MS Chemistry

Dyes and Pigments

CHEM5164
Semester - I

Dr. M. Aslam
Associate Professor of Inorganic Chemistry
 Syllabus
Course Title
Dyes and Pigments

Course Code: CHEM5164 Cr. Hrs: 3(3+0)

Objectives
Students should be able to understand:
• Chemistry, properties and applications of important industrial dyes
and their development.
• Synthesis of different types of pigments and their applications.
• Dyes and Types of Dyes: Dye or dyestuf, The evolution of present-
day dye technology, Historical development from natural to synthetic
dyes, Era of synthetic dyes, Requisites of a true dye, Colour and
chemical constitution, Chemistry of dyestuff intermediates,
Nomenclature of dyes intermediates, Nomenclature of dyes, Synthesis
of different dyestuff and some specific dyes, Diazotization and
coupling reaction, Classification of dyes on the basis of chemical and
mode of application, Theories of dyes, General information about
fibres and dyeing methods, Non-textile uses of dyestuffs, Dyes for
synthetic fibres, Toners, Lakes, Food colours, Food dyes, Dye fixer.

• Pigments and Types of Pigments: Distinction Between dyes and

pigments, Features of the pigments, Physical basis, Development of
synthetic pigments, Raw materials for pigments, Classification and
properties, Manufacture of pigments, Inorganic pigments to color
ceramic materials, Types of pigments, Organic pigment, Dispersion
pigment, White hiding, Black, Red, Violet, Blue, Yellow, Orange,
Green, Brown, Metallic Pigments, Special purpose pigments,
• Requirements of different pigments, Characteristics of Pigments,
Isoindoline and Biological pigments, Modern high-grade pigments.

• Swatches: Printed swatches, Plastic swatches, Computer swatches.

• Pigments by Elemental Composition: Metal-based pigments,

Other inorganic pigments, Biological and organic.

• Fluorescent Brightening Agents: Characteristic properties of

fluorescent brighteners, Classification of fluorescent brightener,
Stilbene derivatives, Stilbene triazoles, Coumarin derivatives,
Benzthiazoles, Benzoxazoles and benziminazoles,
Diarylpyrazolines, Naphthalimide derivative, Pyrene derivatives,
Optical brighteners.
 Recommended Books (Syllabus)
• Hunger, K. Industrial Dyes: Chemistry, Properties, Applications,
Wiley VCH, 2003, ISBN: 978-3-527-30426-4.

• Zollinger, H. Color Chemistry: Synthesis, Properties and

Applications of Organic Dyes and Pigments, VCH, Cambridge,
1987, ISBN: 3-527-28352-8.

• Lang, A. R. Dyes and Pigments: New Research, 2011, ISBN:

978-1- 60692-027-5.

• Panda, H. A Concise Guide on Textile Dyes, Pigments and Dye

Intermediates with Textile Printing Technology, NIIR Project
Consultancy Services.
 Books Recommended By Dr. M. Aslam
• Dyes and Pigments
– Ahmet Gürses
– Metin Açıkyıldız
– Kübra Güneş
– M. Sadi Gürses
• Industrial Dyes: Chemistry, Properties, Applications
– Klaus Hunger
• Analysis and Deformulation of Polymeric Materials: Paints,
Plastics, Adhesives, and Inks
– Jan W. Gooch
• Synthetic Dyes
– Rajbir Singh
• Handbook of Industrial Chemistry: Organic Chemicals
– Mohammad Farhat Ali
– Bassam M. El Ali
– James G. Speight
• High Performance Pigments
– Hugh M. Smith
• The Chemistry of Synthetic Dyes
– K. Venkataraman
• Synthetic dyes
– Gurdeep R. Chatwal
• Microbial Degradation of Synthetic Dyes in Wastewaters
– Shree Nath Singh
• Riegel's Handbook of Industrial Chemistry
– Riegel
– Emil Raymond
– Kent
– James Albert
Color
• There are three terms generally used to describe and specify colour.
• These are:
– Hue Color
– Value • The property possessed by an object of producing different sensations
– Chroma on the eye as a result of the way it reflects or emits light.
Hue
• Hue is a term used for color, for example, pink, mauve (‫)ﮐﺎﺳﻧﯽ‬, scarlet ( ‫ﻧہﺎيت ﺳرخ‬
‫)رﻧگ‬, beige (‫)ﮨﻠﮑﺎ بﺎدامﯽ‬, tan, etc are hues.
• Hue distinguishes one color from another and is described using common color
names such as green, blue, red, yellow, etc.
Value
• Value is a term used to describe lightness, darkness, tone or shade of hues.
• It defines a color in terms of how close it is to white or black.
• A colour is termed light in value when it approaches white and dark in value when it
has a deep colour or approaches black.
Chroma
• Chroma is the attribute that expresses the purity of a color.
• Mixing a pure hue with black, white, gray, or any other color reduces its purity and
lowers the strength of the original hue.
• Chroma is the term used to describe the depth of colour that is the dullness,
brightness, saturation, intensity, vividness (‫ ) َﭼ َمﮏ‬or purity of colour.
• A bright, intense colour is said to have high chroma.
 Dye or Dyestuff

• A dye or a dyestuff is usually a coloured organic compound or

mixture that may be used for imparting colour to a substrate
such as cloth, paper, plastic or leather in a reasonably permanent
fashion.
• In other words, a dyed substrate should be resistant to a normal
laundry or cleansing procedures (wash fast) and stable to light
(light fast).
• All the dyes may not necessarily be coloured substances.
• Therefore, optical brighteners or whiteners which may be called
white dyes may be included in the term dye.
What are colorants, dyes and pigments???
• Dyes and pigments are the most important colorants used to add a
color or to change the color of something.
• They are widely used in the textile, pharmaceutical, food,
cosmetics, plastics, paint, ink, photographic and paper industries.
• All dyes and pigments are colorants.
• Dyes are colored substances which are soluble or go into solution
during the application process and impart color by selective
absorption of light.
• During application to a substrate, a dye either dissolves or passes
through a state in which its crystal structure is destroyed.
• It is retained in the substrate by adsorption, solvation, or by ionic,
coordinate or covalent bonding.
• A dye is a coloured substance but all coloured substances are not
dyes.
• Thus a dye should fix itself on the substrate to give it a permanent
coloured appearance.
• Thus, azobenzene is not a dye even though it has red colour, as it
cannot be attached to substrate.
• However, congo red is a dye as it can be applied on cotton and
retained by it.
• Thus, the dyes should have certain groups which help the
attachment to the fibre.

• A pigment, on the other hand, is insoluble in and unaffected by the

substrate in which it is incorporated.
• Pigments are colored, colorless, or fluorescent particulate organic
or inorganic finely divided solids which are usually insoluble in,
and essentially chemically unaffected by, the vehicle or medium in
which they are incorporated.
• On the other hand, the color, which is highly dependent on the
chemical and physical properties of a matter, is a result of the
interaction between light and substance.
• The two major types of colorants produced today are dyes and
pigments.
• Pigments, both inorganic and organic types, are almost always
applied in an aggregated or crystalline insoluble form that requires
a binder to form a coating on the surface of a substrate.
• Pigments do not interact with the substrate and hence do not destroy
the crystal structure of the substrate.
• Dyes are normally water-soluble or water-dispersible organic
compounds that are capable of being absorbed into the substrate
destroying the crystal structure of the substance.
• The dye molecules are usually chemically bonded to the surface
and become a part of the material on which they are applied.
• The primary use of dyes is in the textile industry, although
substantial quantities are consumed for coloring such diverse
materials as leather, paper, plastics, petroleum products, and food.
• To be of commercial interest, dyes must have high color intensity
and produce dyeing of some permanence.
• The color intensity of the dye molecule depends on how strongly it
absorbs radiation in the visible region, which extends from 400 to
700 nm.
• It was observed earlier that only some types of organic structures
give rise to color.
• The partial structures necessary for color (unsaturated groups that
can undergo π-π* and n-π* transitions) were called chromophores.
• Examples of some chromophores are:

• It was also observed that the presence of some other groups caused
an intensification of color.
• These groups are called auxochromes.
• Auxochromes are groups that cannot undergo π–π* transitions, but
can undergo transition of n electrons.
• Examples of some auxochromes are:

• As the coloration with dyes is based on physico-chemical

equilibrium processes, namely diffusion and sorption of dye
molecules or ions followed by chemical reactions in the substrate,
the shade and fastness of a given dye may vary depending on the
substrate.
• The development of new substrates present new problems, give rise
to new dyes and dyeing methods and thus influence dyeing
technology to a wider scale.
Requisites of a true dye
• All coloured substances are not dyes.
• However, the requisites of a true dye are as follows:
– It must have a stable colour
– It must have an attractive colour i.e., it should not undergo
structural changes readily
– It must be able to attach itself to material from solution or to be
capable to fixed on it. For example, azobenzene is coloured but
cannot fix itself to a fabric. Therefore azobenzene is not a dye.
Further, a dye may not be able to dye all types of substrates. For
example, picric acid is able to dye silk or wool a permanent
yellow but not cotton. Thus, a dye either forms a chemical union
with the substrate being dyed or it may get associated with it an
intimate physical union.
– It must be soluble in water or must form a stable and good
dispersion in water. Alternatively, it must be soluble in the
medium other than water. However, it is to be remembered that
the pick up of the dye from the medium should be good.
– The substrate to be dyed must have a natural affinity for an
appropriate dye and must be able to absorb it from solution or
aqueous dispersion. If necessary, in the presence of auxiliary
substances under suitable conditions of concentration,
temperature and pH.
– When a dye is fixed to a substrate, it must be fast to washing,
dry cleaning. Perspiration (the process of sweating), light, heat
and other agencies. It must be resistant to the action of water,
acids or alkalis particularly the latter due to the alkaline nature
of washing soda and washing soap. There is probably no dye
which can be guaranteed not to alter shade under all conditions.
– The shade and fastness of a given dye may vary depending on
the substrate due to different interactions of the molecular
orbitals of the dye with the substrate, and the ease with which
the dye may dissipate its absorbed energy to its environment
without itself decomposing.
The evolution of present-day dye technology
• The first synthetic dye, Mauveine, was discovered by Perkin in
1856.
• Hence the dyestuffs industry can rightly be described as mature.
• However, it remains a vibrant (‫)متحرک‬, challenging industry
requiring a continuous stream of new products because of the
quickly changing world in which we live.
• The early dyes industry saw the discovery of the principal dye
chromogens (the basic arrangement of atoms responsible for the
color of a dye).
• Indeed, apart from one or two notable exceptions, all the dye types
used today were discovered in the 1800s.
• The introduction of the synthetic fibers nylon, polyester, and
polyacrylonitrile during the period 1830 - 1950, produced the next
significant challenge.
• The discovery of reactive dyes in 1954 and their commercial launch in
1956 heralded (‫ )خبر ديﻧے وال‬a major breakthrough in the dyeing of cotton;
intensive research into reactive dyes followed over the next two decades
and, indeed, is still continuing today.
• The oil crisis in the early 1970s, which resulted in a steep increase in
the prices of raw materials for dyes, created a drive for more cost-
effective dyes, both by improving the efficiency of the manufacturing
processes and by replacing tinctorially (‫ )رﻧگيزی ﺳے‬weak
chromogens, such as anthraquinone, with tinctorially stronger
chromogens, such as (heterocyclic) azo and benzodifuranone.
• These themes are still important and ongoing, as are the current
themes of product safety, quality, and protection of the environment.
• There is also considerable activity in dyes for high-tech applications,
especially in the electronics and nonimpact printing industries.
• The scale and growth of the dyes industry has been inextricably linked
to that of the textile industry.
• World textile production has grown steadily to an estimated 35 × 106 t
in 1990.
• The two most important textile fibers are cotton, the largest, and
polyester.
• Consequently, dye manufacturers tend to concentrate their efforts on
producing dyes for these two fibers.
• The estimated world production of dyes in 1990 was 1 × 106 t.
• The figure is significantly smaller than that for textile fibers
because a little dye goes a long way.
• For example, 1 t of dye is sufficient to color 42 000 suits.
• The rapid growth in the high-tech uses of dyes, particularly in ink-
jet printing, is beginning to make an impact.
• Although the volumes of hi-tech dyes will remain small in
comparison to dyes for traditional applications, the value will be
significant because of the higher price of these specialized dyes.
• Perkin, an Englishman, working under a German professor,
Hoffman, discovered the first synthetic dye, and even today the
geographical focus of dye production lies in Germany (BASF,
Dystar), England (Avecia), and Switzerland (Clariant, Ciba
Specialties).
• Far Eastern countries, such as Japan, Korea, and Taiwan, as well as
countries such as India, Brazil, and Mexico, also produce dyes.
Chromogens
• A substance which can be readily converted into a
dye or other coloured compound.
Mauveine
• Mauveine is a mixture of four related aromatic
compounds differing in number and placement of methyl
groups.
– Mauveine A (C26H23N4+X−) incorporates 2 molecules
of aniline, one of p-toluidine, and one of o-toluidine.
– Mauveine B (C27H25N4+X−) incorporates one molecule
each of aniline, p-toluidine, and o-toluidine.
– Mauveine B2, an isomer of mauveine B with methyl
on different aryl group.
– Mauveine C, which has one more p-methyl group than
mauveine A.
Dyestuffs
A substance yielding a dye
or that can be used as a
dye, especially when in
solution.
Skeletal formula of Skeletal formula of
mauveine A
mauveine B

Skeletal formula of Skeletal formula of

mauveine B2 mauveine C
Evolution of dyes
• The preparation and application of dyestuffs is one of the oldest
forms of human activities.
• Evidences of which were found by excavation (‫ )ﮐهدائﯽ‬at
archaeological sites where ancient fabrics were unearthed.
• There is also mention of it in the Bible and other works of classical
antiquity.
• It was in 2600 BC when earliest written records of the use of
dyestuffs were found in China.
• Perhaps one of the real breakthroughs in the history of dyes came in
1856 when a teenager who was experimenting at his makeshift
laboratory in home made a certain discovery that acted as a sort of
launching pad for the modern chemicals industry.
• William Perkin an 18-year-old student was working on chemical
synthesis of natural products.
• In a classic case of serendipity (‫)اتفﺎقﺎ ً يﺎ غير‬, the young William
Perkin chanced upon his now famous 'Aniline Mauve' dye while he
was attempting to synthesize quinine, the only cure for malaria.
• Perkin named his colour Mauveine, after the French name of non-
fast colour which was made of natural dyes.
• So "Mauve" (a basic dye) was the first synthetic dye stuff.
• Mauve was a derivative of coal tar.
• It was the first mass-produced dye, that was commercially available
and the idea was born that a colour could be made in the factory.
• It was indeed a revolution.

Perkin, Sir William

Henry,1838-1907,
English Chemist
Historical development from natural to synthetic dyes
Era of natural dyes
• These have been used since ancient times for colouring and printing
fabrics.
• Until the middle of last century most of the dyes were derived from
plants or animal sources by long and elaborate processes.
• Ancient Egyptian hieroglyphs contain a thorough description of the
extraction of natural dyes and their application in dyeing.
• Further developments extending over many thousands of years led
to rather complicated dyeing processes and high-quality dyeings.
• Among these the following deserve special mention:
Indigo
• It is one of the earliest natural dyes and it originated in India.
• The art of dyeing with this bluish indigo dye was practised in this
country, using primitive fermentation methods.
• Then the use of this dye spread to Egypt.
• Indigo occurs in the indigo-ferae species of plants as a glucoside
called indican.
• This is extracted with water, when it gets hydrolysed by the enzyme
into indoxyl and dextrose.
• In alkaline medium indoxyl gets oxidized into indigo, which is
precipitated.

Indigo

• Ancient Britons obtained a dye called woad from the plant called
isatis tinctoria.
• The active compound is called indigotin from which indigo was
prepared.
• Indigotin is insoluble and hence it was reduced by fem1cntation and
then applied.
Tyrian purple
• It is a natural dye which originated in the ancient city of Tyre in
Phoenicia.
• This dye was extracted from certain kinds of shell-fish.
• However, at that time the dye was so expensive that it was called
Royal purple.
• Later, Friedlander showed that it was a derivative of indigo.

Alizarin
• It is extracted from the roots of madder plant.
• It occurs as a glycoside called ruberythric acid.
• On hydrolysis with dilute acid it gives dextrose, rhamnose and
alizarin which is 1,2-dihydroxy anthraquinone.
• The extract also contains a dye called purpurine (l,2,4-trihydroxy
anthraquinone).
• Alizarin is a natural mordant dye and it produces various colours
using different compounds of the metals Al, Cr, Cu, etc.

Cohineal
• It was extracted from the insect coccus Cacti which is found mainly
in South America and Mexico.
• The active dye is called carminic acid which is a derivative of
anthraquinone.
• It is also a natural mordant dye and gives different shades of purple
by using compounds of Cr, Al, Fe, etc.
• It is used for dyeing of wool and silk and also as non-poisonous
food colourant.
Logwood
• It is the only natural dye which is still isolated on a large scale from the
wood of the tree Haematoxylon Campechianum.
• It is cultivated and also grows wild in the central America.
• The fermentation of the wood of this tree contains a glucoside of
haematoxyIin which on oxidation yields a colouring matter called
haematin.
• Haematin is an active dye which when mordanted with chromium
compounds gives blue and black shades.
• It is still used for dyeing silk, viscose and acetate fibres, nylon, etc.
• It also gives cheap black shade of good fastness properties.
• Although the isolation of natural dyes has been abandoned, they still
retain the interest of chemists and a great ideal of work is being still
performed for the determination of their structures.
Limitations of natural dyes
• A large number of natural dyes were thus extensively used earlier.
• However, the preparation of dyes by extraction has number of limitations.
• The extractions are unsuitable for large scale preparation as they are
labourious and time consuming.
• Only a small amount of the dye can be obtained by processing a large
amount of the animal or vegetable matter.
• Hence they were invariably expensive.
• The natural dyes are not pure and lack uniformity of quality.
• Further their fastness properties were not good and they fades in light.
• Thus only a handful of natural dyes are still extracted and used.
• Some of them like indigo and alizarin are now prepared by
synthetic methods.
• Otherwise the natural dyes are largely replaced by synthetic dyes.
Era of synthetic dyes
• The era of synthetic dyestuffs started with development of synthetic
organic chemistry.
• The earliest artificial dyes to be prepared were picric acid by
Woulfe and aurine (rosolic acid) by Runge.
• However, they were not prepared commercially at that time due to
high cost of raw materials.

• William H. Perkin is considered as the founder of synthetic

dyestuffs.
• In 1865, he prepared the first synthetic dye called Perkins Mauve or
Mauveine.
• He oxidized crude aniline with potassium dichromate and
concentrated sulphuric acid and extracted the resulting black
resinous mass with alcohol to get a violet compound which was the
dye.
• He was already having a factory for manufacture of aniline.
• Later he set up facilities to manufacture the dye mauveine.

• Later he prepared another dye called safranine by oxidation of

mauve by lead peroxide.
• This dye was found suitable for wool and silk.
• However, only pale shades were obtained with cotton.
• Then Perkin developed the use of tannin and sodium stannite as
mordants in dyeing to get bright shades.
• Almost during the same period (1858) Griess discovered the
diazotization reaction and reactions of diazotised base.
• He prepared the first azo dye by coupling diazotised aniline with α-
naphthyl amine.

