Natural Dyes

-Natural yellow dyes, based on flavones,

chalcones and polyenes, are weakly
colored, unstable and fades by light.
-However, the anthraquinone and indigo
chromogens, respectively found in the
natural red and blue dyes are stable and
form the basis of many of the modern
synthetic dyes.

O
Flavones ( 2-Phenylchromones)

ROOC

Chalcones (benzalacetophenone)

( CH = CH ) n

COOR

n = 7 - 9 ; R = H , Me
Polyenes

H
N

O
anthraquinone

indigo

Classification of Dyes
Chemical Classification :
Nitro dyes, Nitroso dyes
Azo dyes
Diphenylmethane dyes, Triphenylmethane dyes
Xanthene dyes
Anthraquinone dyes
Acridine dyes
Indigoid dyes
Phthalocyanine dyes
Polymethine dyes
Sulphur dyes

Usage Classification of Dyes

Class

Chemical Type

Substrate

Method of Application

Acid
(anionic)

Azo anthraquinone
triphienylmethane

Nylon wool
Silk

From neutral or acidic dyebath

Basic
(cationic)

Cyanine azo - azine

acridine - oxazine

Paper polyester

From acidic dyebath

Direct
(anionic)

Azo - phthalocyanine

Cotton - leather

From neutral or slightly alkaline

containing additional electrolyte

Mordant

Azo anthraquinone

Wool leather
anodized Al

Applied in conjunction with Cr salts

Vat

Indigo - anthraquinone

Wool cotton
rayon

Water-insoluble dyes solubilized by

reduction with sodium hydrogen sulfite,
introduced into the fiber and then
reoxidised

Disperse

Polymethine,
phthalocyanine
Nitro dyes

Mainly used in
photography

dyes,dispersed on synthetic fibres by

Azo

cellulose

Azoic
(Ingrain)

heat&pressure before application

produced in situ

Acid Dyes: sodium salts of sulfonic or carboxylic acids; dyes wool & silk
Basic Dyes: these are cationic dyes
They have high tinctorial strength.
they dye animal fibres directly , and vegetable fibres which have been
mordanted with tannin .

Azoic Dyes ( Ingrain Dyes): insoluble azo dyes produced in situ, dye
cellulose fibres
Example : Para Red

Mordant Dyes: do not dye fibre directly but require a mordant which
is basic (metal hydroxides) for acid dyes and tannic acid or tannin
for basic dyes.
Example : Anthraquinone dyes.

Vat Dyes: insoluble dyes but used in their soluble form (Leuco compounds).
After application they are oxidized to generate the colored dye. They dye
cotton.
Examples: Indigo

Sulfur Dyes: They dye mainly cellulosic fibres. They are usually Yellow.
They are classified to Sulfur Dyes, Leuco Sulfur Dyes & Solubilized Sulfur
Dyes.
Disperse Dyes; Water-insoluble dyes,dispersed on synthetic fibres by
heat&pressure before application.
Nitro, Polymethine, Cyanine , Phthalocyanine Dyes; used mainly in the field
of photography

Nomenclature of Dyes
1] Commercial Trade Name:
3 Parts;
- trademark to designate both of the manufacturer and the class of dye
- colour

- code to indicate the hue ( R: reddish, B: bluish, G: greenish shades, )

and the most important properties ( W: wash fastness, E: exhaust dyes,)
For Solvent and Disperse Dyes, letters A, B, C, or D are used to show heat
fastness (A and D for the lowest and highest levels of heat fastness).

Example: Dispersol Yellow B 6G

Dispersol: trade name, Yellow: main hue of the dye, B: rather low heat
fastness, 6G: 6 steps of green away from yellow, i.e. lemon yellow.

2] Colour Index Name:

C.I. Name is derived from the application class
of the dye, the colour hue of the dye and a
sequential number.
Examples:
C.I. Acid Yellow 3
C.I. Disperse Yellow 42
C.I. Basic Blue 41
C.I. Vat Black 7

Electromagnetic Radiation

A propagating wave of electrical energy with an orthogonal magnetic

component oscillating with exactly the same frequency.

