1.

Aromatic Compounds 1

1.1 Some useful names

1.2 Structure
1.3 Characteristic Chemistry
1.4 Benzene Reactions
a. Nitration B17CB-DRA5
b. Bromination 1.5 Disubstituted Benzenes
c. Chlorination
d. Alkylation
1.6 Aniline Chemistry
e. Acylation 1.7 Reaction Sequences

1.4e Benzene acylation 2

O
O
!+C
R Cl AlCl3 C
R
+ HCl
Lewis acid catalyst
O O
AlCl3
C C
R Cl R Cl AlCl3

Friedel-Crafts acylation

AlCl4

O O O
H H
C C C
R R R
H
Extra connections: 3
O O
C NaBH4,
Me Cl C !+
Me MeOH

AlCl3

1. EtMgBr, dry Et2O

2. H3O+

Aromatic ketones show typical ketone chemistry but are a little less reactive
than aliphatic ketones.

1.5 Formation of Disubstituted Benzenes 4

We've seen 5 key EAS rxns for introducing benzene substituents

What happens when these reactions are applied to a benzene that already has a
ring substituent "X"?
X X X X
E

E
E

Product formed depends on electronic properties of X:

1. Substitution ortho to X: 5
X X X
H H H
E E E E -H

I II III
X X
E

O O O O !+ R, H, OH, OR
X N C TS

If X is EWG = WI

X X X
H H H 6
E E E E -H

I II III
X X
E

R OH, OR, NH2 etc

If X is EDG =
2. Substitution para to X: 7
X X X

E -H

X
H E H E H E
X
I II III

If X is EWG: E

If X is EDG:

3. Substitution meta to X: 8
X X X

E -H
E E E
X
H H H
I II III X

E
If X is EWG:

If X is EDG:
4. Summary of directing effects 9

N
EWG O O O !+ H, R, OH, OR
N C C !+

electron withdrawing groups

O O
EDG R X OH OR O C R HN C R NH2

electron donating groups

10