• This was followed by preparation of other azo dyes like Bismark

Brown (1865) and aniline yellow (1869) and congo red (1884).
• Thus azo dyes gave direct colours for cotton.
• The mordant dye called alizarin was prepared from anthraquinone
by Graebe and Libennann in 1868.
• Later in 1880 von Baeyer established the structure of indigo,
followed by the synthesis of this vat dye.
• In 1901, Bohn prepared indanthrene blue by alkali-fusion of 2-
amino-anthraqumone.
• Then a series of indanthrene vat dyes were prepared between 1901-
1911.
• Around this period many unit processes were discovered, i.e.,
sulphonation, nitration, alkali fusion, thionation etc.
• They were used in preparation of several important intermediates
like β-naphthol, H-and J-acids, anthraquinone derivatives.
• An important dye intermediate, phthalic anhydride, was prepared
by air oxidation of naphthalene using V2O5 as catalyst by Gibbs in
1917.
Colour and chemical
constitution
The chemistry of colour
• Coloured substances absorb radiation in the visible region
of the spectrum.
• The energy absorbed causes changes in electronic energy.
• Electrons are promoted from a ground state to an excited
state.
• The electrons excited in this case are the outer bonding
electrons or lone pairs.
• Not all electronic transitions are brought about by visible
light as some require ultra-violet radiation.
• Those which absorb UV radiation appear colourless
(unless they fluoresce).
• The energy needed to excite an electron in a coloured
compound and in a colourless compound is shown below:
Color and constitution
• The absorption of electromagnetic radiations in the UV
and visible regions by a molecule causes to the electronic
excitation and an electron moves to higher electronic
energy level from a lower.
• A covalently unsaturated group responsible for absorption
in the UV or visible region is known as a chromophore.
• For example, C=C, C≡C, C=O, C≡N, N=N, NO2 etc.
• If a compound absorbs light in the visible region (400–
800 nm), only then it appears colored.
• Thus, a chromophore may or may not impart color to a
compound depending on whether the chromophore
absorbs radiation in the visible or UV region.
• Following table shows the some organic dyes and their
chromophoric groups.
• Chromophores like C=C or C≡C having π electrons undergo π
→ π* transitions and those having both π and non-bonding
electrons, e.g., C=O, C≡N or N=N, undergo π → π*, n → π* and
n → σ* transitions.
• Since the wavelength and intensity of absorption depend on a
number of factors, there are no set rules for the identification of
a chromophore.
• Characteristics of some common unconjugated chromophores
are given in following table.
• A covalently saturated group which, when attached to a
chromophore, changes both the wavelength and the intensity of
the absorption maximum is known as auxochrome, e.g., NH2,
OH, SH, halogens etc.
• Auxochromes generally increase the value of λmax as well as εmax
by extending the conjugation through resonance.
• These are also called colour enhancing groups.
• An auxochrome itself does not show absorption above 200 nm.
• Actually, the combination of chromophore and
auxochrome behaves as a new chromophore having
different values of λmax and εmax. (Epsilon → ε)
• For example, benzene shows λmax 256 nm, εmax 200,
whereas phenol shows λmax 270 nm, εmax 1450 (both
increased).
• Hence, OH group is an auxochrome which extends the
conjugation involving the lone pair of electrons on the
oxygen atom resulting in the increased values of λmax and
as εmax.
• When two or more chromophoric groups are conjugated,
the absorption maximum is shifted to a longer wavelength
(lower energy) and usually to a greater intensity compared
to the simple unconjugated chromophore, e.g., ethylene
shows λmax 171 nm, εmax 15,530 and 1,3-butadiene λmax
217 nm, εmax 21,000.
• In conjugated dienes, the π molecular orbitals of the separate alkene
groups combine to give two new bonding molecular orbitals
designated π1 and π2, and two antibonding molecular orbitals
designated π3* and π4*.
• Following figure shows the π2 → π3* transition, i.e. the promotion
of an electron from a highest occupied molecular orbital (HOMO)
to the lowest unoccupied molecular orbital (LUMO) of a
conjugated diene, is of very low energy, 1,3-butadiene shows λmax
217 nm which is lower than the π → π* transition of an
unconjugated alkene, ethylene shows λmax 171 nm.
• Similarly, in case of other conjugated chromophores, the energy
difference between HOMO and LUMO is lowered resulting in the
bathochromic shift.
• Thus, α,β-unsaturated carbonyl compounds show both π → π* and
n → π* transitions at longer wavelengths (e.g., acrolein, λmax 210
and 315 nm) compared to unconjugated carbonyl compounds
(acetaldehyde, λmax 180 and 290 nm).
Acrolein
• It is known that as the energy of electronic transitions decreases,
their probability usually increases and so εmax also increases.
• Since conjugation lowers the energy required for electronic
transitions, it increases the value of λmax and usually that of εmax
also.
• Thus, ethylene shows λmax 171 nm, εmax 15,530 and 1,3-butadiene
λmax 217 nm, εmax 21,000.
• For more examples of various conjugated chromophores, see
following table.
• In general, the longer the conjugated system, the higher are the
values of λmax and εmax.
• Thus, a compound with sufficient conjugation absorbs in the visible
region (400–800 nm) and becomes colored.
• For example β-carotene, an orange pigment present in carrots, has
eleven carbon-carbon double bonds and absorbs in the visible region
(λmax 450 nm, εmax 14 × 104)
and is colored.
• The historical development of theories with respect to the
relationship between the color of a dye and its chemical constitution
has been thoroughly investigated.
• As previously stated, during the mid-nineteenth century, since
organic chemistry was only at its embryonic stage of development,
chemists utilized mostly empirical methods to synthesize dye.
• However in 1867, Graebe and Liebermann proposed that the color
of dye molecules was related to unsaturation within the molecules,
having observed that reduction destroyed the color of dyes.
• An early theory of dyes first formulated by O. Witt provided a basis
for understanding the relation between color and the structure of
molecule.
• According to this theory, a dye consists of: one or more the fused
benzene rings attached to the unsaturated groups called as
chromophores (e.g., –N=N–, –NO2, –C=O) and basic groups called
as auxochromes (e.g., NH2, OH groups).
• Both of them are responsible for the color.
• Witt’s theory was expanded by Dilthey and Wizinger in 1927.
• They realized that a chromophore is usually an electron-
withdrawing group, while an auxochrome is commonly an
electron-donating group and the two are linked through a
conjugated system.
• This particular approach can be considered as the starting point
of the donor–acceptor chromogen concept.
• Although Witt’s theory applied to anthraquininoid and azo dyes,
it was less successful in comparison with the theory proposed by
Armstrong and Nietzki regarding triphenylmethane dyes and an
alternative quinonoid theory since color was attributable to the
presence of quinonoid ring structure.
• While the following approaches were investigated to link
tautomerism with visible and UV light absorption by dyes
together the progress in quantum mechanics during the mid-
1920s contributed to the development of qualitative approaches
to associate color to chemical constitution.
Figure: The components of 4-
hydroxyazobenzene
• In simple terms, it can be considered that the organic dye
molecules contained three main components such as chromogen,
chromophore and auxochrome.
• The chromogen is a chemical compound that is either colored or
could be made
• colored by the attachment of suitable substituent.
• The chromophore and the auxochrome(s) are also part of the
chromogen.
• The chromophore is a chemical group that is responsible for the
appearance of color in compounds (the chromogen) where it is
located.
• The colorants are sometimes also classified according to their
main chromophore (e.g., azo dyes contain the chromophore –
N=N–).
• The auxochrome is a substituent group found in a chromogen that
influences its color.
• Whereas, the chromophore or chromophoric group is responsible for
chromogen which will be colored.
• The chromophore itself is not capable of determine a particular color
and hue.
• Also, Gurr differentiates two types of auxochrome namely
colligators, which are responsible for dye–substrate interactions and
which are either ionic (e.g., acidic: –SO3-, –COOH, etc., or basic: –
N+, –NH2) or non-ionic and non-colligators which modify color.
• The components responsible for color are presented in following
figure for 4-hydroxyazobenzene (Solvent Yellow 7).
• Unlike most organic compounds,
colorants possess color because
they:
– Absorb light in the visible
spectrum (400–700 nm)
– Have at least one chromophore
(color-bearing group) Figure: The components of 4-
hydroxyazobenzene
 – Have a conjugated system, i.e. a structure with alternating double
and single bonds
– Exhibit resonance of electrons, which is a stabilizing force in
organic compounds
• When any one of these features is lacking from the molecular
structure, the color is lost.
• In addition to chromophores, most dyes also contain groups known
as auxochromes (color helpers), examples of which are carboxylic
acids, sulfonic acid, amino, and hydroxyl groups.
• While these are not responsible for color, their presence can shift the
color of a colorant and they are most often used to influence dye
solubility.
• Following table shows the relationships between wavelength of
visible and color absorbed/observed.
• The wavelength spectrum of absorbed light, which determines the
color of the matter, is affected by its chemical structure consisting of
components such as the chromophores and auxochromes.
• Other factors contributing to color are illustrated in
following table and scheme.
• The structures in following table demonstrate the
importance of having an extended conjugated system.
• It is evident that doubling the length of the conjugated
system in β-carotene and its synthetic homologues causes
a significant bathochromic shift, i.e. to a darker color.
Figure: The components of 4-
hydroxyazobenzene
• In addition, resonance also exists across molecules with
delocalization of electrical charge among the conjugated
atoms and affects the color.
• Consequently there is always more than one way to draw
the structure of a dye.
• For example, methylene blue, commonly used in textile
and paper industry is represented by figure.
• The alternating double bonds are all equivalent.
• The positive charge is shared by the nitrogen and sulfur
atoms; in fact it is distributed across the whole cation and
not localized at any particular atom.
Figure: Different resonance structures of
methylene blue
• Regarding the requirement of a chromophore generating color in
organic compounds, it is important to note that the chromophore
must be part of a conjugated system.
• This is illustrated through the examples in following figure where it
can be seen that placement of an azo group between methyl groups
produces a colorless compound, while a yellow-orange color is
obtained when the azo group is placed between aromatic rings.

Figure: The relation of chromophore group, conjugation

and color.
• In addition to influencing solubility, auxochromes are essential ring
substituents in providing target colors.
• This is illustrated in following figure, where the following effects of
substituents are shown:
– Adding groups of increasing electron-donating ability to the
azobenzene structure has a bathochromic effect (cf. OH vs.
NH2).
– Electron-donating (NH2) and electron-accepting (NO2) groups
placed in conjugation provide a bathochromic effect. In this
regard, nitro groups are especially beneficial, contributing to
their prevalence in disperse dye structures.
– Increasing the number of electron-attracting groups conjugated
with the electron-donor has a bathochromic effect.
– The electron-donating effects of an amino group are enhanced by
adding alkyl groups to the N-atom.
Figure: Effects of substituent groups within an azo-dye system.
Dyestuff intermediates
Chemistry of dyestuff intermediates
Primaries
• The raw materials used for the manufacture of dyes are mainly
aromatic compounds, such as benzene, toluene, naphthalene,
anthracene, pyrene, phenol, pyridine and carbazole.
• These raw materials are known as primaries.
• In the past, the primaries came almost exclusively from the
distillation of coal tar but in recent years increasing quantities of
primaries, especially of benzene and toluene, have become
available from petroleum and natural gas.
• The term "coal-tar dyes", still widely considered synonymous with
synthetic dyes, is no longer an entirely correct description.
Coal tar
• When coal is subjected to destructive distillation, it yields coal gas
and coal tar.
• Coal gas is mainly used as a fuel while coal tar when subjected to
fractional distillation gives different products which are given in
following table.
• The black residue, left in the still after the distillation is over, is
called pitch.
• It contains 92-94 per cent of carbon and small amounts of pyrene
and chrysene.
• The later compounds (i.e., pyrene and chrysene) may be isolated
from pitch by steam distillation followed by fractional distillation
and crystallisation from solvent naphtha.
• When light oil is subjected to fractional distillation, it yields three
main fractions :
• Low Boiling Fraction: It contains acetonitrile, carbon disulphide and
fatty hydrocarbons.
• High Boiling Fraction: It is mixed either with the carbolic or creosote
oil.
• Middle Boiling Fraction: It is treated with cold conc. H2SO4 to
remove basic substances, e.g., pyridine, and then washed with
water and treated with caustic soda to remove acidic substances,
i.e., phenol and excess sulphuric acid.
• It is then washed with water and subjected to fractional distillation
when the following fractions are obtained:
• 90% Benzol (80-110°C): It contains benzene and toluene. It
contains 70% of benzene.
• 50% Benzol (110-140°C): It contains the same two hydrocarbons
in two different proportions along with xylene. It contains 46% of
benzene.
• Solvent Naphtha or Benzine (l40-170°C): It contains xylene,
mesityiene. etc.
• The various benzols and benzine on fractional distillation yield
benzene, toluene and xylenes.
• Middle oil contains mainly naphthalene and phenol.
• This layer on keeping for sometime deposits naphthalene which is
separated by centrifuging and pressing.
• The residue is treated with caustic soda and the aqueous solution is
separated and treated with dil. sulphuric acid to regenerate phenol.
• Crude naphthalene is first washed with sodium hydroxide, then
with conc. sulphuric acid to remove bases and finally with very
dilute caustic soda.
• It is next purified by sublimation.
• Heavy oil contains mainly cresols.
• It is used as such for the preparation of dyes.
• Anthracene oil contains anthracene and phenanthrene which are
deposited as crystals on cooling.
• Petroleum: In recent years, petroleum source has become
important especially for the production of primaries such as
benzene, toluene, xylene, naphthalene. etc.
• Potentially important developments in the production of these
primaries lie in the cracking and hydrogenation processes.
• Other sources: In recent years it has become a common practice to
obtain aromatic hydrocarbons from water gas, methane and olefins
by catalytic processes.
• Inorganic Raw Materials: A great variety of inorganic materials
are required by the dye industry.
• These include sulphuric acid, oleum, nitric acid, chlorine, bromine,
caustic soda, sodium nitrite, hydrochloric acid, sodium carbonate,
sodium hydrosuiphite, sodium sulphide, aluminium chloride,
sodium dichromate and manganese dioxide.
Unit process
• This denotes a synthetic step in organic synthesis of a compound
on a large scale.
• The common unit processes involved in the dyestuff production are
sulphonation, nitration, amination by reduction, ammonolysis,
oxidation, halogenation, hydrolysis, dehydration, Friedel-drafts
reaction, etc.
• It is important that all unit processes should be well-planned and
controlled.
• Some of the processes like nitration are inherently dangerous.
• For these reasons, close supervision by technically trained men is
the rule in plants where intermediates are manufactured.
Intermediates
• The primaries for dyes are almost never directly useful in dye
synthesis.
• It is necessary to convert them to a variety of derivates which are
in tum made into dyes.
• These derivatives are called intermediates.
• They are called such because they are really intermediates
between the primaries and the final dyestuffs.
• Intermediates are produced by reactions such as nitration,
reduction, sulphonation, halogenation, oxidation and
condensation.
• Most of these reactions lead to the formation of substituted
hydrocarbons which are functional in nature, i.e., they bear groups
which are capable of undergoing further chemical reactions.
• Intermediates in the dye industry are referred to the organic cyclic type
compounds used for the manufacture of synthetic dyes.
• These compounds are considered as chemical stepping stones between the
parent organic raw materials and the final products.
• The starting raw materials are mainly aromatic hydrocarbons such
as benzene, toluene, naphthalene, and the like, which are derived
from petroleum.
• The products are various dyes.
• The manufacture of a dye from primary raw materials involves a
number of prior synthetic stages and transformations, commonly
referred to as unit processes.
• Such processes include nitration, sulfonation, diazotization,
oxidation, reduction, chlorination, and others.
• The products, precursors of the dyes themselves, are collectively
known as intermediates.
• Intermediates are produced by a variety of reactions.
• Many dye intermediates are manufactured by repeated, and often
difficult, chemical reactions to obtain the desired product.
• Such conversion may be exemplified by the manufacture of a
relatively simple intermediate, for example, N,N-dibenzylaniline
disulfonic acid.
• This conversion requires a number of unit processes, namely the
nitration of benzene, the reduction of nitrobenzene, to give aniline,
the alkylation of aniline leading to N,N-dibenzylaniline the
sulfonation of which gives, finally, the disulfonic acid.
• Relatively few reactions are available for direct introduction of
substituent groups into the aromatic nuclei that are sufficiently
general to be applicable to benzene, naphthalene, and higher
polynuclear hydrocarbons.
• Although each of these reactions has specific characteristics, they
can be classified into two somewhat differentiated types:
• Different substitution reactions are influenced by substituent
groups already present in the benzene ring.
• Rules of substitution are covered in detail in several books on
organic chemistry.
• Substituents are important beyond their contribution to
molecular geometry in that they can alter the solubility of the
molecule in acid or basic solvents and possess directional
effects on ensuing nucleophilic substitution.
• Some of the more common unit processes employed in the
manufacture of dye intermediates are discussed with emphasis
on the general character of these processes below.
Electrophilic or nucleophilic substitution processes
• Most dye intermediates are prepared by reactions involving
electrophilic or nucleophilic substitution processes.
• The electrophilic processes include:
– Nitration
– Sulfonation
 – Halogenation reactions
while the nucleophilic processes include:
– Hydroxylation
– Amination reactions
• Electrophilic substitution reactions are of the form shown in
following figure.
• In this regard, the incoming electrophile (electron-seeking species)
reacts with the more electron-rich positions.
• When the aromatic ring contains ring activating groups (e.g.,
hydroxy, alkoxy, amino, alkyl), the incoming group will attack
ortho/para positions.
• If ring deactivating groups (e.g., nitro, sulfonic acid, carboxylic) are
present, the positions meta to the deactivating groups will be
attacked. Activating groups
Hydroxy, alkoxy, amino, alkyl

Deactivating groups
Nitro, sulfonic acid, carboxylic
 Deactivating groups

Activating groups

Figure: Electrophilic attack of an aromatic ring containing deactivating and

activating groups.
Sulfonation
• Most aromatic compounds can be sulfonated by the action of
concentrated or fuming sulfuric acid to form sulfonic acids.
• The reaction may be represented as:
• The readiness with which sulfonation takes place, however, varies
considerably.
• Benzene and toluene can be sulfonated in the cold, whereas
anthraquinone requires fuming sulfuric acid and high temperatures.
• Unlike the other electrophilic substitution reactions of benzene,
sulfonation is a readily reversible reaction.
• If water is not removed continuously during the reaction then the
hydrolysis of sulfonic acid will lead to the inverse reaction to the
starting product containing no sulfonate grouping.
• The overall process of sulfonation, if water is present in the reaction
mixture, is represented by the following equation:

• Sulfonation of aromatic compounds is very important in the

manufacture of dyes.
• As sulfonic acids are generally water-soluble, the sulfonation of
aromatic compounds provides a means to make aromatic
compounds water-soluble.
• Also, the sulfonic acid group is easily displaced by a variety of other
groups.
• Therefore, aryl-sulfonic acids are useful synthetic intermediates.
• Benzene is usually sulfonated by means of fuming sulfuric acid
(H2SO4 + SO3); a temperature of 80 to 100 0C is used at the end for
completing the reaction.
• Toluene reacts more readily than benzene under similar conditions
forming a mixture of the o- and p-acids.
• At low temperatures the o- is the major product, and at high
temperatures the p-acids.
• Naphthalene sulfonates to give a mixture of 1- and 2-
naphthalenesulfonic acids:
• At low temperatures naphthalene-1-sulfonic acid predominates
whereas at higher temperatures (up to 1600C) the 2-product is
formed in higher yields (85 percent).
• Further sulfonation at 150 to 1600C gives rise to di-, tri-, and tetra-
sulfonic acids.
• The important naphthalene-1,3,6-trisulfonic acid can be obtained
directly from naphthalene by progressive sulfonation with fuming
sulfuric acid first at 400C, then at 600C, and finally at 150 to 155°C.

