B17CB2 1

Organic Chemistry Classes

Prof. D R Adams WP123 • D.R.Adams@hw.ac.uk
• Lectures Weeks 1-12 (Thurs 09:15)
• Workshops Weeks 3, 5, 8, 11 (Thurs 17:15)
• Tutorials Weeks 3, 5, 8, 11
• Webtests To be announced

• Course text: ‘Chemistry’ Blackman et al

Check list of organic chemistry topics

for B17CA and B17CB appended.

This semester's menu – to study the chemistry of: 2

O O O O O
C C C H C R C
R H R R R O R O R Cl

O O
C C
R O R

H H R
N N N
R H R R R R
 3
1. Aromatic Compounds
1.1 Some useful names
1.2 Structure
1.3 Characteristic Chemistry
1.4 Benzene Reactions
a. Nitration
b. Bromination 1.5 Disubstituted Benzenes
c. Chlorination
d. Alkylation
1.6 Aniline Chemistry
e. Acylation 1.7 Reaction Sequences

4
1. Aromatic Compounds
1.1 Some useful names
Me
Me OH O

O OH O H
NH2 C C
1.2 Structure 5
H
H H
benzene • colourless liquid bp 80°C
•
H H
•
H

Single Lewis structure — Kekulé structure — is an inadequate

description of the structure:

A B

Note: 6

In resonance ...
The connectivity between bonded atoms REMAINS THE SAME

In equilibria ...
The connectivity between bonded atoms CHANGES
O
C H O
R O H H
So benzene pi-electrons are delocalised by resonance 7
The real 'aromatic' benzene structure
is 152 kJ/mol more stable than either
theoretical structure A or B.
A B

Bond analysis:
C ground state sp2 hybridised
px py pz
H
2p2
2s2
hybridisation
1s2

6 !-electrons are delocalised in 'donut-shaped clouds' 8

formed by sideways overlap of one pz orbital on each carbon

So benzene chemistry is dominated by...

NOTE: substituents distort !-electron distribution and will 9
affect the site for electrophilic attack.
There are two types of distortion:
(1) Pushing or pulling electrons through the #-bond

(2) Delocalisation of electrons in !-bonds and lone pairs

(a) Alkyl substituents

"H ~ 2.1 "C ~ 2.5
H H
H H H H
C C

10
(b) Resonance donating groups:

X OH OH OH OH
H H
eg

(c) Resonance withdrawing groups:

O O H O H O H O H
X
H H
eg

H
 11
Summary
• Understanding the structure of molecules (electron distribution)
is the key to understanding their chemical reactivity.

• Resonance delocalisation of electrons has a profound influence

on structure and chemical reactivity.

• A special resonance situation occurs in benzene where 6 pi-

electrons are delocalised around an uninterupted cycle of 6
overlapping p-orbitals –– this a stable AROMATIC structure.

• The aromatic structure leads to a unique type of chemical

reactivity – AROMATIC CHEMISTRY

Next class ... characteristic chemistry of aromatic compounds.

12