Electomagnetic Spectrum
Harmful
High energy
High frequency
Short wavelength
X-rays
g-rays

safe
low energy
low frquency
long wavelength
UV

IR

Visible

Microwave

Radio

Colour
Colour (absorbed A )

4000-4350 Violet

Visible(complementary colour)

Yellow-green

4350-4800

Blue

Yellow

4800-4900
4900-5000
5000-5600
5600-5800

Green-Blue
Blue Green
Green
Yellow-Green

Orange
Red
Purple
Violet

5800-5050

Yellow

Blue

5050-6050 Orange
6050-7500 Red

Green-Blue
Blue Green

Colour
ray-X-ray-UV- Visible -IR-MW-Radio
4000-7500A

It is either the reflected colour or its complementary colour.

Absorbed
0000
4000-4350A (violet)
4350-4800
(blue)


5600-5800
(yellow-green)
4000-7500

appearance
white
yellow-green
yellow

violet
black

e.g. a substance appears blue because it absorbs the yellow portion

of the light OR because it absorbs all portions of light except the
blue.

Relation between Colour and Constitution

Colour of an organic compound is due to the presence of
unsaturated groups (chromophores), e.g.

Nitro Nitroso Azo Azoxy Azoamino Carbonyl thiocarbonyl,

NO2 N=O
N=N N=N-O CH=N
C=O
C=S
If only one chromophore is present, the compound (chromogen) is
usually yellow, sometimes colourless.
Deepening of colour from yellow orange red purple
violet blue green black
requires the presence of more than one chromophore
e.g. CH2=CH2 is colourless
while CH3 (CH=CH)6 CH3 is yellow.

Auxochromes: groups with lone pair of electrons

that deepens color when introduced into a colored
molecule, e.g. - OH, -NH2, -NHR, NR2, Cl,

Bathochromic groups: deepen colour

Bathochromic effect : deepening color
(yellow to black )
Hypsochromic effect : lightening color.
Replacement of H in NH2 by R generally has a
bathochromic effect

While Acetylation of NH2 or OH generally

has a hypsochromic effect.

1] To Generate Colour in Azo and

Anthraquinone Dyes:
Introduce an auxochrome with lone
electrons capable of delocalization into the
system of azobenzene or 9,10anthraquinone.
examples

N=N

N=N

colourless

yellow

colourless

NEt2

yellow

OH

O
red

NHMe

The ease of excitation of the following

groups is

N=O > C=S > N=N > C=O > C=C

Thus, colour due to the presence of one of
these groups will deepen from right to left.

2] Resonance
a) In nitrobenzene the
contribution of the
charged stuctures is
larger than that in
benzene, consequently
the absorption band is
shifted to the longer
wavelength (blue),
thereby producing a
yellow colour.
The intensity of
absorption is also
increased due to the less
of symmetry.

O
N

-O

O
N
+

b) In p- nitroaniline,
there is a larger
contribution of
charged structures,
so the colour is
deeper (orange-red)
and still more
intense.

O-

O
N+

O-

O
N

NH 2

NH 2

NH 2

NH

c) Both o- & p-
quinones exhibit
resonance.
Since the number of
resonating structures
in o-quinone is
greater, its colour will
be deeper. The o- is
red and the p- is
yellow.

O
O

O
p-quinone
4 resonating structures

o-quinone
5 resonating structures

Resonance in o- & p-quinones

O

O
O

O
O

O
O
+

2] Bathochromic Effect without

adding an auxochrome
Aminoazobenzene with
only one charged
structure contributing to
the resonance hybrid is
yellow.
In acid solution,
2 charged structures
contribute to the
resonance, the reason
why the colour became
violet.

N=N

NH+ = N

NH2

NH2

N-N

NH - N

NH2+

NH2+

3] The longer the conjugation, the

deeper will be the colour
The effect of conjugation
is due to the increase of
the number of electrons
involved in the oscillation.
When the conjugated
system contains hetero
atoms, N, S, O the
molecule will be less
symmetrical and the
colour will be deeper.

C=C-C=C

C=C-C=C-C=C

C=C-C=C-X

..