• The intermediate derived from naphthalene-1,3,6-trisulfonic acid

along with the class of derived dyes are shown in following table.
• 2-naphthol undergoes sulfonation to produce two important
monosulfonic acids: schaeffer's acid and crocein acid.
• At 1000C Schaeffer’s acid predominates; at lower temperatures
more crocein acid is formed.
Preponderant → predominant in
influence, number, or importance

Crocein acid

Schaeffer’s acid
• Further sulfonation of 2-naphthol leads to the formation of two
isomeric disulfonic acids.
• At low temperatures, G acid is preponderant, whereas at higher
temperatures R acid predominates.
• Both R and G acids are important intermediates for azo dyes.
Effect of mercuric salts on sulfonation…….
• Anthraquinone is sulfonated by reacting with fuming sulfuric acid at
120 to 1400C.
• The product is mostly the 2-sulfonic acid and small quantities of the
2,6 and 2,7-disulfonic acids.
• The presence of mercuric salts in the sulfonation mixtures favors the
formation of anthraquinone-1-sulfonic acid; further sulfonation
leads to a complex mixture of disulfonic acids, chiefly 1,5 and 1,8
with lesser quantities of 1,6 and 1,7-isomers.
 Anthraquinone-1-sulfonic
acid

1,5 1,8

The compounds listed in following table are intermediates for the

anthraquinone series of dyes.
Mechanism of sulphonation
• Various mechanisms have been proposed for sulphonation.
• However, the accepted mechanism is that sulphonation proceeds
with free SO3 which is produced as follows:

• The SO3 is electrophilic reagent.

• It attacks the benzene ring to form the intermediate carbocation.
• Then, this loses a proton to form the resonance-stabilised
substitution product, the anion of benzene sulphonic acid, which
takes a proton to give benzene sulphonic acid.
• The step involving the loss of proton by carbocation is slow and,
therefore, becomes the rate determining step.
Substitution rules
• These rules for sulphonation are similar to those of nitration.
• However, these rules are as follows:
• Rule I: The groups -NO2, -COOH and -SO3H direct the entering group
to the meta position. e.g.,
• Rule II: The alkyl groups (e.g., methyl) direct the entering group predominantly
to the ortho and para positions.
• Generally, a mixture of isomers is obtained.

• Rule III: The chlorine is similar to the methyl group in its effect on orientation
but gives less of the ortho isomer.

• Rule IV: The directing effect of amino groups depends on their basicity.
• The less basic amines are ortho-para directing.
• Aniline is an example of this type.
• However, more basic amines (e.g., dimethyl amine) form meta-directing salts in
acid.
Halogenation
• The benzene nucleus is readily substituted by chlorine or bromine
atoms on interaction with the halogens in the presence of ferric
chloride or bromide, aluminum chloride, or iodine.
• The replacement of nuclear hydrogen by chlorine or bromine in the
benzene series is mostly done directly using gaseous chlorine or
liquid bromine.
• Chlorination may also be achieved by reacting with thionyl chloride,
phosphorus oxychlorides, phosphorus pentachloride, or sulfuryl
chloride.
• For example, the dye disperse violet 28 is prepared by the
chlorination of lenco-l,4-diaminoanthraquinone with sulfyryl chloride
by the following reaction:
• Toluene undergoes catalyzed chlorination or bromination in the
same manner as benzene, with equal quantities of o- and p-
chlorotoluenes being produced.
• When, however, the catalyst is omitted and the hydrocarbon is
treated with either halogen at the reflux temperature, preferably
with exposure to light, the chlorine or bromine atoms enter the
methyl side chain rather than the nucleus, with formation in
succession of the mono-, di-, and trihalo derivatives.
• Benzyl chloride is used in the manufacture of ethylbenzylaniline and
dibenzylaniline for triarylmethane dyes.
• The direct chlorination of naphthalenes results in the formation of
numerous isomers.
• This reaction is seldom used.
• In the anthraquinone series an indirect chlorination method is used.
• The advantage is taken from the fact that the —SO3H group may be
replaced by —Cl through the action of hot concentrated
hydrochloric acid and 10 to 15 percent aqueous sodium chlorate
NaClO3.
• Such a case is the preparation of 1,5-dichloroanthraquinone.
Nitration
• Nitration conducted with nitric acid alone or in combination with
sulfuric acid, provides an efficient method for preparation of mono, di,
and trinitro derivatives of many aromatic hydrocarbons and of
hydroxy, halo, and other substitution products.
• The polynitro compounds accessible by the direct route have the m-
orientation, and o- and p- dinitro compounds, though obtainable by
indirect methods, are rare.
• Products of nitration are useful dye intermediates.
• Nitrobenzene can be produced on a technical scale in yields up to 98
percent by nitration of benzene with mixed acid.
• The sulfuric acid serves as a solvent and generates the nitronium ion
NO2+, which is the attacking electrophile.
• Nitrobenzene itself may be further nitrated with a mixed acid giving
m-dinitrobenzene.
• The o- and p-dinitrobenzenes are removed as water-soluble products
by treating the nitration product with aqueous sodium sulfite, sodium
o- and p-nitrobenzenesulfonates being formed.
• The residual m-nitrobenzene is separated from the aqueous layer,
washed with water and finally dried.
• The nitration of toluene is carried out as in the case of benzene, but
the temperature is maintained below 200C to avoid oxidation of the
methyl group.
• A mixture of o-, p-, and m-nitrotoluene is obtained in the
approximate percentage of 63, 35, and 2.
• On cooling to -10°, part of the p-nitrotoluene crystallizes and is
separated in a centrifuge.
• The residual oil is separated by a combination of fractional
distillation and a process of crystallization known as sweating.
• When benzene derivatives (such as phenols and chlorobenzene) are
nitrated, isomers of the desired product are obtained.
• For example, nitration of phenol by nitric acid gives o- and p-
nitrophenol:
• The nitration of chlorobenzene, dichlorobenzene, and chlorotoluene
leads to substances of considerable value in dye chemistry in that
nitro groups in position 2- and 4- relative to chlorine having an
activating effect.
• Mononitration of naphthalene with mixed acid at a temperature of
35 to 500C gives a good yield of 1-nitronaphthalene; this is the main
source of 1-naphthylamine and its derivatives.
• Anthraquinone on nitration at about 500C gives mainly 1-
nitroanthraquinone.
• At 80 to 95°C, dinitration occurs to give a mixture of 1,5- and 1,8-
isomers.
• These isomers are important as starting materials for the preparation
of other intermediates.
Figure: Nitration of naphthalene using mixed acid.
Amination
• The process of making an amine (RNH2) is generally referred to as
amination.
• The methods commonly used are:
– Reduction of a nitro compound and
– Action of ammonia on a chloro-, hydroxy-, or sulfonic acid
compound
• The main method, both in the laboratory and in technical practice,
for the introduction of an amino group into an aromatic compound,
is nitration and reduction.
• Reduction of nitro compounds is accomplished by:
– Catalytic hydrogenation
– Iron reduction (Bechamp method)
– Sulfide reduction
– Zinc reduction in an alkaline medium
• The most widely used method of converting nitro compounds into an
amine is the Bechamp method, which uses iron turnings in water
containing a small quantity of hydrochloric acid.
• The reaction may be represented by the equation.
• The Bechamp method can also be used in reducing the nitro
derivatives of sulfonic acids.
• A typical example being the manufacture of metanilic acid and
related substances.

• An example of direct action of ammonia on substitute aromatic

compounds is the conversion of p-nitrochlorobenzene to p-
nitroaniline.
• This reaction may be carried out continuously with 40 percent
aqueous ammonia under 200 atmosphere at 235 to 2400C
• Aniline can also be prepared by the amination of phenols under a
pressure of 15 to 16 atm at a temperature of 380 to 385°C in the
presence of a silica-alumina catalyst (Halcon process).

• The Bucherer reversible reaction of conversion of naphthols to

anilines by aminolysis is of outstanding importance in naphthalene
chemistry.
• The reaction is used for the replacement of aromatic amino groups
by hydroxy groups, in the naphthalene series.
• The reaction is valuable in the synthesis of naphthalene dye
intermediates and may be represented as follows:
• Two important azo dye intermediates, Amino J acid and Amino G
acid, are also produced by the Bucherer reaction represented as
follows:

7-Aminonaphthalene-1,3-disulphonic acid
6-Aminonaphthalene-1,3-disulphonic acid
• In a process known as the Bucherer reaction, naphthols are heated
under pressure with a mixture of ammonia and sodium bisulfite.
• As the second and third examples indicate, the reaction works with
aromatic amines and is selective.
• Note that the β-hydroxy group reacts preferentially when an α-
hydroxy group is also present, and that two hydroxy groups in the
same compound can be replaced.

Figure: Amination of naphthalene compounds via the Bucherer reaction.

• An alternative route to the synthesis of aminoanthraquinones is the
2-step sequence shown in following figure.
• In this case, amination occurs via the condensation of para-
toluenesulfonamide with chloroanthraquinone followed by
hydrolysis of the sulfonamide bond.
• This method provides a way to introduce an NH2 group without the
use of ammonia gas and the associated high temperatures and
pressures.

Figure: An indirect amination of the anthraquinone ring system.

Hydroxylation
• The main general method for the hydroxylation of aromatic
compounds is the alkali fusion of sulfonic acids:

• A second general reaction is hydrolysis of chloro compounds:

• The phenates thus obtained can be converted to phenol by reaction

with an acid.
• In a similar way resorcinol is made by fusion of m-benzene
disulfonic acid:
• 2-naphthalene sulfonic acid can be converted to 2-naphthol by the
hydrolysis with sodium hydroxide:

• 2-anthraquinosulfonic acid can be converted to the hydroxy

compound by heating with calcium hydroxide in water.
• Alkaline fusion of the same sulfonic acid gives alizarin.
• The short sequence in following figure shows that aqueous alkali
can also be used in hydroxylation reactions.
• In both cases, however, elevated temperatures are required.

Figure: Synthesis of two key dye intermediates using hydroxylation steps.

Oxidation
• Controlled oxidation of aromatic compounds is an important
process.
• The most common reagent is air or oxygen gas in the presence of a
catalyst.
• One of the classical examples is the catalytic vapor phase oxidation
of naphthalene to phthalic anhydride.
• This reaction is carried out over a vanadium pentoxide catalyst at
4500C.

• Phthalic anhydride is used in very large quantities in the plastic

industry and plays a significant role in dye chemistry.
• Currently, phthalic acid is mainly produced by the catalyzed
oxidation of o-xylene obtained by a cracking process from
petroleum.
• The oxidation of the methyl group in toluene derivatives to the
aldehyde is an important stage in triarylmethane dye manufacture,
p-toluene sulfonyl chloride is first hydrolyzed in concentrated
sulfuric acid and then subjected to the oxidizing action of a
manganese compound to produce benzaldehyde-4-sulfonic acid.
• Similarly, the oxidation of the methyl group in an anthraquinone
derivative leads to the formation of the corresponding carboxylic
acid.
Reduction
• The most important reduction reactions are those leading to
aromatic amines that are suitable for azo dye formation.
• While this usually involves the reduction of a nitro group to an
amino (NH2) group, the reduction of azo groups to amino groups is
also an important process.
• Agents that are commonly used to effect chemical reductions
include:
– Fe + HCl or H2SO4
– Na2S
– NaSH (Sodium hydrosulfide)
– Zn + NaOH
– H2 + transition metal catalysts
– Na2S2O4 (Sodium dithionite)
• Examples of these reductions are given in following figures.
• While the reduction of nitrobenzene can be conducted in a number
of ways, a key commercial process involves the method in
following figure, where high temperature hydrogenation is used.
 Figure: Commercial process for the reduction of nitrobenzene.

Figure: Reduction of (a) azo and (b) nitroanthraquinone compounds.

Figure: Formation of Koch acid via nitration and reduction steps.

 Figure: Reduction of nitrobenzene in acidic and alkaline media.
• The reduction of azo compounds using sodium hydrosulfite
(Na2S2O4) and NaOH is an important reaction, as it provides an
indirect method for the amination of phenols and naphthols.
• The reduction of nitro groups in anthraquinone compounds works
best when a mild reducing agent (e.g., sodium hydrosulfide, NaSH)
is used.
• In this way one avoids reducing the quinoid system.
• It must also be pointed out that the medium employed in the
reduction process can play a major role in the outcome of the
reaction.
• A good example is the reduction of nitrobenzene in the presence of
acid or alkali.
Miscellaneous reactions
Alkylation
• Alkylation on nitrogen and alkylation on oxygen are of some
importance in dye chemistry.
• Large quantities of mono- and di-alkylamines are manufactured
annually for use in the organic chemical industry.
• The usual alkylating agents are methanol, ethanol, methyl and ethyl
chlorides, and dimethyl and diethyl sulfates.
• N,N-Dimethylaniline is probably the most important of the
alkylanilines and is made by heating a mixture of aniline, methanol,
and concentrated sulfuric acid at 230 to 235°C and a pressure of 25
to 30 atm.

• Phenol may be methylated with methyl sulfate in cool alkaline

medium to give anisole:
Arylation
• The introduction of arylamino groups is often needed in the
synthesis of intermediates and dyes.
• An important intermediate, 3-ethoxy-4-methyldiphenylamine is
prepared from resorcinol and p-methylaniline as follows:
Condensation and addition
• In both condensation and addition reactions, two or more molecules
combine by the elimination of a simple molecule (condensation), or the
reaction is stopped after the molecules are joined (addition).
• There are only a few intermediates manufactured in any considerable
quantity by these reactions.
• An example of a condensation reaction is the formation of the
diphenylamine derivative, commonly called nitro delta acid.

• The formation of cyanuric acid from cyanogen chloride is a good

example of an addition reaction.
Diazotization
• The conversion of a primary aromatic amine to a diazonium
compound is known as diazotization.
• While this process will be covered in more detail in our
discussion of azo dye synthesis, it is worthwhile to point out that
the diazonium group (N2+) is used to produce a wide range of
intermediates.
• As indicated in following figure diazotization is often achieved
through the action of nitrous acid (HNO2) and the resultant
diazonium group can be replaced by various groups or reduced to
give arylhydrazines.
Figure: Diazotization of aniline and its conversion to other types of intermediates.
Carboxylation
• The introduction of carboxyl groups into the structures of phenols
and naphthols produces some important dye intermediates, including
salicylic acid and BON acid.
• This process is conducted under pressure at elevated temperatures
using the sodium salts of phenols/naphthols and in the case of β-
naphthol, the carboxyl group enters the 3-position (following
figure).
• The free acid (CO2H) group is produced by acid treatment in the
final step.

Figure: Carboxylation of phenol and β-naphthol.

BON acid = 3-hydroxynaphthalene-2-carboxylic acid

Nomenclature of dyes intermediates
Nomenclature of dyes
Nomenclature
• Nomenclature of dyes intermediates
• Nomenclature of dyes

Nomenclature of dyes intermediates

• A large number of variety of intermediates involved in dyestuff
production cannot always be named by their chemical names
because chemical nomenclatures may lead to confusion.
• For example, H-acid may be named chemically as:
– l-amino-8-hydroxy-naphthalene-3,6-disulphonic acid or
– l-hydroxy-8-amino-naphthalene-3,5 disulphonic acid
the chemical names are different but the compounds are identical.
• The usual practice is to name dyes intermediates by commercial
names such as H-acid, Y acid, naphthol AS, Fast blue B base, Fast
scarlet G base, etc.
• These commercial names as compared to the nomenclature are
short, symbolic and simple even for a layman in trade.
Nomenclature of dyes
• Hundreds of dyes are being synthesised in the laboratory.
• Of these about 3600 are used commercially.
• Various systems of nomenclature are known.
• Two of these are as follows:
Commercial naming of dyes
• In the earlier times, the commercial names of dyes are coined by
individual manufacturers and these usually consist of three or four parts.
• The trademark name of the class comes first and is followed by words,
letters or numbers.
• These describe the shade and other characteristics, strength, physical form
etc.
• The code letters used by different manufacturers are not standardized
• The alphabetical letters following the trade names may refer to the shade
of the dye, e.g.,
– Y or G = Yellow (gelb)
– R = Red (rot)
– B = Blue
– O = Orange, etc.
• Similarly, other letters indicate the type of dye, fastness property,
temperature of dyeing etc.
– D = Direct dye for cotton
– S = Acid dye (German. Sauer = acid)
– F = Fastness to specific agencies
– L = Light fastness
– C = Cold brand reactive dye
– H = Hot brand reactive dye
– I = Vat dye
– Ik, In = Dyeing in cold (katt) and normal temperature
• Thus, 'G' stands for (German word gelb = yellow) 'R' for (German
word rot = red) and 'B' for (German word blau = blue) yellowish,
reddish and bluish tones respectively.
• For example, Astrazon Yellow 3G is a basic dye having considerable
yellowish tone, Chrysophenine G is a direct dye with a yellowish tone.
• Similarly, Acridine Orange R and Astrazon Orange R both are basic
dyes and Rhodamine B (basic dye) and Remazol Red B (reactive dye)
with bluish tone.
• Similarly, in Vat Pink R, 'R' indicates the red tone of the pink.
• The repetition of the above letters indicates the greater intensity of the
tone.
• For example, methyl violet 6B is a very deep purple (close of bluish)
tone, similarly Alkali Fast Green 3B is a green acid dye having
considerable bluish tone.
• Sometimes the letters are used to represent the class of the dye.
• For example, in Alizarin Blue D, the letter ‘D' indicates that dye is a
direct cotton colour.
• In Fuchsines, the letter 'S’indicates that the dye is an acid (saver).
• Sometimes the letters are also used to represent the property of a dye.
• For example, the letter 'F' is used to indicate that the dye is fast to
certain agencies such as light washing, etc.
• The letter 'L' appears in the name of the dye, indicating that this dye
produces a shade on a fibre and is fast to light.
• Examples having this letter are Basacryl Yellow 5 GL, Basacryl
Yellow 5 RL and Basacryl Violet RL, disperse dyes for polyester
fibres such as Foron Grey S-4 GL and Foron Scarlet E-2 GFL; direct
dyes such as Kiton Fast Yellow 2 GL, Chlorantine Fast Blue 10 GL
and Benzo Fast Red 8 BL.
• In the case of reactive dyes, belonging to the chlorotriazine class,
reactivity has been found to depend upon the number of chlorine
atoms present in the molecule.
• If the molecule of a dye has two chlorine atoms, they are highly
reactive and can be used in the cold condition.
• Hence they are termed as cold brand (cold dying) reactive dyes.
• Thus, their names have the letter 'C’ e.g., Premactive C and Goldazol
C.
• There are also dyes which have only one chlorine atom.
• These dyes are less reactive and, therefore, the dye solutions have to
be heated for their greater reactivity.
• Thus, they are termed as hot brand (hot dyeing) reactive dyes and
hence their names have the letter 'H', e.g., Procion H and Premactive
H.
• The letter ‘T' generally indicates that the dye belongs to a special class
of vat dyes, the solubilised vat dyes.
• They are subdivided into various groups such as Ik, Iw, In depending on
the condition of temperature used.
• For example, Ik group of vat dyes are employed in the cold condition,
i.e., at 20-30°C.
• Further, Iw and In group of vat dyes are employed under conditions of
temperature 30-40°C and 50-60°C respectively,
• The letters 'N' and 'K' indicate that it is vat dye which can be applied to
cellulosic fibres by a particular method of dyeing involving normal
and cold temperature conditions respectively e.g., Indanthrene Golden
Yellow GK, Indanthrene Brilliant Orange RK, Algol Yellow GCN,
Calcdon Jade Green BN.
• Hence the intensity of the tone, tone of the colour and condition of
temperature of dyeing are indicated as in Indanthrene Yellow GK,
Indanthrene Yellow 4 GK, Indanthrene Yellow 5 GK and Indanthrene
Yellow 7 GK (In this case, yellowish tone tends to increase).
Advantage
• The commercial names as compared to the nomenclature are short,
symbolic and simple even for a layman in trade.
• Chemical nomenclature may often lead to confusion.
Drawback
• The main drawback of this system of nomenclature is that the same
dye has been given various names by different manufacturers, e.g.,
rose-red dye is named either by pararosaniline, magneta or fuchsine.
• In order to overcome this difficulty, a colour index has been compiled.

