Organic Chemistry for the 12th Class

By El Wathan
Diazonium
Azo Dyes
Salt
1
What is the conection between
diazonium salt and azo dyes (azo
compound)?

This test is designed to

explore how far you know
about amine compound

2
What is the conection between
amine compound and
diazonium salt?

3 Explain what do you know about

some colored chemical compound!
#purpose #use of diazonium salt #use of azo dyes
_> azo dyes

• to know one kind of colored chemical

compound that is generally use

_> diazonium salt

• to know an intermediate compound which is

material to synthesize azo dyes
_> an intermediate compound

• diazonium salt is a compound that can be a

material to synthesize many important chemical
compounds such as azo dyes

_> an electrophile (E+)

• diazonium salt is an electrophile that can be a

substituent in aromatic compound by electrophilic
aromatic substitution reaction
_> coloring agent

• azo compound is a dye which is a colored chemical

compound, use to be a coloring agent in
spectrophotometer analysis (Vis) or in
industrial product such as in the textile
industry

_> conventional analysis indicator

• some of azo dyes can be used as indicator in conventional

analysis such as red methyl or orange methyl
 azo group

N
N

H 3C C
N O OH

CH3
Red Methyl
an azo dye
 O
ONa
S
azo group O

N
N

H3C
N
Orange Methyl
CH3 an azo dye
#structure #properties #preparation #reaction
_> structure

N
N

_> properties

• diazonium salt is an electrophile (E+)

• so, it can be a substituent in aromatic compound by
electrophilic aromatic substitution reaction
_> reaction between amine and nitrite acid

• The amine compund must be primary amine

• Nitrite acid is unstable compound, so this reaction use
HCl and sodium nitrite as reagents beside
primary amine in low temperature
N H 2 N
H C l, N a N O N C l
2

0 - 5 oC

Exercise: Try to analyze what happens if this

reaction temperature is more than 5oC???
_> azo coupling  azo dyes

N Cl
N N
N aO H
+ N
- N aC l
- H 2O

_> sandmayer  chloro/bromo benzene

N Cl Cl Br
N
HCl / HBr OR
+ CuCl / CuBr
- N2
_> hydrolysis  phenol (alcohol)

N Cl O
H
N
c
al
or
+HO
2
-N
2

_> deamination  benzene

NC
l
N
H
P
3O
2

-
N2
_> substitution (KI)  iodo benzene

NC
l I
N
K
I
-
N2

Exercise: Try to design pathway reaction of

synthesis benzene from benzaldehide as starting
material !!
#structure #properties #preparation #azo coupling
#ortho meta para director
_> structure
azo group

N
N

_> properties

• The characteristic of azo dyes is there are conjugated double

bond in it’s structure (chromophore group), therefor it is a
colored chemical compound
_> made from diazonium salt

• reaction between diazonium salt and an aromatic

compound, called azo coupling
H O

N
N
N C l O H
N
N aO H O R O H
+
- N aC l
- H 2O
N
N
_> ortho and para director
• if the first substituen in benzene molecule has lone
pair (except alkyl), the second substituent will be
directed to ortho or para position (benzene activator)
N
H
2 O
H C
H
3

_> meta director

• if the first substituen in benzene molecule has no lone
pair (except alkyl), the second substituent will be
directed to meta position (benzene deactivator)
O O O

N C C
O N
H
2 O
H
Try to make conclution from this leraning of amine