403221

aromatic compounds
. .

403221-aromatic

 aromatic

electrophilic substitution

403221-aromatic

 C6H6
Kekule structure
H

H
H
H

1
6
5
4

H
H

H
H

6
5

1
2
3
4

H
H

H
2

H
H

H
Br
Br

Br

403221-aromatic

Br

Resonance C6H6
H
H
H

1
6
5
4

H
2
3

H
H

6
5

1
2
3
4

H
H

403221-aromatic

Resonance C6H6

C-C 139 pm
C-C C=C 147 133 pm
H
H

120o

139pm

147pm

CH2

133pm

403221-aromatic

Resonance C6H6
6 p electron delocalize ()

403221-aromatic

Aromaticity

p-orbital ( conjugated
double bond)
p electron delocalize
p electron 4n+2 (Huckel rule)
2, 6, 10, 14

addition

aromatic ion
cyclic conjugated system p electron
4n+2
403221-aromatic

.
5p

-H.

H
..-

-H+
cyclopentadiene

6p

-HH

+
4p

403221-aromatic

.
7p

-H.

H ..

-H+

8p

-Hcycloheptatriene

H
+

403221-aromatic

6p

 aromatic
+
2p

6p

10p

..-

6p

6p

14p

14p

non aromatic
+

4p

4p

403221-aromatic

8p

10

 aromatic
1. acetylene

heat
sealed tube

HC CH

2. Friedel-Craft alkylation
Cl

H3C C CH3
H

AlCl3

CH3
CH
CH3

3. Wurtz-Fittig reaction
Cl

+
Cl

R Cl

Cl

Na

Na

H3C C CH3
403221-aromatic
H

CH3
CH
CH3

11

 aromatic
Electrophilic aromatic substitution
H+

E+
electrophile

E
X2, FeX3

(X= Cl, Br)

HONO2
H2SO4
H

SO3
H2SO4
R-Cl
AlCl3
O
R C Cl
AlCl
403221-aromatic
3

H+

X
NO2
SO3H
R
O
C R

12


1
+
H+

E+

H
E

arenium ion
-complex

+
H

2 rearomatization
+

403221-aromatic

H+

13

1. Halogenation
H

X2, FeX3

(X= Cl, Br)

Cl2, FeCl3
Br2, FeBr3

403221-aromatic

Cl

Br

14

403221-aromatic

15

2. Nitration
H

HONO2

NO2

H2SO4

403221-aromatic

16

3. Sulfonation
H

SO3
H2SO4

SO3H
benzene sulfonic acid

Fuming sulfuric acid

= SO3+H2SO4

403221-aromatic

17

4. Friedel-Crafts Alkylation
R-Cl
AlCl3

AlCl3

CH3 -Cl

CH3
AlCl3
Cl CH
CH3

403221-aromatic

H Cl

CH3

H Cl

CH3
CH + H Cl
CH3

18

403221-aromatic

19

5. Friedel-Crafts Acylation
H

O
R C Cl
AlCl3

O
H3C C Cl
O
C Cl

+
O
R C
acyl group

O
C R + H Cl

AlCl3

AlCl3

O
C CH3
O
C

H Cl

H Cl

O
C

O
H3C C
acetyl

benzoyl
403221-aromatic

20

403221-aromatic

21

 electrophilic aromatic substitution

1. Activating group =
= ortho-, para- director
O2N
H3C

HONO2
H2SO4

H3C

NO2

H3C
O2N

CH3O

HONO2
H2SO4

CH3O

403221-aromatic

NO2 + CH3O

22

ortho-attack CH

NO2
H

CH3

para-attack
+
H

NO2

Arenium ion ortho-, para- attack

inductive effect
meta-attack

CH3
+
NO2
H

403221-aromatic

23

ortho-

O CH3
+

NO2
H

OCH3

para+
H

NO2

Arenium ion ortho-, para- attack

resonance effect
403221-aromatic

24

1. Activating group : ortho-, para- director

resonance effect
-NH2, -NHR, -NR2,
-OH, -OR,
inductive effect
-R, -Ar

O
O CR

O
N CR
H

403221-aromatic

25

2. Deactivating group =
= meta- director
CF3

CF3
HONO2
H2SO4

NO2
O
CH

O
CH
HONO2
H2SO4

NO2
403221-aromatic

26

CF3

ortho-attack

NO2
+

CF3

para-attack
+
H

NO2

Arenium ion ortho-, para- attack

inductive effect
meta-attack

CF3
+
NO2
H

403221-aromatic

27

2. Deactivating group : metadirector

O
O
O
CH
C N
CF3

CR

O
C OR

C OH

O
C Cl

SO3H
+

NO2

NH3

403221-aromatic

28

3. Halogen
Deactivating group : X- e- inductive effect
ortho-, para- director : X- e- resonance effect
O2N
F

HONO2
H2SO4

NO2

F
O2N

Br

HONO2
H2SO4

NO2 +

Br

Br

403221-aromatic

29

para-

ortho-

meta-

NO2

NO2
H

NO2

All unstable

NO2
H
H

NO2

403221-aromatic

30


bromonitrobenzene
Br
Br 2, FeBr 3

Br

Br

NO2

HNO3

H2SO4

NO2
para-

ortho-

NO2
HNO3

Br
Br 2, FeBr 3

H2SO4
meta-

403221-aromatic

NO2

31

 aromatic

alkyl

1. oxidation
R
R = CH3-

KMnO4

COOH

CH3CH2-

alkyl

2. Halogenation
Br

CH2 CH3

Br2, FeBr 3

CH2 CH3

CH2 CH3
Br

Br 2
h

Br
CH CH3
benzylic C

403221-aromatic

32

3. Reduction C=O
NH2NH2 / KOH

C O

Zn(Hg) / HCl

O
CH

NH2NH2 / KOH

O
C CH3

Zn(Hg) / HCl

CH2

CH3

CH2 CH3

4. organometallic
Br

Mg

Cl

Li

ether

ether
403221-aromatic

X
Mg Br

Li
33


m-chlorobenzoic acid
O
p-acetyltoluene H C C
CH
o-chloronitrobenzene
p-chlorosulfonic acid
m-ethyltoluene
3

403221-aromatic

34