Colour index naming of dyes

• The best method for the nomenclature of dyes is that used jn the
Colour Index, a publication sponsored by the Society of Dyers and
C.olourists (England) and the American Association of Textile
Chemists and Colourists.
• In this, each dye is given two reference numbers, one relating to its
class with respect to dyeing method (e.g.. C.I. Vat Blue 4 for
indanthrone) and the other to its chemical description in five digits
(e.g., C.1. 69800 for indanthrone).
• All the commercial names under which dye is sold (over 37 of
indanthrone e.g., lndanthrene Blue RS, Cibanone Blue RSN, Caledon
XRN, Ponsol Blue GZ, etc.) are also listed in the colour Index.
• A five digit C.I. (Constitution) number is assigned to a dye when its
chemical structure has been disclosed by the manufacturer.
• It is important to recognise that although a dye has a C.I. number,
the purity and precise chemical constitution will vary depending
upon the name.
• Thus, the dye C.I. Direct Blue 99 from company A will not be
identical to C.I. Direct Blue 99 from Company B.
• The following example illustrates these points:
 Diazotization
and
coupling reaction
Nitrosation
• Nitrosation is a process of converting organic compounds into
nitroso derivatives, i.e., compounds containing the R-NO
functionality.
• Nitrosating agents to be considered include; nitrites (e.g., sodium
nitrite, NaNO2) and nitrous acid (HNO2), nitric oxide (NO), nitrosyl
halides (e.g., ClNO, BrNO), dinitrogen trioxide (N2O3), dinitrogen
tetroxide (N2O4) and organic nitrites (e.g., t-BuONO).

Formation of N-Phenyl-nitrosamine
Diazotisation
• In 1858, Peter Griess, a German Chemist, discovered that when a
primary aromatic amino compound such as aniline, toluidine, etc.,
is acted on in aqueous acid medium by ice-cold nitrous acid, a
second nitrogen atom has been introduced into the molecule, giving
the new compound ArN2Cl.
• This new compound ArN2Cl is called diazo compound and the
formation of this compound is called diazotisation.
• This process may be envisaged as taking place as follows:

• The diazotisation is believed to take place through the following

steps:
• The actual nitrosating species has been found to vary according to
condition and may be:

• At low acidities, it is probable that dinitrogen trioxide N2O3 is the

effective reagent.
• This may be arising from the equilibrium.
• The mechanism with N2O3 in the case of aniline being as follows:

• The primary aliphatic amines do not form stable diazonium cations and on
treatment with nitrous acid, breakdown occurs with the formation of non-
nitrogenous products, nitrogen gas being evolved.
• On the other hand the relative stability of the aromatic diazonium cation is the
result of delocalisation of the positive charge by the π-electron system, thus
Diazo coupling (Coupling reaction)
• It may be regarded as an electrophilic substitution by a diazo group.
• Thus, normally coupling reaction takes place at sites of increased
electron density.
• The coupling takes place in aromatic or heterocyclic systems
having aromatic character or at activated carbon atoms in aliphatic
systems such as acetoacetanilide.
• The diazo ion compared to nitronium ion or SO3 is a weak
electrophile.
• It reacts only when the aromatic nucleus possesses powerful
clectrondon donating groups like OH or NH2.
• The mechanism of coupling may be depicted as follows:
• With tertiary amines a similar situation arises:

• Coupling with phenols are usually carried out under alkaline conditions while the
coupling with amines are carried out under slightly acidic conditions.
• The electron-withdrawing groups such as nitro in o- and p-position to the diazo
ion increases its electrophilic character and the coupling reaction takes place even
with weak electron donating groups in the aromatic nucleus, e.g., anisole.
 Summary of diazotization and coupling reaction

Diazotization
Requirement for azo dye
• An aromatic amine or arylamine e.g., phenylamine, C6H5NH2 is
needed to make an azo dye.
Preparation of phenylamine

• Nitrogenate benzene

• Reduce
• Phenylamine reacts with HNO2 (Nitrous acid)
– HNO2 is unstable at room tempertature
– HNO2 has to be made "in situ" (this means "in the reaction”).
How HNO2 is made?
• NaNO2 → sodium nitrate (III) / sodium nitrite
• HCl reacts with sodium nitrate (III)
Benzene dizonium ion

• The product is benzene dizonium chloride and it is unstable so the

reaction mixture must be kept cold i.e., 0 - 5 oC.
• The diazonium ion acts as an electrophile.
 "An electrophile is a positively charge specie that is attracted to a
region of high electron density and react with it, accepting a pair of
electrons to form a covalent bond".
• It substitutes a H-atom on the phenol (the hydrogen at from C-4 of
the phenol ring).
• So it is a substitution reaction.
• Azo dyes are stable molecules because they contain a highly
delocalized electron system which takes in both benzene rings and
the two nitrogen atoms bridging the rings.
Diazonium salt formation mechanism
• The diazonium salt formation involves addition of NO, followed by
a series of acid-base reactions that turn the oxygen to water and
creates a triple bond between the two nitrogen atoms.
• The water is then booted off as a leaving group.
• Diazonium salt formation is only possible with primary alkyl and
aryl amines.
Nitrosoamine
 Coupling reaction
• Three types of dyes are obtained from:
– Phenol → dye obtain has orange color
– Aniline → dye obtain has yellow color
– Naphthol → dye obtain has red color
Phenol → dye obtain has orange color

• As two units combine to form one unit so it is called as coupling.

• As there is -N=N- linkage which is known as azo linkage and due
to this, it is known as azo coupling.
• This dye has extended resonance and due to this resonance it is
coloured (orange, -OH group and from O → orange).
Mechanism

Note: O- and C- are electron donor and best of them is C-

Aniline → dye obtain has yellow color
• The dye obtain is yellow in colour and this reaction do not required
basic medium because it itself is basic in nature.

β-Naphthol → dye obtain has red color

α α
β β
Phenyl-2-naphthol
β-Naphthol Red
2o and 3o amines are not suitable for reaction
 Assignment
Q: Identify the aromatic amine and coupling agent (arene)
needed to react with cold sodium nitrate (III) and HCl to
make the following azo dye.

Ans:
 Assignment
Q: Which of the following amines will produce benzene diazonium
chloride when reacted with cold NaNO2 and HCl?
Synthesis of different
dyestuff and some
specific dyes
Synthesis of an azo dye
• Many early dyes were made from plants.
• Alizarin is an example extracted from the madder root.
• Alizarin only sticks fast to cloth which has been impregnated with a
metal compound such as aluminium sulphate.
• The process is called mordanting.
• The colour obtained depends on the mordant used.
• An aluminium mordant gives a red colour, tin (II) give a pink
colour and iron (II) gives a brown colour.
• Mordanting takes place under alkaline
conditions so that the metal hydroxide is
precipitated in the fibres.
• The metal ions firmly attach themselves to the
cloth and then bind the dye molecules by
forming chelate rings.
• A range of dyes have been developed based on
phenylamine (aniline) as the starting material
known as azo dyes.
• Phenylamine reacts with a solution of sodium nitrate (III)
and hydrochloric acid at a temperature below 5oC
(remember keeping that test-tube in ice?) to produce
benzene diazonium chloride.
• This type of reaction is known as diazotisation.
• The hydrochloric acid first reacts with sodium nitrate (III)
to form unstable nitrous acid.
NaNO2(aq) + HCl(aq) → HNO2(aq) + NaCl(aq)
• The nitrous acid then reacts with the amine.

• If the temperature is allowed to rise above 5oC, the

benzenediazonium chloride decomposes to form phenol
and nitrogen gas is given off.
• If the benzenediazonium chloride is reacted with another
compound containing a benzene ring, called a coupling
agent, an azo compound is produced.
• The diazonium salt acts as an electrophile.
• Phenols and amines are often used as coupling
compounds.
• Many of the products are important dyes.
• With phenol the following reaction occurs:

Yellow-orange shade
• A similar reaction occurs with phenylamine:

Bright yellow shade

• The first dye is a yellow-orange shade, the second bright
yellow.
• Many azo dyes are coloured in the range from red
through to yellow.
Red → yellow

• Some azo dyes are green, blue or even purple.

• Many azo dyes are produced using a derivative of
naphthalene, one example of which uses naphthalen-2-ol
to produce a red azo dye.
• Notice how this compound is formed from two benzene
rings joined (naphthalene differs since there is no
hydroxy group present).
• Also note that in this reaction sodium hydroxide is
needed.
• All coupling compounds contain a benzene ring that
performs the coupling because it stablises the delocalised
electron structure.
• Without a coupled benzene ring the compound would
remain unstable and break down at over 5oC like
benzenediazonium chloride.
The coupling reaction of benzenediazonium ion with
naphthalen-2-ol
• The azo dye 1-(4-hydroxyphenylazo)-2-naphthol by the
diazonium coupling reaction of naphthalen-2-ol with the
benzenediazonium ion obtained from 4-aminophenol:
• There are many different classes of dyes in which azo dyes are
certainly one of the most important classes.
• About half of the dyes used in industry are azo dyes.
• Azo dyes have the basic structure, Ar−N=N−Ar', where Ar and
Ar' are two aromatic groups.
• The unit containing the nitrogen-nitrogen double bond is
called an azo group.
• The nature of the aromatic substituents on both sides of the
azo group controls the colours of the azo compounds as well
as the water-solubility of the dyes and how well they bind to a
particular fabric.
• Preparation of the 1-(4-hydroxyphenylazo)-2-naphthol azo dye
involves the conversion of 4-aminophenol to the diazonium
ion intermediate 4-hydroxybenzenediazonium ion followed by
the reaction with naphthalen-2-ol.
Experimental procedure
• Prepare 30 cm3 of ~10% aqueous sodium hydroxide solution by
dissolving 3 g of sodium hydroxide in 27 cm3 of water in an 150-
cm3 conical flask.
• Weigh 1.44 g of naphthalen-2-ol (0.01 mol) and dissolve it into the
sodium hydroxide solution. Stir the mixture until complete
dissolution. Cool the solution with an ice-water bath.
• The benzenediazonium salt solution can be prepared as below:
– Dissolve 0.70 g of NaNO2 (0.01 mol) in 5 cm3 of water.
– Put 1.20 g of 4-aminophenol (0.011 mol) into 45 cm3 of water in
a 100-cm3 conical flask. Add slowly 12 cm3 of concentrated
hydrochloric acid and stir the mixture until the 4-aminophenol is
dissolved completely.
– Cool the 4-aminophenol solution in an ice-bath. Some 4-aminophenol
may precipitate out upon cooling. While keeping the solution at 0 °C
add the sodium nitrate(III) solution slowly with a dropper. The
mixture should be well-stirred during addition. When the addition is
completed, stir the mixture for another 2 - 3 minutes. The slightly
turbid pale grey solution is the benzenediazonium salt solution.
• To the alkaline naphthalen-2-ol solution add the benzenediazonium
salt solution slowly. A large amount of brick red precipitate forms
during addition. The addition takes about 5 minutes. The reaction
mixture should be stirred efficiently and cooled in an ice-water bath
during the addition.
• When the addition is completed, stir the mixture at 0 °C for 5 - 10
minutes. This is to ensure the reaction goes to completion.
• Filter the mixture by suction filtration. Wash the solid product on
the Büchner funnel with a small amount of cold water. Dry the
product on the Büchner funnel with the suction turning on for a few
minutes.
• Transfer the product to a watch-glass. Allow the product to dry for
1 - 2 days.
• Weigh the product and determine the percentage yield for the
reaction.
• Determine the melting-point of the product. Compare the melting-
point with the literature value of 197 - 198 °C. (Optional)
 Assignment

Q: What is the role of aromatic substituents about

−N=N− functionality?

Ans:
• The nature of the aromatic substituents on both sides of the
azo group controls the colours of the azo compounds as well
as the water-solubility of the dyes and how well they bind to a
particular fabric.
 Assignment
Explain every step of following scheme for the synthesis of indigo
dye.
1. Conversion of naphthalene into phthalic acid
• Naphthalene firstly oxidizes in the presence of V2O5 in a packed bed
reactor with cooling.
• Temperature should be constant along the whole length of reactor, it can
be varied between 600 to 675.
• Pressure will be 1atm while partial pressure of naphthaline can be vary
between 0.01 to 0.02 atm.
• After oxidation phthalic anhydride will be formed.
• Then phthalic anhydride react with base (NaOH) and then hydrolyze to
form phthalic acid.
2. Conversion of phthalic anhydride into phthalimide
• Phthalimide is an imide derivative of phthalic anhydride.
• Phthalimide can be prepared by heating anhydride with aqueous ammonia.
• It can also be prepared by treating with urea or ammonium carbonate.
• In this, addition of imide group will occur with the rearrangement of
bonds, at the end phthalimide will formed with the elimination of carbon
dioxide and water.
3. Conversion of phthalimide into phenylglycine-o-carboxylic acid
• In this conversion, phthalimide react with base (NaOH) and base will
abstracts N-H acidic proton and form anion this anion take Cl from
sodium oxychloride and give N-chloroamide.
• This chloroamide group rearranges the other groups at carbonyl carbon
and gives anthranilic acid at the temperature of 70-80 0C.
• Then it oxidize with glycine and gives phenylglycine-o-carboxylic acid.
4. Conversion of phenylglycine-o-carboxylic acid into
indigo
• In this process, water molecule release and then after
oxidation indigo dye will formed.
Non-hazardous chemical synthesis of indigo
• Green chemistry is the design of chemical products and
processes that reduce or eliminate the generation of
hazardous substances.
Principle
• According to this principle, the synthetic method should
be designed in such a way that substance having little or
no toxicity to human’s health or environment should be
used wherever possible.
• Hence green chemistry recommends the design of
synthesis to use and generate substances with little or no
toxicity.
Conventional route
Greener route
 Synthesis of dyestuff
(direct dyes, acid dyes, reactive dyes, disperse dyes)
Primulin base
• A yellow thiazole derivative, C₂₁H₁₅N₃S₂, which is obtained when p-
toluidine is heated with sulphur and is an intermediate in dye
manufacture.
 Synthesis of direct dyes
Monoazo dyes
• Diazotization of dehydrothio-p-toluidinesulfonic acid and coupling
to acetoacetic acid o-anisidide results in the direct yellow 27.

Dehydrothio-p-toluidinesulfonic
Direct Yellow 27
acid
• Substantive (‫ )بﻧيﺎدی‬yellow monoazo dyes are also obtained by
oxidation of dehydrothio-p-toluidine and its derivatives.
• Oxidation of the sodium salt of the monosulfonic acid of the
primulin base in the alkaline pH range with sodium hypochlorite
(NaClO) results, for example, in direct yellow 29.
 Direct Yellow 29
Disazo dyes
• Diamines used for the synthesis of symmetrical substantive disazo
dyes are following (Structure 23 and 24).
• An example of the use of 24 as diamine is direct red 75.

Direct Red 75

H-acid = 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid

Rock salt or halite
Table salt or common salt is a mineral composed primarily of
sodium chloride, a chemical compound belonging to the larger
class of salts; salt in its natural form as a crystalline mineral is
known as rock salt or halite.
Trisazo dyes
• In the manufacture of trisazo dyes, good yield and purity during final
coupling are often obtained only in the presence of pyridine or other bases
as coupling accelerators.
• Intermediate isolation and separation of impurities prior to continuation
of coupling are also frequently necessary.
• The use of pyridine during final coupling (pyridine coupling) is illustrated
in the following abridged (‫ )مشترﮐہ‬manufacturing specification for direct
green 33: 2-aminonaphthalene-8-sulfonic acid → 2,5-xylidine → 2-
ethoxy cleve acid 6 → N-acetyl H acid
Diazotization
• The disazo dye is produced by the usual method aminocroceic acid →
sym. m-xylidene → 2-ethoxy-cleve acid 6.
• Aminocroceic acid is stirred in water with 50 % acetic acid.
• Then sodium nitrite solution is
added at 25°C.
• After stirring overnight,
a reddish brown solution is obtained.

Direct Green 33
Coupling
• To H acid (1-amino-8-hydroxynaphthalene-3,6-disulfonic acid),
dissolved in water, are added 40% sodium hydroxide solution and soda;
the mixture is heated to 70°C and acetic acid anhydride is added.
• After acetylation is completed, the mixture is transferred to pure pyridine
and ice.
• The diazotizing solution is added at 0 - 12°C over 30 min.
• After a further hour, sodium hydrogencarbonate is added, and after 1 h the
mixture is heated to 60°C.
• Following the addition of rock salt, and maintaining 60°C for 1 h, the dye
is filtered and dried at 110°C.
Direct black 166
• The first step is the acid coupling of 3,3´-diaminobenzanilide to 1-amino-
8-hydroxynaphthalene-3,6-disulfonic acid (H-acid), followed by alkaline
coupling of aniline to the monoazo dye and finally coupling of the disazo
dye to m-phenylenediamine.

Direct Black 166

Direct dyes with a urea bridge
• By the end of the 19th century, it was discovered at Baden Aniline
and Soda Factory (BASF is a German chemical company) that the
reaction of aminoazo dyes with phosgene (COCl2) in aqueous
solution in the presence of soda resulted in valuable symmetrical
urea azo dyes:

• Direct yellow 50 is obtained, for example, by phosgene treatment of

two equivalents of the aminoazo dye prepared from diazotized 2-
aminonaphthalene-4,8-disulfonic acid coupled to m-toluidine.

Direct Yellow 50
 Synthesis of acid dyes (anionic azo dyes)
• The term “acid dye” derives from the dyeing process, which is
carried out in an acidic aqueous solution (pH 2-6).
• γ-acid (2,8-aminonaphthol-6-sulfonic acid) and H acid (1,8-
aminonaphthol-3,6-disulfonic acid), from which many important
wool dyes are derived.
• Especially in γ-acid coupling acid yields dyes with very good
lightfastness, which is presumably attributable to the formation of a
hydrogen bond between the azo bridge and the hydroxyl group peri
(The peri- prefix is used to describe substituents at the 1 and 8
positions. It is seen specifically in naphthalenes) to the azo bridge.

