NH2

H 3C H 3C H 3C H 3C
O O O O O O O O
Bromination of aniline

The aromatic ring of aniline is electron rich.

This increases the rate of bromination compared to benzene.

NH2 NH2

HBr
Br Br Br

Which position(s) of aniline will be brominated?

Bromination of aniline
NH2 NH2
Br
HBr
Br Br

The nitrogen lone-pair electrons direct bromination to the ortho and para positions.
Bromination of aniline

NH2 NH2

HBr
Br Br

Br

The nitrogen lone-pair electrons direct bromination to the ortho and para positions.
 Summary

Today we have:
• Discussed how resonance structures can help predict reactivity.
• Building upon this concept we have looked at the acidity of phenol.
• Building upon this concept we have looked at the basicity of aniline.