Wool have
amine groups.

• Two outstandingly lightfast dyes of good leveling power whose

dyeings on wool exhibit moderate wetfastness are acid red 42 and
acid red 37.
 Acid Red 37

Acid Red 42

• Through the choice of suitably substituted diazo components, bluish

red to blue wool dyes with good light- and wetfastnesses can be
produced, e.g., acid violet 14.

Acid Violet 14
Manufacturing of 4-amino-3-(4-toluenesulfonyl)acetanilide
• The manufacture of 4-amino-3-(4-toluenesulfonyl)acetanilide,
which is used as the diazo component: p-phenylenediamine is
oxidized with iron(III ) chloride to 1,4-benzoquinonediimine, to
which p-toluenesulfinic acid is added.
• The final step is partial acetylation (following scheme).

p-toluenesulfinic
acid
1,4-Benzoquinone
p-phenylene
diimine
diamine

Scheme 4-amino-3-(4-toluenesulfonyl)
acetanilide
• Further examples are acid red 32and acid blue 117.
• On wool both dyes exhibit quite good wetfastness and high leveling
power.

Acid Red 32

Acid Blue 117

• To achieve valuable dyes with alkaline coupling to γ-acid, the
amino group must be acylated [introduction of an acyl (RCO-)
group] or arylated [addition of one or more aryl (Ph-) groups].
• For example: acid Red 68.
• On wool it exhibits high leveling power and yields light- and
wetfast dyeings.

Acid Red 68
 Synthesis of reactive dyes
Triphenodioxazines (dioxazines) dyes
• The most important industrial process for synthesizing
triphenodioxazines for cellulose fibers involves reaction of two
equivalents of an aromatic amine with 2,3,5,6-tetrachloro-1,4-
benzoquinone (p-chloranil) and subsequent oxidative closure of the
ring.
• All commercially available dioxazines thus contain chlorine atoms
at the 6- and 13-positions.
• The process was discovered in 1911, and its simplicity, coupled with
excellent availability of raw materials, was the basis for the
commercial success of early dioxazines.
Step I
• In the first reaction step the starting materials are condensed in the
presence of an acid-binding agent such as soda ash or magnesium
oxide to form the 2,5-diarylamino-3,6-dichloro-1,4-benzoquinone.
Step II
• Ring closure is then
induced by heating
either with a metal Aromatic amine
halide or an acid
Soda ash /
halide catalyst in a Magnesium oxide (2,3,5,6-tetrachloro-
high-boiling solvent 1,4-benzoquinone)
(e.g., nitrobenzene)
or, in the case of
sulfonated dyes, by
heating with an 2,5-diarylamino-3,6-
oxidant in dichloro-1,4-benzoquinone

concentrated (Metal halide or acid

halide catalyst)
sulfuric acid.

Soda ash → sodium carbonate Triphenodioxazines

Improvement in ring closure
• The use of oleum in the second step is a significant improvement,
because oleum serves not only as a solvent but also as an oxidant,
permitting cyclization to proceed at or below room temperature.
• Ring closure continued to prove difficult with starting materials
containing sulfonic acid groups, which are of great importance in
reactive dyes, but this problem was overcome by resorting to a
mixture of oleum and peroxosulfate compounds.
• The halogens, manganese dioxide, and aqueous hydrogen peroxide
can also used as alternatives to peroxosulfate (Potassium
peroxodisulfate, K2S2O8).
Precautions
• The cyclization process needs a very careful choice of starting
materials and reaction parameters to obtain a product with the
desired brilliance and tinctorial (‫ )جس ﺳے رﻧگ بﻧے‬strength.
Symmetrical triazines (s-triazines)
• The triphenodioxazine chromophore can be converted to a reactive
dye by incorporating anchors that are attached to the dioxazine core
either directly or via bridging groups.
• The usual starting material is 2-chloro-5-nitrobenzenesulfonic acid,
which is treated with a diamine.
• Reduction produces the p-phenylenediamine derivative, which is
condensed with chloranil, and the resulting diarylamino-3,6-
dichloro-1,4-benzoquinone is isolated, dried, and then cyclized in
oleum containing peroxosulfate to yield the desired dye base.
• The base is converted to a reactive dye by reaction of the two
primary amino groups with two equivalents of an acylating agent Z-
Cl (monochloromonomethoxy-s-triazine).
• The reactive anchors are almost always derivatives of s-triazines
(following scheme).
Bridging groups
• Typical diamine bridges include 1,4-phenylenediamine-2-sulfonic
acid, ethylenediamine, and 1,3-diaminopropane.
 Diamine
p-Phenylenediamine derivative

2-Chloro-5-nitrobenzenesulfonic
acid

Condensation
Chloranil

Primary amino
group
← Primary
↓
amino group

Diarylamino-3,6-dichloro-
1,4-benzoquinone
(oleum + peroxosulfate)

s-triazines
Scheme: Synthesis of s-
triazines.
Z = Monochloromonomethoxy-s-triazine
Asymmetrical triazines
• Because of symmetry, all above triphenodioxazine reactive dyes
feature double or even fourfold anchor systems.
• However, dyes with only one anchor group can be prepared by
adding a single equivalent of acylating agent.
• Most asymmetric products (following) of this type are based on 1,4-
phenylenediamine-2-sulfonic acid and characterized by somewhat
reddish-blue hues (λmax = 560 nm).

← Z = monochloromonomethoxy-s-triazine
Use of 2-hydroxyethylsulfonylaniline
• 2-Chloro-5-nitrobenzenesulfonic acid or one of the above
mentioned derivatives can also be reacted with a 2-
hydroxyethylsulfonylaniline instead of with a diamine.
• After reduction of the 4-nitroaniline product, the reactive
intermediate followed by condensation with chloranil, the
cyclization takes place in oleum where, besides ring closure, the 2-
hydroxyethylsulfonyl groups are also esterified to
sulfooxyethylsulfonyl groups [vinylsulfone (VS) groups].
• Thus, the reactive anchor is formed along with the cyclization
reaction (following scheme):
2-Chloro-5-nitrobenzenesulfonic 2-Hydroxyethylsulfonylaniline
acid

Scheme.
• Other similar fiber-reactive triphenodioxazines are prepared by
replacing the sulfonic acid group in 2-chloro-5-nitrobenzenesulfonic
acid with a 2-hydroxyethylsulfonyl group.
• 4-Chloro-3-(2-hydroxyethylsulfonyl)nitrobenzene, which leads to
products containing a VS (vinylsulfone groups) group bound
directly to the dioxazine ring (following scheme).
4-Chloro-3-(2-hydroxyethylsulfonyl)
nitrobenzene

Scheme.
• In an analogous reaction, use of a diamine affords dyes with both
VS (vinylsulfone groups) and amino groups.
• Subsequent acylation of the free amino groups produces the four
anchor system (following).

Z = reactive anchor ← Z = reactive anchor

↓
Anchor
 Synthesis of disperse dyes
Chemical Constitution
• Industrially applied disperse dyes are based on numerous
chromophore systems.
• Approximately 60 % of all products are azo dyes, and ca. 25 % are
anthraquinone dyes, with the remainder distributed among
quinophthalone, methine, naphthalimide, naphthoquinone, and nitro
dyes.
• Azo dyes are currently employed to create almost the entire range of
shades; anthraquinone derivatives are used for red, violet, blue, and
turquoise.
• The remaining dye classes are used mainly to produce yellow
shades.
• Fastness properties and often also the structures are disclosed in the
Colour Index.
Synthesis
Monoazo dyes
• Frequently, weakly basic amines, such as negatively substituted 4-
nitroanilines or aminoheterocycles, must be diazotized.
• These reactions require concentrated sulfuric acid, phosphoric acid
(85 wt %), glacial acetic acid, propionic acid, or mixtures of thereof
as the reaction medium, with nitrosylsulfuric acid as the reagent.
• On an industrial scale, this reaction is conducted preferably in
enameled, stirred vessels.
• Whenever the stability of the amine or the diazonium salt permits,
diazotization is carried out in concentrated sulfuric acid at slightly
elevated temperature (10.40°C).
• With regard to safety, factors such as temperature and concentration
must be controlled carefully to avoid explosion.
• The sulfuric acid diazotization mixture is generally added directly
to the ice cold solution or suspension of the coupling component.
• If the diazonium salt is stable in dilute sulfuric acid, the
diazotization mixture may first be quenched with ice, possibly
clarified, and only then combined with the coupling component.
• Strongly negatively substituted 4-nitroanilines, such as 2,4,6-
trinitroaniline [489-98-5], 2,4-dinitro-6-cyanoaniline [22603-53-8],
2-methanesulfonyl-4-nitro-6-cyanoaniline, and 2,6-dicyano-4-
nitroaniline [20033-48-1], are difficult to diazotize,and their
diazonium salts tend to decompose extensively during the coupling
• process.
• This results in diminished yields and loss of clarity of the dyes.
• These difficulties can be avoided if 2-halogo azo dyes, preferably 2-
bromo azo dyes, are generated first, and the halogen is then
exchanged for the NO2 or CN group.
• These copper-catalyzed reactions proceed especially smoothly in
dipolar aprotic solvents such as ethylene glycol monoalkyl ethers,
dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone,
and they occur under considerably milder conditions than those in
the starting amine.
• In this process, the bromo-cyano exchange yields clear blue
polyester dyes (e.g., 22) of a shade which, until recently, could only
be obtained by using anthraquinones.

• By modification of the substituent in the 4-position of the diazo

component, this process yields further 2,6-dicyanoazo dyes, for
example, 4-methyl- or 4-bromo-2,6-dicyano derivatives, for which
the basic diazo component is otherwise not readily accessible.
• In this way clear red shades on polyester can be obtained.
Disazo dyes
• The simplest route to disazo dyes is by using p-aminoazobenzene.
• As p-aminoazobenzene has been classified in the EU as
carcinogenic, the use of derived disazo dyes like Disperse Red 151,
Disperse Yellow 7, Disperse Yellow 23, and Disperse Yellow 56
has diminished.
Aftertreatment
• Chemical synthesis produces dyes of varying particle size.
• When the dyes are applied in this form, uneven and spotty dyeing
results, and the dyeing process may be slow and frequently
accompanied by incomplete absorption.
• To assure high yield, good reproducibility, and faultless dyeing and
printing in commercial use, especially when densely woven fabric
or wound material is involved, the dye must be applied as a fine
dispersion that is stable under the process conditions.
• Therefore, the first requirement is that the dye itself be present in a
stable crystal modification that does not change during application.
• If such a modification cannot be obtained by synthesis, attempts
must be made to generate it by thermal posttreatment, for instance,
by heating the dye in an aqueous suspension in the presence of
nonionic detergents.
• The eventual dispersion process consists of grinding the moist dye,
generally in a ball, bead, or sand mill, in the presence of dispersing
agents.
• Since the dyeing rate depends on particle size, the aim is to reduce
the particle size to <1 m.
• A narrow particle-size distribution is important to minimize
recrystallization during storage and application.
• The dispersion agents used are primarily lignin sulfonates (sulfite
cellulose liquors); condensation products of naphthalene, sulfuric
acid, and formaldehyde; condensation products of m- and o-cresol,
formaldehyde, and 2-hydroxynaphthalene-6-sulfonic acid [93-01-
6]; or mixtures of these products.
• Literature on dispersing agents is relatively scarce.
• Difficulties in the production of disperse dyes may be encountered,
for example, in grinding or drying dyes with low melting points.
• Therefore, only dyes that have a melting point > 120°C, and
preferably > 140°C, should be used.
• Disperse dyes are sold either as aqueous pastes obtained by
grinding or as powders obtained by gentle drying of the paste.
• Powders are generally produced by spray drying.
• Important requirements for industrial products are the storage
stability of the paste and the ease with which the powder can be
redispersed in water.
• The actual dye content of commercial products is generally 20.40%
for pastes and 20.50% for powders.

Note:
The synthesis of monoazo disperse dyes by diazotization and
coupling is described under Azo Dyes (see Section 2.2).
 Nitro dyes
• Nitro dyes are the nitro derivatives of phenols having at least one
nitro group in the o- or p-position to the hydroxyl group.
• They have:
– The nitro group as the chromophore
– The hydroxyl group as the auxochrome
• Nitro dyes are of two types, namely:
– Acid dyes
– Disperse dyes
• Acid dyes are having a solubilising group such as sulphonic acid.
• An example of acid dyes is naphthol yellow S.
• Disperse dyes do not have any solubilising group and generally have o-
nitrodiphenylamine structure.
• An example of disperse dyes is disperse yellow.
Limitations
• These dyes are not very fast and hence have very little commercial
importance.
• These dyes have greenish yellow to yellowish brown colour.
• Some examples of nitro dyes are described as following:
Different examples of nitro dyes
Picric acid (2,4,6-trinitrophenol)
• It is the simplest member of this class.
• It is the oldest artificial dyestuff, prepared by Woulff (1771) by the
action of nitric acid on indigo.
• However, it is now prepared from chlorobenzene or phenol by the
following sequence of reactions:
(c) It is also prepared by oxidising s-trinitrobenzene with potassium
ferricyanide.

• It is a yellow crystalline solid, m.p. 122°C, with a bitter taste

(Greek: pikros → bitter).
• The yellow colour is probably due to the presence of quinonoid
structure.
Limitations
• It is generally used to dye silk and wool yellow.
• But the colour is fugitive (‫)ﻧﺎپﺎئيدار‬.
• Therefore, it is mainly used as an explosive.
Naphthol Yellow-S (2,4-dinitro-1-naphthol-7-sulphonic acid)
• It is obtained by the nitration of 1-naphthol-2,4,7-trisulphonic acid.
• The latter is obtained by the nitration of 1-naphthol.
• It is also obtained by the nitration of 4-nitroso-1-naphthol-2,7-
disulphonic acid.

• It is used as the sodium or potassium salt.

Advantage
• It is a cheap dye for wool and silk in an acid bath, giving pure
yellow shades.
• It is non-poisonous and is used as a food colour.
Disperse Yellow
• It is obtained by the condensation of 2,4-dinitrochlorobenzene with
p-aminophenol or with p-anisidine and dmethylation.
 Nitroso dyes
Conditions
• In these dyes, nitroso group being the chromophore and
generally hydroxy (phenolic) group being as auxochrome in
the ortho position with respect to each other.
• Nitroso dyes are obtained by the action of nitrous acid on
phenols or naphthols.
• The tautomeric oxime form is mainly involved in the
formation of lakes or metallic derivative because this form
gets stabilised by hydrogen bonding.
• Some important nitroso azo dyes are as following:
Some examples of nitroso dyes
Fast Green O (dinitroso resorcinol)
• It is obtained by the action of nitrous acid on resorcinol.
• Fast Green O forms a green lake with iron (III) which is fast to
light and washing.
• Iron green lake of fast green was one time important in calico
(‫ )رﻧگﺎئﯽ‬printing.
Naphthol Green Y or Gambine Y
• It is α-nitroso-β-naphtho1.
• With iron(III), it forms a green lake which is known as
Fast Printing Green.
Advantage
• This α-nitroso-β-naphthol is also used for the detection of
cobalt in the presence of nickel.
• The α-nitroso-β-naphthol is known as Gambine R .

Naphthol Green β
• The ferrous complex of 6-sulphonic acid derivative of α-nitroso-β-naphthol in the
form of sodium sulphonate is named as Naphthol Green-β.
• It is prepared by the treatment of ferrous sulphate, lime and sodium carbonate
with α-nitroso-β-naphthol 6-sulphonic acid which is prepared by the action of
HNO2 on β-naphthol-6-sulphonic acid (Shaffer's acid).
• It dyes wool to give fast green in an acid bath. [Octahedral ferric complex is
named as Naphthol Green β; (C30Hl5FeN3Na3O15S3].
 Azoic dyes
(Ingrain azo dyes)
• Azoic dyes are water insoluble azo colours which are formed on
cellulose fibres from selected diazo and coupling components.
• These are prepared on the cellulose or cotton fibres in two district
stages:
– The fibre is treated with an alkaline solution of a coupling
component.
– This is then developed with a diazonium salt.
• 2-Naphthol was originally used as the coupling component.
• Later on it was replaced by anilides of 2-hydroxy-3-naphthoic acid
(BON-acid).
• These new compounds had much greater substantively ( ‫مﺳتقل طور‬
‫ )پر‬to cotton and gave a range of bright shades.
• At present about 30 such coupling components and 50 different
diazo components are marketed.
• Azoic dyes give bright yellow, scarlet red, maroon and chocolate
shades of excellent fastness.
• These dyes are very popular due to their cheapness and bright
shades.
Some examples of azoic dyes
Para Red or Nitroaniline Red
• It is prepared by padding (dipping) the fibre with an alkaline
solution of β-naphthol containing Turky red oil and then dipping in
a solution of the diazotised primary aromatic amine.
Turkey Red Oil
• Turkey Red Oil is also known as Sulfated Castor Oil.
• This oil is obtained thru the process of adding salt of sulfuric acid
to ordinary castor oil, creating what is often called Turkey Red Oil.
• The addition of the sulfuric acid makes this oil completely water
soluble, thus when added to water it will disperse evenly without
needing a suspension agent.
• It is the only oil that will completely disperse in water.
• The oil is expressed from the seed.
• Sulfated castor oil is created by adding sulfuric acid to castor oil,
and is considered the first synthetic detergent.
• Turkey Red Oil has a distinct and heavy scent.
• It is a surfactant and therefore makes a wonderful base for a bath
oil as it mixes well with water, producing a milk bath.
Naphthol AS (R = Ph)
• Para red (nitraniline red) is an important azoic dye which has least
affinity for the fibre.
• Hence a carbonamido group is introduced at 3-position in β-
naphthol,e.g., Naphthol AS (R = Ph).
Fast Blue B-base
• It is prepared by reducing o-nitro anisole with zinc dust and sodium
hydroxide in water or in ethyl alcohol.
• The o-nitroanisole for this reaction is prepared by treating o-
chloronitrobenzene with methanol at 70-95°C under pressure in the
presence of sodium hydroxide.
• It is an azoic diazo component.
• It can be diazotised and coupled with a phenol like naphthol AS to yield
azoic dye on the fibre.
• However, it is mainly used to produce blue colour of moderate fastness on
cellulose fibres.
• Other azoic diazo components are as fo1lows:
 Triphenylmethane dyes
• This group of dyes is one of the oldest known synthetic dyestuff
groups.
• They are of brilliant colour due to resonance and cover a ranges of
shades from red to blue, including violet and green.
• However, the colour fades rapidly in light and due to this reason
they find less uses in textiles but are used for colouring papers, type
writer ribbons and other articles where fastness to light is not of
much significance.
• These dyes have the quinonoid group as their chromophores.
• These dyes are obtained by the introduction of NH2, NR2 or OH
groups into the para positions of the benzene ring of triphenyl
methane.
• The compounds so obtained are colourless and are called leuco-
compounds.
• These on oxidation are converted into the corresponding tertiary
alcohols called colour bases which on treatment with acid are changed
from the colourless benzenoid forms to the quinonoid dyes due to salt
formation.
• The coloured salts on treatment with alkali are converted into the
leuco-bases.
• Some structures of this class of dyes involve an aryl group than
phenyl and, therefore, in general this class can be called
triarymethane dyes.
Crystal Violet (hexamethyl parfuchsine or hexamethyl-
pararosaniline hydrochloride
• It may be obtained by heating michler's ketone with dimethylaniline
in the presence of phosphoryl chloride or carbonyl chloride.
• If the latter compound is used, then crystal violet may be prepared
directly by heating carbonyl chloride and dimethylaniline.
Change of colour with change of pH
• Its weak acid solution is violet, its strongly acid solution is green
and its very strongly acid solution is yellow.
• The colour changes may be explained as follows:
• In weakly acid solution, the crystal violet has been found to exist as
the singly charged ion (I).
• In this state, two-thirds of the charge will undergo oscillation in the
horizontal direction.
• In strongly acid solution, it has been found to exist as the doubly
charged ion (II).
• In this state, the whole unit of charge will undergo oscillation in the
horizontal direction and, therefore, the colour deepens.
• It is important to remember that the vertical direction of oscillation
gets inhibited due to the fixation of the lone pair by proton addition.
• In very strongly acid solution, it has been found to exist in form
(III) having three charges.
• In this ion relatively little resonance (with oscillanon. of charge) is
possible and therefore the colour lightens.
Applications
• Crystal violet is used to dye silk, wool and tannin-mordanted cotton
to bluish violet colour but the colour is not fast to light.
• Crystal violet is used in making indelible (‫ )جو مٹﺎيﺎ ﻧہ جﺎﺳﮑے‬ink and
pencils, in stamping pad, etc.
• It is used as an indicator in the determination of hydrogen ion
concentration of solution .
Chrome Violet
• It is prepared by heating salicylic acid and formaldehyde in the
presence of conc. sulphuric acid and an oxidising agent like
NaNO2.

• It is used as a mordant dye with reddish violet shade, though it

lacks in light fastness.
 Phthaleins
• These are used as indicators because they are sensitive to the action
of alkali solutions.
• Phenolphthalein is the most important member of this group.
Phenolphthalein
• It is prepared by heating phthalic anhydride (1 molecule) with
phenol (2 molecules) in the presence of conc. sulphuric acid as a
condensing agent.
• It is a white crystalline solid insoluble in water but soluble in alkalis
to form deep pink solution.
• Phenolphthalein is a white crystalline benzenoid (m.p. 261 oC),
insoluble in water but soluble in alcohol.
• It is also soluble in alkalis where it gives a red colour due to the
formation of its salt having quinonoid structure (dianion).
• On addition of a large excess of alkali, a colourless teranion is
formed which is again benzenoid.
• The coloured dianion may alkali, colourless ter anion formed which
is again benzenoid.
• The coloured diamon may easily revert back to colourless
benzenoid form in acid; because of this fact, phenolphthalein is
used as an acid-base indicator.
• On addition of concentrated hydrochloric acid, the colourless
teranion miraculously, gives yellow colour, while the dilute acids
simply protonate the ter-anion.
• The following reactions explain the whole gamut ( ‫ﮐﺳﯽ شے ﮐﺎ ُم َﮑ ﱠمل‬
‫) ِﺳﻠ ِﺳﻠہ‬.
• If the excess of strong alkali is added to the pink solution, it
becomes colourless again due to the loss of quinonoid structure and
resonance.
• Its 1 % solution in alcohol is used as an indicator in acid-alkali
titrations.
• It is also used as a laxative (‫ )دافع قبض‬in medicine.
 Xanthene dye
• These are derivative of xanthene.
• This group gives rise to brilliant fluorescent dyes having red to
yellow colour.
• Xanthene dyes obtained from xanthene by introduction of
auxochrome such as amino or hydroxyl group into position 3 and 6
i.e., the ortho and para position with respect to carbon linking the
two benzene nuclei:

Reason
• When auxochrome present at ortho and para position of xanthene
nucleus it extended the conjugation because xanthene nucleus has
electron density at ortho and para position.
• That's why it intensify the colour of xanthene dye.
Preparation of oxonium salt
• These are prepared on the same lines as phthaleins but these dyes
have dibenzo-1,4-pyran (xanthene nucleus).
• This dibenzo-1,4-pyran on oxidation form xanthone (9-keto-
xanthene), which on reduction changes into xanth-hydrol (9-
hydroxyxanthene).
• Xanth-hudrols yield oxonium salts with mineral acid.
 (9-Keto-xanthene)
Dibenzo-1,4-pyran (HgNa)
Reduction

9-Hydroxyxanthene
Different types of xanthene dyes
• The introduction of auxochrome into 3 and 6 position in
the xanthene nucleus gives dyes of various shades.
• Some important members of this group of dyes are
described as follows:
– Fluorescein
– Eosin
– Erythrosin
– Mercurochrome
Fluorescein
• It is prepared by heating phthalic anhydride and
resorcinol in concentrated sulphuric acid at temperature
of 200oC or 120oC in the presence of anhydrous oxalic
acid.
• First of all, a phthaline is formed, by the removal of one
water molecule then phthaline eliminates a second
molecule of water by interaction of two phenolic groups
to produce xanthene nucleus.
• Fluorescein is an orange solid, insoluble in water.
• Since fluorescein is coloured, hence it exibsts in p-quinonoid and
o-quinonoid forms (the latter being in the form of dipolarion,
predominates).
• It dissolve in alkalis to a reddish brown solution, which on dilution
exhibits a strong yellowish green fluorescene (persists upto 4 x 106
times dilution).
• As fluorescein is coloured, the structure (I), which is the non-
quinonoid uncharged structure, is unsatisfactory.
• However, two quinonoid structures have been postulated in which
the structure (II) is having the p-quinonoid structure while the
structure (III) is having o-quinonoid structure (this contains
tercovalent oxygen).
Confirmation of structure
• When the infrared spectra (1954) was recorded of phenol,
phenolphthalein, fluorescein and some of their alkali
derivatives, conclude that structure (I) is preferred over
other structures (II) and (III).
• The structure (II) is eliminated due to the absence of the
characterized absorption of the carboxyl group.
• Similarly, the structure(III) is eliminated because of the
frequencies of the carboxylate ion in (III) are absent.
• When fluorescein is dissolved in alkalis, it gives a
reddish-brown solution which on dilution gives a strong
yellowish-green fluorescein.
• The structure of fluorescein anion is (IV).
Uranine
• The sodium salt of fluorescein is known as uranine.

• It is used to dye wool and silk yellow from an acid bath;

the colors are fugitive.
• Fluorescein is used in tracing underground currents in sea
and rivers as well as a marker during accident.
Eosin
• It is tetrabromofluorescein.
Preparation of eosin
• It is obtained by the action of bromine on fluorescein in
glacial acetic acid solution.
• As eosin is red powder, its structure may not be (V) but may be (VII)
or (VIII).
• The alkaline solution of eosin shows a yellow-green fluorescence
which is attributed to the doubly charged structure (VI).

• Eosin is used to dye wool and silk a pure red, with a yellow
fluorescene.
• It is also used for poster printing.
• Most red inks are dilute solution of eosin.
Erythrosin
• It is tetraiodofluorescein.
Preparation of erythrosin
• It is prepared by iodination of fluorescein (similar manner as
eosin).

• As erythrosin is dark red powder.

• So, according to Arm’s strong theory it show two quinonoid
type structure i.e., ortho quinonoid and para quinonoid.
• The alkaline solution of this dye exhibit yellowish green
fluorescence due to their anionic (dianionic) structure.
• It is used as food colouring matter.
• It is also used as spectral sensitizer in photography.
Mercurochrome
• It is the disodium salt of dibromo-
hydroxymercurifluorescein.
Preparation of mercurochrome
• It is prepared by heating dibromofluorescein with
mercuric acetate or mercuric oxide in acetic acid and
sodium hydroxide.
• It forms green scale or granules.
• It dissolves in water forming a cherry-red solution
• It is used as an antiseptic in 2-5% solution for the skin
and in 1% solution for mucous membranes.
• It has also found application as a biological stain.
• Unlike eosin, mercurochrome is extremely fast to light;
preparations stained with this dye do not fade even when
exposed to strong sunlight for very prolonged period of
time.
• If mercurochrome is swallowed, it causes severe
mercurial poisoning.
 Heterocyclic dyes
• These include dyes mvolvmg heterocyclic rings and are not
grouped under other specific groups.
• They can be further divided as follows:
1. Quinoneimine dye
• A group of dye that are derivative of para-quinone imine or
para-diimine, in which the hydrogen atom of an imine group is
replaced by an aromatic residue containing OH-group or NH2.
• These dyes are obtained by replacing hydrogen atoms of the
amino group of quinonemonoimine of dimme by hydroxy or
amino substituted aryl groups.
• For example, indophenols and indammes derived from the
above two compounds are employed as dyes.
Indophenols
• The simplest member of this group of dyes is indophenol
blue.
• It is obtained by oxidising a mixture of p-
phenylenediamine and phenol with an alkaline
hypochlorite solution.

• The indophenols are blue.

• These are very sensitive to acids and these are, therefore,
not now used for textile coloration.
• However, these are applied in colour photography and also
serve as intermediates for sulphur dyes.
Indamines
• The simplest member of this group of dyes is phenylene blue.
• It is obtained by oxidising a mixture of p-phenylenediamine
and aniline with potassium dichromate in acetic acid.

• These dyes are blue or green.

• Like indophenols these are very sensitive to acids and they are,
therefore, not now used for textile coloration.
• However. they serve intermediates for the synthesis of azines,
thiazmes and oxazines.
2. Azine dyes
• These are the derivatives of phenazine which acts as chromophore.
• The amino and hydroxy groups para to one of the ring nitrogens are
the usual auxochrome.
• The strong colour of the products is due to resonance stabilisation
related to several contributing structures.
Safranine T
• It is obtained from o-toluidine which on diazotisation followed by
coupling with another molecule of o-toluidine yields
aminoazotoluene.
• This compound on reduction with iron and hydrochloric acid yields
a mixture of o-toluidine and 2,5-diammotoluene.
• The mixture is next oxidised with sodium dichromate and
hydrochloric acid.
• The indamine obtained is treated with aniline followed by oxidation
to form the dye safranine T.
It is used for dyeing tannin mordanted
cotton, bast fibres, wool, silk, leather and
paper.
It has also various applications in textile
printing.
It gives a bright red but has poor
fastness properties.
3. Thiazine dyes
• These dyes are analogues of the oxazines, an atom of
sulphur replacing oxygen in the heterocyclic ring.
• These dyes have phenazonium nucleus as chromophore
with amino groups para to the ring nitrogen as
auxochromes.
• These dyes have a colour range from green to blue and
have been used for colourmg paper, tannin mordanted
cotton and silk.
• Fastness to light is usually only fair.
• The most important thiazine dye is methylene blue,
discovered by Caro in 1876.
Methylene blue
• It is obtained by oxidising p-dimethylaniline with acid dichromate
in the presence of sodium thiosu1phate, followed by condensing the
resulting 4-(dimethylamino)aniline-2-thiosulphonic acid with
dimethyl aniline to form an indamine, and oxidising by dichromate
and copper sulphate to yield methylene blue.
• It is used in calico printing.
• It is used as an indicator and in medicine.
• Its zinc double chloride salt is used for dyeing tannin-mordanted
cotton.
• The change in colour in methylene blue has been attributed to the
following structural changes:
4. Thiazol dyes
• This group of dyes has the thiazole ring system, the presence of
this ring system, increases the substantivity for cellulosic fibres.
• The important examples of thiazole dyes is primuline.
Primuline
• When p-toluidine is heated
with sulphur, it leads to a
mixture of primuline base
and dehydrothio-p-toluidine.
• The latter is removed from
the mixture solution by
means of ethanol.
• This dye gives greenish yellow shades on cellulosic fibres but the
direct shade is of no interest because of its low fastness properties.
• This dye may be diazotised on the fibre and coupled with 2-
naphthol to a red shade.
• Similarly other shades are obtained with different coupling
components.
 Synthesis of some specific dyes
Eriochrome Black T (Chrome azo dye)
• β-Naphthol is first of all converted into nitroso derivative
and then reduced to get 1-amino-2-naphthol.
• Now it is sulphonated and nitrated to get l-amino-6-nitro-
4-sulpho-2-naphthol.
• This amine is diazotised and coupled with α-napthol in
alkaline medium to give Eriochrome Black-T.
• It is a chrome azo dye.
• The fibres are made to treat with solution of chromium
salts, followed by the dye to deepen the colour.
• Eriochrome black T is used as an mdicator for
complexometric titrations using EDTA.
Formation of 1-amino-6-nitro-4-sulpho-2-naphthol
HNO2 NaHSO4 Conc. H2SO4

Reduction
β-Naphthol

Conc. H2NO3
Conc. H2SO4 1-Amino-6-nitro-4-sulpho-2-
naphthol

Diazotisation and coupling

NaNO2, HCl Na2CO3

0 – 5 oC Coupling
α-Naphthol
Diazo oxide
(Diazonium ion)

Eriochrome Black T
Eriochrome Black A (Chrome azo dye)
• Its preparation is similar to Eriochrome Black T.
• Diazotization of 4-amino-7-nitro-3-naptho-1-sulfonic acid
in the presence of a small quantity of CuSO4 is followed
by coupling the product obtained with naphthol.
• It is an azochrome dye which can be applied to wool by
the modified method.
 Diazotisation
NaNO2, HCl Coupling
0 – 5 oC
CuSO4
β-Naphthol in alkali

4-Amino-7-nitro-3-
naptho-1-sulfonic acid

Eriochrome Black A
Eriochrome Red B (Chrome azo dye)
Preparation of pyrazolone derivative
Acetoacetic ester
↓

-H2O
C2H5OH
← Phenylhydrazine
(Keto) (Enol)
3-Methyl-1-phenyl-5-pyrazolone

• Acetoacetic ester is first of all made to condense with

phenylhydrazine to obtain a pyrazolone derivative which is the
coupler.
• l-Amino-2-naphthol-4-sulphonic acid is diazotised and coupled
with the pyrazolone derivative.
 Diazotisation
NaNO2, HCl
0 – 5 oC

Diazo oxide
l-Amino-2-naphthol-4-sulphonic acid (Diazonium ion)

Coupling
Na2CO3

Coupler Eriochrome Red B

Celliton Scarlet B (Disperse azo dye)
• Aniline is condensed with ethyl bromide (1mole) followed by
ethylene oxide to get the ethanol amine derivative, which is used
as the coupler.
• Then p-nitroaniline is coupled with the ethanol amine derivative
to get celliton scarlet-B.
• This is a disperse azo dye.
• The hydroxyethyl group (-CH2CH2OH) is the solubilizing group.
• Their dispersions are used to dye hydrophobic fibres like
cellulose acetate, nylon etc.
Preparation of coupler

1mole

Ethyl bromide
Aniline

Ethylene oxide
N-Ethyl-N-(2-hydroxy)ethylaniline
 Diazotisation
NaNO2, HCl
0 – 5 oC
p-Nitroaniline Diazonium ion

Coupling
Na2CO3

Celliton Scarlet B
Coupler
Diamond Black-F
• 5-Amino salicylic acid is diazotised and coupled with 1-
naphthyl amine in mild medium.
• The resulting amino azo compound is again diazotised
and coupled with 1-naphthol-5-sulphonic acid (sometimes
1-naphthol-4-sulphonic acid is also used).
• This is a disazo mordant dye which forms complex with
chromium.
• The fabric is mordanted by boiling with sodium
dichromate in presence of a reducing agent.
• This dye has good fastness to light and washing.
 Diazotisation
NaNO2, dil. HCl
0 – 5 oC

5-Amino salicylic acid (salt)

Diazotisation 1-Naphthylamine
Coupling NaNO2, dil. HCl
HCl 0 – 5 oC

Coupling
HCl

1-Naphthol-5-sulphonic acid (salt)

Diamond Black-F
Safranine-T (Heterocyclic dyes → phenazine group dyes)
• o-Toluidine is made to diazotise and couple with o-toluidine.
• The azo compound on reduction with iron and acid yields back o-
toluidine and 2,5-diaminotoluene.
• These products are condensed and oxidized with sodium
dichromate in acidic medium.
• The resulting indamine is condensed with aniline and the product is
again oxidized with sodium dichromate to give safranine-T.
• It is a basic dye belonging to phenazine group dyes.
• Mauveine belonging to this group, is the first synthetic dye
prepared by Perkin.
• This red dye is especially used for dyeing of paper.
• It is also used for dyeing of wool, silk and also cotton mordanted
with tannin.
Formation of 2,5-diaminotoluene

Diazotisation
NaNO2, dil. HCl

0 – 5 oC
o-Toluidine

Reduction
Fe + HCl
4 (H)
o-Toluidine
2,5-Diaminotoluene
Conversion into Safranine-T Condensation
and oxidation
Na2Cr2O7
HCl + 2[O]
- 2H2O
2,5-Diaminotoluene o-Toluidine

- HCl
Indamine

Aniline

Oxidation
Na2Cr2O7
HCl + 2[O]
- 2H2O

Safranine-T
Cyanine Green G
• The p-nitrotoluene is made to reduce by steam and iron filings
(Bechamp reduction).
• The product, p-toluidine, is sulphonated to yield 4-amino-toluene-3-
sulphonic acid.
• Phthalic anhydride is condensed with quniol in presence of
concentrated sulphuric acid.
• The resulting quinizarin is condensed with 2 moles of 4-
aminotoluene-3-sulphonic acid under pressure to get alizarin cyanin
green G.

p-nitrotoluene 4-Amino-toluene-3-sulphonic
acid
Quinizarin
Dispersol Blue
• Phthalic anhydride is made to fuse with quinol in the presence of
concentrated sulphuric acid to get quinizarin.
• This is condensed first with methyl amine under pressure and then with
mono ethanol amine under pressure to get dispersol blue.
• This is an anthraquinone disperse dye.
• Ethanolamine is the group which helps the formation of dispersion of the
dye.
Sulphur Black T
• Sulphur dyes get solubilized by reduction and the cellulosic
fabric is impregnated with this solution.
• Then the dye is regenerated by atmospheric oxidation.

• Sulphur dyes yield dark shades and they are cheap.

• They have good fastness towards light and washing.
• Sulphur black-T is used for dyeing umbrella cloth.
Drawback
• Their drawback is that they are affected by chlorine.
• They cannot be used for dyeing wool and silk as they are
damaged by sodium sulphide.
Classification of dyes on the basis of:
–Chemical and mode of application
Classification systems for dyes
• Dyes may be classified according:
– To chemical structure or
– By their usage or application method
• The former approach is adopted by practicing dye chemists, who
use terms such as azo dyes, anthraquinone dyes, and
phthalocyanine dyes.
• The latter approach is used predominantly by the dye user, the dye
technologist, who speaks of reactive dyes for cotton and disperse
dyes for polyester.
• Very often, both terminologies are used, for example, an azo
disperse dye for polyester and a phthalocyanine reactive dye for
cotton.
Classification of dyes on the basis of mode of application
• There are different methods by which dyes are applied on the
fibres.
• This depends on:
– The structure of the dye
– Nature of the fibre
– Physical properties such as solubility
• Thus, a method used for one group of dyes may not be suitable for
another group of dyes.
• Therefore, dyes can be classified on the basis of mode of
application.
• When dyes are classified in this way, the dyes with similar
structure will be placed in different groups.
• Some dyes are prepared in the final form and then applied on the
fibres whereas some of them are prepared on the fibre itself
(Ingrain dyes).
Direct dyes (salt dyes or substantive dyes)
– Examples: Azo dyes (congo red), stilbene, phthalocyanine dyes
Acid dyes
– Examples: Nitro dyes (picric acid, naphthol yellow), azo dyes
(metanil yellow, orange II)
Basic dyes
– Examples: Triphenylmethane dyes (crystal violet, malachite
green, megenta), xanthene dyes (rhodamine B), thiazinc dyes
(methylene blue)
Developed dyes (Ingrain dyes)
– Fast blue B base (azoic base), aniline black, naphthol AS (azoilc
coupler)
Mordant dyes
– Examples: Anthraquinone dyes (alizarin), azo dyes (Erichrome
black T), alizarin is applied to cotton mordanted with Al(OH)3.
Vat Dyes
– Example: Indigoid dyes (indigo), anthraquinone dyes
(indanthrene yellow GK)
Solubilized vat dyes
– These are an exterision of the vat dyes.
– They are sodium salts of the sulphuric estes of leuco
compounds.
– Example: Indigoid and anthraquinone
Sulphur dyes
– Example: Sulphur black T for umbrella cloth
Disperse dyes
– Example: Celliton scarlet B
Reactive dyes
– A reactive dye can be obtained by action of cyanuric chloride on
a dye containing amino group at low temperature and in neutral
medium.
– One of the chlorine atoms of the cyanuric chloride is substituted
by amino group of the dye.
– This is called cyanuration.
• Procion brilliant red M-2B, cibracron brilliant red B.

Solvent dyes
– Examples: Azo, anthraquinone and triphenylmethane dyes.
Note:
• In addition to these, there are many other dyes used in variety
of applications such as:
– Food colours
– Photographic dyes
– Optical brightners etc.
Chemical classification of dyes
• The dyes have different chemical structures derived from aromatic and
heteroaromatic compounds.
• They mainly differ in chromophores and auxochromcs.
• Hence, dyes can be classified on the basis of chemical structure,
particularly considering the chromophoric system.
• However, it should be noted that the dyes of a particular chemical class
may not have same properties, or mode of application.
Advantages
• This is most appropriate system for the classification of dyes which has
many advantages.
• First, it readily identifies dyes as belonging to a group that has
characteristic properties, for example, azo dyes (strong, good all-round
properties, cost-effective) and anthraquinone dyes (weak, expensive).
• Second, there are a manageable number of chemical groups (about a
dozen).
• Most importantly, it is the classification used most widely by both the
synthetic dye chemist and the dye technologist.
• Thus, both chemists and technologists can readily identify with phrases
such as an azo yellow, an anthraquinone red, and a phthalocyanine blue.
Nitroso dye
• Example: Fast green O, naphthol green G
Nitro dyes
– Example: Picric acid, naphthol yellow S
Azo dyes
– Example: Orange II (acidic azo dye), aniline yellow (basic azo
dye), congo red, para red
Diphenylmethane dyes
– Example: Auramine O
Triphenylmethane dyes
– Example: Malachite green, crystal violet
Phthalein dyes
– Example: Phenolphthalein
Xanthene dyes
– Example: Fluorescein, rhodamine B
Heterocyclic dyes
– Example: Phenazine, safranine T, phenathiazine, methylene blue
Polymethine dyes
– Example: Astrazone pink FG
Indigoid dye
– Example: Indigo, thio indigo
Anthraquinone dyes
– Example: Alizarin, indenthren yellow 4GK
Sulphur dyes

Phthalocynines
– Example: Isoindole, phthalonitrile, phthalogen, monastral fast
blue BS
Theories of dyes
 Shifting of λmax
Bathochromic shift (or red shift)
It is the shift of λmax to a longer wavelength due to substitution with
certain functional groups (e.g., -OH and -NH2) and conjugation.
• If a structure change in a dye molecule shifts the absorption towards
higher wavelengths, it will deepen, the colour of the dye in
accordance to the following sequence:
yellow → orange → red → purple → violet → blue → green
• Any group or a factor that produces the deepening of the colour in
accordance to the above sequence is knwn as bathochrome and the
effect, i.e., the deepening of colour, is known as bathochromic
effect.
• When a bathochromic group is introduced into a dye, it will increase
the resonance which in turn decreases the energy gap of the ground
state-excited state transitions with visible colour production.
• The shifting of the absorption towards higher wavelengths with the
introduction of bathochromes has been illustrated in following
figure.
 Figure: Absorption spectra of benzene, aniline, nitrobenzene
and p-nitroaniline.
Hypsochromic shift (or blue shift)
It is the shift of λmax to a shorter wavelength due to removal of
conjugation.
• If a structural change in a dye molecule shifts the absorption from
higher to lower wavelength, it will lighten the colour of the dye in
accordance to the following sequence:
green → blue → violet → purple → red → orange → yellow
• Any group or a factor that will lighten the colour of the dye in
accordance to the above sequence is known as hypsochrome and its
effect produced is known as hypsochromic effect.
• The hypsochrome group diminishes resonance, often by forcing π-
orbitals out of coplanarity.
Hyperchromic effect (or shift)
• Changes in the structure of a dye due to which the intensity of
absorption increases are said to be hyperchromic.
• This effect involves an increase in the intensity of absorption.
• It is usually brought about by introduction of an auxochrome.
Hypochromic effect (or shift)
• On the other hand, structural changes which decrease the intensity
of absorption are termed as hypochromic.
• It involves a decrease in the intensity of absorption.
• Bathochromic, hypsochromic, hypochromic and hyperchromic
effects are represented by the absorption spectra (following figure)
which are obtained by plotting the intensity of absorption against
wavelength (λ).

Figure: Absorption spectrum of a particular dye.

• The introduction of certain groups in a dye molecule causes the
bathochromic and hypsochromic effects.
• This is summarised in the following facts :
– The bathchromic effect is produced by the introduction of additional
auxochromes such as -OH and -NH2 groups in a dye molecule. For
example, when an additional-NH2 group comes in the aniline yellow,
chrysodine is produced which is an orange coloured dye.
– In addition to the auxochromes, the o- and p- directing groups,
when present on the aromatic ring, also deepen the colour. For
example, alkyl, aryl and halogens deepen the colour and are
therefore known afo bathochromes.
– When the alkylation of amino group is done, it produces the
bathochromic effect. On the other hand, when the alkylation as
well as acylation of phenolic groups are done, these will produce
hypsochromic effect. A good example of illustrating the
bathochromic effect is to introduce six methyl groups in
pararosaniline (red dye) nucleus to give crystal violet (violet
colour).
• The bathochromic effect is also produced by salt formation because
it increases the possibility of resonance which is again due to the
formation of dye ions.
What is theory of dyes?
• The psychological sensation which is produced when the light of
certain wavelength reaches the eye is known as the colour.
• A dye consists of a chromophore group and a salt-forming groups,
called auxochromes, which are polar substituents that modify their
colors.
Relation between colour and chemical constitution
• The colour of a compound is related to its chemical constitution.
• It is evident from the following examples.
– Benzene is colourless while its isomer fulvene is coloured.
– Reduction of coloured organic compounds results in the loss of
colour and oxidation of the reduced compounds regenerates the
original colour (Graebe and Libermann 1868).

• From this example, Graebe and Libermann concluded that

unsaturation was responsible for the development of colour.
• The relation between colour and chemical constitution of a
substance has been explained by different theories which are
described as follows:
The chromophore-auxochrome theory (Witt’s theory)
• In 1876, Otto Witt put forth a theory as to correlate color with
molecular structure (chemical constitution) and further a dye is
made up of two parts, chromophores and auxochromes.
• The theory is also named "The chromophore - auxochrome
theory".
Postulates
• Its main postulates are:
(i) Chromophore: The color of the organic compounds is due to
the presence of certain multiple bonded (unsaturated) groups
called chromophores (Greek word chroma = "color" and
phoros = "bearer").
An atom or group whose presence is responsible for the
colour of a compound.
• For example, diazomethane contains the unsaturated group, azo
group, and is, therefore, yellow in colour.
• On reduction, the azo group is reduced and methylhydrazine is
produced which is colourless because it does not contain unsaturated
group.
• A chromophore is the part of a molecule responsible for its color.
• The color arises when a molecule absorbs certain wavelengths of
visible light and transmits or reflects others.
• Some important chromophores are listed in following table.
Table: Some typical chromophores.
• Any isolated covalently bonded group that shows a characteristic
absorption of electromagnetic radiation in the UV or visible region.
• The presence of chromophore is not necessarily sufficient for color.
• To make a substance colored, the chromophore has to be conjugated
with an extensive system of alternate single and double bonds as
exists in aromatic compounds.
• The chromophore part of the colored substance (dye) absorbs some
wavelengths from white light and reflects back the complementary
color.
• A colored compound having a chromophore is known as chromogen
(by Witt).
• For example: C=C, C=O, NO2, –N=N–

Chromogens
A substance which can be
readily converted into a dye
or other coloured compound.
Classification of chromophore
Independent chromophore
• When a single chromophore is sufficient and does not need
auxochrome to impart color to the compound, then it is called
independent chromophore.
• Examples: —N=O (Nitroso), —NO2 (Nitro), —N=N— (Azo) etc.
Dependent chromophore
• When more than one chromophore is required to impart color in the
chromogen, then it is called dependent chromophore.
• Examples: >C=C< (Ethylenic), >C=O (Keto) etc.
• This type is exemplified by various examples.
• For example, acetone, containing one carbonyl groups, is yellow.
• A single C = C group does not produce colour in the compound but
if a number of them are present in conjugation, the colour usually
appears.
• For example, ethylene, CH2=CH2 is colourless while
CH3(CH2)6CH3 is yellow.
• Diphenylpolyenes provide another example.
• The formula of these is Ph(CH=CH)nPh.
• When n = 0, 1 or 2, the compound is colourless.
• However, when n is 3, the compound becomes yellow and when n
is further increased, the colour gets deepened, i.e., when n is 5, the
colour is orange, when n is 7, the colour is copper-bronze and when
n is 11, the colour is violet-black.
• The shade of the colour is also influenced by the proximity of the
chromophores.
• If these are separated by other groups, the compound becomes
colourless.
• For example
(ii) Auxochrome: Certain groups, while not producing color
themselves, when present along with a chromophore in an organic
substance, intensify the color.
• Such color assisting groups are called auxochromes (Greek word,
auxanien = to increase; chrome = color), i.e., they make the color
deep and fast and fix the dye to the fabric.
• An auxochrome is a functional group of atoms attached to the
chromophore which modifies the ability of the chromophore to
absorb light, altering the wavelength or intensity of the absorption.
• They are color helping or color intensifying groups.
• The auxochrome by itself does not produce color but it:
– Generally deepen the color of a chromogen.
– Helps the chromogen to adhere to the textile fiber.
• The auxochromes are acidic or basic functional groups.
• An auxochrome is a functional group of atoms with nonbonded
electrons when attached to a chromophore, alters both the
wavelength and intensity of absorption.
• If these groups are in direct conjugation with the π-system of the
chromophore, they may increase the wavelength at which the light
is absorbed and as a result intensify the absorption.
• A feature of these auxochromes is the presence of at least one lone
pair of electrons which can be viewed as extending the conjugated
system by resonance.
Table: Some typical auxochromes.
• The auxochromes serve two functions, namely.
(a) They increase the intensity of the colour
• This is illustrated by the toll owing example
– Benzene (no chromophore) is colourless
– Nitrobenzene (-NO2 as a chromophore) is pale yellow
– p-Nitroaniline (NO2 as a chromophore and -NH2 as an auxochrome) is dark
yellow
(b) They make the chromogen a dye by fixing it to the fabric or the
material to be dyed either by association or by salt formation
• The fixing of the dye to the fibre is generally due to the formation
of chemical bond between the fibre and the auxochrome.
• This is best illustrated by the following example:
Types of auxochromes
• Auxochromes are mainly of two types:
Bathochromic auxochromes
• These are the groups which increase the depth of the colour.
• These shift the absorption maxima from the violet towards the red
and thereby bring about the deepening of the colour.
• It is called red shift.
• When the hydrogen atoms in an amino group -NH2 are replaced by
-NHR or -NR2, a bathochromic effect is produced.
Hypsochromic auxochromes
• These are the groups which decrease the depth of the colour.
• These shift the absorption maxima from the red to violet and this
results in the fading of the colour.
• It is called blue shift.
• A hypsochromic effect is observed when -OH or -NH2 group of a
dye is replaced by –OCOCH3 or -NHCOCH3 group respectively.
• Witt's theory has been proved extremely useful empirical guide in
developing many of the dyes.
Effects of auxochrome on chromophore
• Auxochrome increases the color of any organic compound.
• For example, benzene does not display color as it does not
have a chromophore; but nitrobenzene is pale yellow color
because of the presence of a nitro group (-NO2) which acts as
a chromophore.
• But p-hydroxynitrobenzene exhibits a deep yellow color, in
which -OH group acts as an auxochrome.
• Here the auxochrome (-OH) is conjugated with the
chromophore -NO2.
• Similar behavior is seen in azobenzene which has a red color,
but p-hydroxy azobenzene is dark red in color.
• The presence of an auxochrome in the chromogen molecule is
essential to make a dye.
• However, if an auxochrome is present in the meta position to
the chromophore, it does not affect the color.
• An auxochrome is known as a compound that produces a
bathochromic shift, also known as red shift because it
increases the wavelength of absorption, therefore moving
closer to infrared light.
• Woodward-Fieser rules estimate the shift in wavelength of
maximum absorption for several auxochromes attached to a
conjugated system in an organic molecule.
• An auxochrome helps a dye to bind to the object that is to be
colored.
• Electrolytic dissociation of the auxochrome group helps in
binding and it is due to this reason a basic substance takes an
acidic dye.
Explanation for the colour modification
• A molecule exhibits colour because it absorbs colours only of
certain frequencies and reflects or transmits others.
• They are capable of absorbing and emitting light of various
frequencies.
• Light waves with frequency very close to their natural frequency are
absorbed readily.
• This phenomenon, known as resonance, means that the molecule can
absorb radiation of a particular frequency which is same as the
frequency of electron movement within the molecule.
• Chromophore is the part of the molecule where the energy difference
between two different molecular orbitals falls within the range of the
visible spectrum and hence absorbs some particular colours from
visible light.
• Hence the molecule appears coloured.
• When auxochromes are attached to the molecule, the natural frequency
of the latter gets changed and thus the colour gets modified.
• Different auxochromes produce different effects in the chromophore
which inturn causes absorption of light from other parts of the
spectrum.
• Normally, auxochromes which intensifies the colour are chosen.
• The important auxochromes are:
OH, NH2, NHR, COOH, CN, Cl

Classification
– Acidic: -COOH, -OH, -SO3H
– Basic: -NHR, -NR2, -NH2

• However, Otto witt

chromophore-auxochrome concept
fails to explain the color of certain dye Indigo
stuffs like indigo.
Armstrong's theory (1888)
• The colour of a compound is due to the presence of quinonoid type
of structure (ortho or para).
• This was based on the observation that benzene is colourless
whereas benzoquinone is yellow coloured.
• Thus according to this theory the aromatic compounds (benzenoid
structure) which can change into quinonoid structure are coloured.
• The quinonid ring is only a combination of the chromophores i.e., C
= C and C = O.
• Thus Armstrong‘s theory can be considered as an extension of
chrornophore theory.
• Hence this is called quinonoid theory to explain the cause of the
colour in the compounds.
• On the basis of this theory, it could be possible to explain the
colouring properties of some of the important compounds.
• For example,
– Benzene is cloudless whereas benzo-quinones are coloured.

– For example, when phenolphthalein is present in benzenoid

form, it is colourless. But its sodium salt can assume quinonoid
structure. Hence it is coloured (pink) in alkaline medium.
• However, Armstrong's theory has the following limitations.
– The iminoquinone and di-iminoquinone have quinonoid structures,
yet they are colourles.

– There are large number of coloured compounds but they cannot be

represented by qumonoid structures.

– Although this theory has a number of limitations, yet this theory

stimulated further research on the problem of colour and
constitution. It has found some practical applications in the dye
industry. Armstrong attempted to explain the colour of p-
nitrophenol (I) on the basis of a quinonoid structure (II) but there
was no evidence for the existence of such a structure.
• The actual preparation of two series of ethers (III) and (IV) of p-
nitrophenol by Hantzsch proved that there exists the phenomenon of
tautomerism in nitrophenols.

• Hantzsch presumed that a change in colour of a compound could be

attributed to a change in structure from benzenoid to quinonoid or vice
versa.
• However, Hantzsch also realised that colour is all additive property.
• It means that the state of the molecule as a whole should be taken into
consideration for explaining the colour of a compound.
• For example, the groups –NO2 and -ONa, if simultaneously present,
impart visible colour but if present alone do not do so.
• It means that the two groups must be interacting to yield a new
structure for the molecule.
• Thus, the change of colour is taken to be the evidence of the change of
structure.
• This phenomenon is known as chromoisomerism.
Baeyer's theory
• According to this theory (1907), the colour might be due to the structural
oscillation of the quinonoid condition between the two benzene rings.
• The change from one from to the other involved movement of electrons
and not movement of atoms.
• This theory is illustrated by considering fuchsonimine.
• It is a colourless.
• If an amino group is introduced in one of the benzene rings, it produces
deeply coloured Deobner's violet.
• This colour is due to the structural oscillation of the quinonoid condition
between the two benzene rings.
Nietzki's theory
• According to this theory, the colour of dye is deepened by the
addition of substituents.
• Further the deepening of colour is proportional to the increase
in molecular weight.
• For example, when benzene is replaced by naphthalene in azo
dyes, the colour is deepened from yellow to red.
• The Nietzki's rule is generally true but for the deepening of the
colour the nature of the groups added is important and not the
weight of it.
• This can be understood by considering the compound:
CH3-(CH2)a-X-(CH2)b-CH3
in which X is the chromophore.
• If X remains same but a and b are having different values, it is
interesting to note that the depth of the colour is found to be
independent of a and b.
Watson's theory
• According to this theory, the depth of the colour depends upon
many other factors besides the length of the conjugated chain.
• If the weight of the dye is increased without changing the
length of conjugated chain the shade becomes deeper because
vibrations become slower due to increase in molecular weight.
• For example, fluorescein on bromination gives eosin which
has a much deeper hue than fluorescein.
• Similar to other theories this theory is only empirical.
 General information
about fibres and dyeing
methods
General information about fibres and dyeing methods
• The application of dyes to textile fibres is one of the most important use
of dyestuffs.
• Dyeing is the process of application of dyes to the fibres to make it
permanently coloured.
• The exact method used for dyeing depends on two factors:
– The chemical structure as well as physical properties of the dyestutf.
– The chemical nature and also physical characteristic of the fibres.
Fibres
• The fibres are high molecular weight organic polymers having linear
structure.
• They may have different chemical structures.
• The fibres are classified on the basis of their source:
• The fibres are also classified as follows:
Hydrophilic fibres
• They have affinity to water (wetted by water) e.g., cotton, wool, silk.
• The presence of many hydroxyl groups make the fibres hydrophilic.
Hydrophobic fibres
• They have no afinity to water (not wetted by water), e.g., synthetic fibres
like nylon, polyester, acetate rayon, etc.
• These fibres should have sublimation fastness.
Table: The types of dyes used for various types of fibres.
How do dyes stick to fibres?
• This depends on the dye and the fibre to which the dye is attached.
• Protein-based fibres such as wool and silk have free ionisable
CO2H and NH2 groups on the protein chains which can form an
electrostatic attraction to parts of the dye molecule.
• For example the sulphonate group, SO3-, on a dye molecule can
interact with a NH3+ group on the protein chain.
• Cotton is a polymer with a string of glucose units joined together.
• Indigo which is used to dye denim jeans is a vat dye.
• Indigo is insoluble in water.
• The reduced form (leuko/leuco-form) of indigo is soluble.
• Cotton is soaked in a colourless solution of the reduced form.
• This is then oxidised to the blue form of Indigo which precipitates
in the fibres.
• Direct dyes are applied to the cotton in solution and are held to the fibres
by hydrogen bonds and instantaneous dipole-induced dipole forces.
• These are weak compared with covalent bonds hence these dyes are only
fast if the molecules are long and straight.
• Fibre reactive dyes actually form
covalent bonds with fibre molecules
and are therefore extremely colour fast.
• A dye molecule is reacted with the
molecule trichlorotriazine:

Leuco dye
• A leuco dye is a dye which can switch
between two chemical forms; one of which
is colorless.
• Trichlorotriazine can react with either –OH groups (present in
cotton) or –NH groups (present in wool and nylons), thus effectively
bonding the dye to the fabric.
Dyeing
• It is a process which is used to transfer the colour to the substances
being dyed.
• The dyeing process even now is being extensively studied with the
help of modem instruments.
• However, the dyeing of fibres involves one or more of the following
four types of forces:
Ionic interactions
• These arise from ionic sites of opposite charge in the fibre and the
dye molecules.
• For example, the dyeing of wool with acid dyes of the levelling type
(i.e., those with fairly simple structures) is mainly due to the
formation of salt-type chemical links between dye anions and
cationic groups in that fibre.
• This is shown in following figure.
• As the salt-type chemical links between dye anions and cationic
fibres are easily broken, the resulting dyeings have somewhat poor
fastness to wet treatments.
• Basic dyes are attached to wool, silk or acrylic fibres containing
anionic sites by salt-type linkages.
• Fastness to washing on wool and silk is in most cases rather poor
but usually reaches a high standard grade on polyacrylonitrile fibres.
• This has been attributed partly to difference in the strength of salt
bonds and partly to the hydrophobic nature of the synthetic fibre.
Hydrogen bonds
• These interactions are weak and are formed by sharing a lone pair of
electrons on nitrogen, oxygen or fluorine in a molecule with
covalently bonded hydrogen atom.
• The hydrogen bonds are involved in dyeing of wool, silk and man-
made fibres.
• Several hydrogen bonds forming between the dye molecule and the fibre structure
at a time may be sutliciently strong to hold the dye molecule to the fibre structure.
• This is shown in above figure.
• However, the dyeing of cellulose is not explained through hydrogen bonding
because water has more affinity for cellulose than dye molecules.
van der Waal's interactions
• These interactions are weak and mainly arise due to interactions between
molecules close to one another.
• In dyeing, these interactions arise due to the interaction between π orbitals of dye
and fibre molecule in linear fashion.
• van der Waal’s interactions become stronger between similar groups, e.g., alkyl
aryl in polyester dyes.
• When the tolal effect of such interactions become greater than a critical
requirement, the dye will attach to the fibre.
• This is shown in following figure.
• It appears that van der Waal's forces are effective only when the dye and fibre are
brought into proximity by some means as a salt-type link.
Covalent bonds
• These bonds are formed between dye and fibre molecules due to the reaction
between a reactive dye and a group such as -OH.
• Such reactive dyes were first introduced by ICI in 1956 under the name procion
dyes.
• They were soon fol1owed by Cibacron dyes by CIBA.
• These dyes are fast to washing.
• When a reactive dye having, dichloroazine reactive system undergoes reaction
with the cellulose structure having alcoholic hydroxy groups, one of the chlorine
atoms undergoes reaction with the hydroxy group of the fibre yielding a dye-fibre
attachment.
• This is shown in following figure.
• When the dyeing is carried out in aqueous medium, one chlorine atom gets
replaced by the oxygen of the hydroxy groups originally present in the cellulose
while the other chlorine atom gets replaced by hydroxy group by the reaction with
water.
• On the basis of various types of interactions between fibre and dye, it becomes
possible to know that which fibre should be dyed with particular dye (or dyes) or
not.
• The various conclusions are summarized as follows : .
– Cotton may he dyed or printed by direct dyes, vat dyes, solubilized vat
dyes, Sulphur dyes, ingrain dyes, azoics, reactive dyes and pigment
emulsions.
– Wool may be dyed with acid dyes. acid-mordant dyes, basic dyes and
reactive dyes.
– Silk may be dyed with direct dyes, acid dyes, mordant dyes and basic
dyes.
– Polyamide fibers may be dyed with acid dyes, disperse dyes and
disperse reactive dyes.
– Polyester fibres may be only dyed with disperse dyes.
– Modified polyprolene fibres may be dyed with only specially selected
disperse dyes.
– Polyacrylonitrile fibers may be dyed most suitably by cationic dyes.
– However, disperse dyes can be employed but with certain limitations.

Leuco dye
• A leuco dye (from the Greek leukos: white ) is a dye which can
switch between two chemical forms; one of which is colorless.
Cross dyeing
• The polymer chemist is now successful in increasing the versatility of the
new fibres by incorporating dye sites of a varying nature as required to
achieve dyeability with a predetermined class of dyes.
• It has now become possible to have polyesters, acrylics and polyamide
fibres which may be dyed with positive (basic, cationic), negative (acid,
anionic) or neutral (disperse) dyes.
• These developments have made possible for fabric designer to produce
materials (textiles, carpets) fabricated in patterns which can be dyed for
three different colours from one dye bath having three types of dyes.
• This concept is known as cross dyeing.
• This has now become popular as a low cost method of colouration.
Basic operations in the dyeing process
• The basic operation of the dyeing process involves the following steps:
– Preparation of the fibre
– Preparation of the dye bath
– Application of the dye
– Finishing
• We shall discuss these steps one by one.
Preparation of the fibre
• In order for the dyeing to be successful, it is essential that the preceding
operations must be performed carefully.
• The raw fibres get associated with foreign substances like oils, waxes,
lubricants used while spinning.
• These also get associated with sizing material and dirt processing.
• Hence the fibres are scoured with soap and other detergents before these
are dyed.
• This step helps the dye liquor to penetrate through the fibrous material and
thus produces level dyeing.
• This treatment has been found to depend upon various factors like the
nature of the fibre, the depth of the shade and the processing material to
which the dyed material is submitted.
Preparation of the dye bath
• The dye bath is prepared by adding necessary chemicals to the solution of
water soluble acidic, basic and direct dyes.
• If there are insoluhle vat dyes in the dyeing bath, they are reduced with
alkaline hydrosulphite to render them water soluble leueo compounds.
• After dyeing, the fibres are subjected to air oxidation when the original
colour on the fibres is generated.
• Beside dye, some other substances like wetting agents salts, carriers,
retarders and other assistants are also added to the dye bath.
• The function of the carriers is to improve the dyeing rate of hydrophobic
fibres (e.g., polyester) because they act as swelling agents.
• The function of retarders, which are colourless compounds, is to slow
down the dyeing process to the desired level by competing with the dye
for the reactive sites on the fibre.
• For example, acetic acid is used as retarder when dyeing of wool is done
with acid dyes.
Application of the dye
• In order to dye the fibre, it is immersed in the dye for a specified time at
optimum temperature.
• For getting level dyeing, stirring arrangement is used.
• Level dyeing indicates the uniformity of the dye on the fabric.
• This depends on the nature of the dye, the absorptive power of the fibre
and the conditions of the dyeing.
• Dyeing can be achieved by a hand operation or on a machine.
• In hand operation the fibrous material is moved in an open vat containing
the dye colour.
• In continuous dyeing process, two types of dyeing machinery are used.
• In one type, the dyeing bath is kept stationary while the yarn or cloth is
moved in it.
• This agitates the liquor kept in the dyeing bath.
• The excess dye is squeezed out by passing the yarn or cloth through a pair
of rollers.
• This also assures penetration of the dye.
• In second type, the fibrous material is properly supported while the dye
liquor is passed through it under pressure in one direction.
• At intervals, the direction of flow or the dye liquor is reversed.
• As the dyeing process is continued, there occurs the gradual decrease of
the concentration of the dye in the dyeing bath but there occurs the gradual
increase of the concentration of the dye on the fibre.
• At last a stage is reached when the dyeing bath contains practically no dye
and it is then said to be exhausted.
Finishing
• Various finishing processes are applied to dyed fibres or cloth.
• These processes are essential to produce lustre resistance to shrinkage and
creasing the other desirable qualities of feel and appearance.
• Dyeing processes are generally carried out using water as the medium.
• Hence purity of water is very important.
• It is necessary to soften water if not pure.
• The above operations may not be carried out in stated sequence.
• For example, in the dyeing of wool, first of all finishing treatments are
carried out and then the dyeing operations are carried out.
• On the other hand, in the dyeing of cotton, the dyeing process may be
carried out in between the two preparatory treatments.
Various methods of dyeing
• These are as follows:
Direct dyeing
• The method of dyeing depends on the absorptive power of the fibre, the
nature of the dye and the conditions of dyeing.
• However, it is necessary that the dye applied is fast to light, washing,
bleaching and other treatments and possesses an intensity comparable to
the standard sample.
• As wool and silk are amphoteric proteins, they can be dyed directly either
by acidic or basic dyes.
• However, mordant dyeing is used to get faster and brighter shades.
• The dye bath is prepared by dissolving the dye in cold water and to this
small quantities of sodium sulphate and sulphuric acid or acetic acid are
added.
• The material to be dyed is now introduced into the dyeing bath.
• Then, the temperature of the bath is gradually raised to about 60°C.
• At this juncture, exhausting agent like common salt or Glauber's salt
(Na2SO4.10H2O) is added and the temperature is raised to boiling.
• The material is rinsed cold and dried after dyeing is complete.
• The washing fastness is improved by after treatments of the dyed
fibre in a separate bath.
• The various treatments are as follows:
– Development with diazonium salts
– Diazotisation and development
– Treatment with chromium fluoride or sulphate and sulphate
– Treatment with formaldehyde
– Treatment with copper salts
• Treatments (i) and (ii) are quite useful in modifying the shade of the
dyed fibre.
• The cotton, linen and rayons do not show affinity for many dyes which are
used for dyeing wool and silk.
• However. they can be dyed with substantive dyes by direct dyeing method.
• The dye is dissolved in hot water.
• To this dye bath 5-20% sodium sulphate and 0.5-2% sodium
carbonane are added.
• Now the fibres are introduced in the dyeing bath which is first
maintained at 50-60°C and then raised in half an hour to 85-95°C.
• The dyeing is completed in about 1 hour.
• As the synthetic fibres are hydrophobic, they are resistant to the
usually cotton dyes.
• However, they can be best dyed from an aqueous dispersion of a
water-insoluble anthraquinone or azo dye in the presence of a
dispersing agent such as soap.
• In this process of dyeing, the dye enters the fibres in the form of a
solid solution.
Vat dyeing
• The ability of a colouring substance to function as a vat dye has
been found to depend upon:
– The property of the insoluble dye to form a soluble alkali salt by
reducing with alkaline reducing agent such as sodium hydrosulphite
 – The affinity of the leuco salt for textile fibres especially the
cellulose fibres.
• If fibre is immersed in the alkaline solution of a reduced dye (called
vat) and exposed to atmospheric oxygen or oxidising agent the
insoluble dye is regenerated by oxidation which remains fixed to the
fibre.
• The dye bath for vat dyeing is prepared by adding the dye (in the
form of paste with water) and a dispersing agent to water containing
caustic soda and hydrosulphite.
• Vat dyeing is carried out partly by a continuous process in which the
cotton cloth is impregnated with vat liquor.
• Then, it is steamed so that there occurs proper fixation of the leuco
compound to the fabric.
• Further, it is allowed to pass through a bath which contains
oxidising agent such as chromate and acetic acid or perchlorate.
• This generates the colour.
• Finally, it is soaped, rinsed and dried.
• When sulphur dyes are applied by vatting, sodium sulphide is used as a reducing
agent.
• Vatting method cannot be used to dye wool and silk because the
alkali used damages the fibre.
• The best example of vat dye is Indigo.
• Its two carbonyl groups are reduced to hydoxyls.
• The sodium salts of these hydroxyl groups are substantive to cotton.
• The two of the four carbonyl groups of Indanthrene Blue RNS are
reduced to hydroxyl groups.
• Vat dyes are quite expensive and must be applied with care.
• They offer excellent fastness when properly selected.
• They are the dyes most often used on cotton fabrics.
Mordant dyeing
• Whenever mordant dyes are applied, a pretreatment of the fibre with
a mordant material designed to bind the dye is essential.
• The mordant becomes attached to the fibre and then combines with
the dye to form an insoluble complex called a lake.
• An example of mordant is aluminium hydroxide which is precipitated in
cotton fibre.
• This mordant binds such dyes as Alizarin by formation of an aluminium
lake.
• When the mordant dyes are applied to wool, there occurs the
combination of a metal with the wool fibre and the lacking of the
dye with combined metal gives the fibre very good fastness to
washing.
• The metal used for wool is commonly chromium which can be
applied before, during or after dyeing.
• The colour can be changed using various metals.
• The dyeing bath for mordant dyeing is made by adding 2-5% acetic
acid (40% solution) and 10% sodium sulphate solution to the dye
solution.
• The temperature of the bath is initially maintained at 50-60%.
• When the fibre is introduced in the dyeing bath, the temperature of
the bath is gradually raised to boil till level dyeing is obtained.
• The temperature is allowed to drop and sodium dichromate, equal to half
the weight of the dye is added.
• Finally the material is rinsed.
• Mordant dyes have declined in importance mainly because equal or
superior results can be obtained with other classes of dyes at less expense
in time and labour.
Disperse dyeing
• This method is now used for dyeing polyester fibres although it was
original1y developed for cellulose acetate and polyamide fibres.
• In disperse dyeing, the dye is pasted to the fibre with water at about
40oC.
• Now a suitable dispersing agent and carrier (trichlorobenzene,
biphenyl or o-phenyl phenol) are added to the dye bath for
maintaining a fine dispersion and the dyeing is carried out at 80oC.
• Altematively, disperse dyes may be applied by a dry heat
(Thermosol) process to polyester fibres.
• In this case, the dye achieves molecular form by sublimation
(vaporisation) from the solid dye to the fibre surface.
• Extremely small particle size is also important for this process.
Formation of dye on the fibre
• Azoic dyes are produced inside textile fibres by zao coupling.
• In the usual procedure, the fibre is first impregnated with an alkaline
solution of the coupling component and then treated with a solution
of the diazonium compound.
• Finally, the dyed goods are soaped and raised.
• Special techniques have been devised for forming azoic dyes on
synthetic fibres.
• It is sometimes possible to apply both the diazo component and the
coupling component simultaneously from aqueous dispersion and
then to treat the goods with nitrous acid to produce the colour.
Dyeing of the wool with acid dyes
• The dyeing bath is prepared by dissolving the dye in cold water.
• To this small quantities of sodium sulphate and sulphuric or acetic
acid are added.
• Now the fibre to be dyed is introduced into the dye bath.
• Then the temperature of the dye bath is gradual1y raised.
• The dyeing is completed at the boiling temperature in one and half
hours.
• The fibre is then rinsed and finally dried.
• This process of dyeing is simple and cheap.
• It gives the brightness of the shades.
Dyeing with the reactive dyes
• Two methods are used for dyeing fibres with the reactive dyes.
• These methods are as follows:
– Impregnation by padding
– Dyeing in the dye bath
• In the first process (i), the dye is dissolved in one vessel.
• Wetting agent, sodium sulphate and sodium bicarbonate are dissolved in
another vessel.
• The two solutions are mixed before use.
• The cotton fabric is first padded through it and then dyed above 100oC.
• The function of bicarbonate is to yield alkali which fixes the reactive dye
on the fabric.
• The function of sodium sulphate is to prevent the movement of the dye
during drying because if unlevel results are obtained, they are difficult to
correct.
• The treatment is concluded with a light scour so as to remove unfixed
colour.
• In the second process (ii), the dyeing with certain reactive dyes may be
carried out in cold, using 2-3% of the dye along with relatively high
concentration of common salt.
Fastness properties
• These are the properties of the dyes which indicate the tolerance of
the dyes on the fibres towards the action of various foreign agencies
like light, washing, heat (sublimation), rubbing, perspiration (the
process of sweating), milling (rotating in wash wheel) etc.
• These fastness properties have been carefully standardised by
various agencies.
• For a given dye to be a commercial dye, it should have at least the
minimum rating number in each fastness concerned with the type of
the dye.
• However, certain exceptions are known.
• For example, most of the triphenylmethane (TPM) basic dyes have
low light fastness but they owe commercial value due to the
brilliancy of shades obtained on the fibres.
• The various fastness properties are as follows:
Colour fastness
• This measures the resistance of the textiles when they are exposed to
various agencies.
• The usual practice is to apply the dye on the fabric in specified
strength and subjected to the various agencies.
• For this, a scale or 1-5 is employed.
• In this scale, 1 means poor fastness while 5 means excellent.
Light fastness
• This measures the resistance of dyed fabric to light under standard
conditions.
• For this a scale of 1-8 is employed.
• In this scale, 1 denotes poor light fastness while 8 denotes best
fastness to light.
Sublimation fastness
• A dyed piece is kept in contact with undyed piece and subjected to
heat.
• Alteration in colour and degree are noted.
• This fastness is graded from 1-5.
• 1 denotes lowest rate in sublimation while 5 denotes highest rate in
sublimation.
• Sublimation fastness is useful for synthetic fibres.
Burnt gas fumes fastness
• A dyed piece is exposed to oxides of nitrogen.
• Alternation in colour is assessed.
• This test is largely used for synthetic fibres.
• Many other fastness properties, e.g., bleaching, milling, hand
washing, rubbing perspiration, etc. are also determined.

Table: The types of dyes used for various types of fibres.

 Non-Textile
Uses of Dyestuff
Non-textile uses (application) of dyestuffs
• The main application of dyes is for colouring textiles.
• However, dyes are also used for colouring a number of other
substrates such as leather, paper, food-stuffs, drug, polymers,
cosmetics, printing inks, lacquers, varnishes, paints, oils,
soaps, plastics; etc.
• These are also used in photography for sensitizing and
desensitizing photographic plates and as indicators in
analytical work.
• Dyes are also useful as staining agents in bacteriological work.
• The chromophoric and auxochromic groups in the dyes used
for dyeing these substrates have been found to be similar to
those used for textile fibres.
• However, their choice should be such that resultant dyed
substrate must be quite satisfactory.
• The various non-textile uses of dyestuffs are as follows:
Leather Dyes
• Natural leather is a protein substance and can be dyed with acid
dyes among others.
• Finished leather can also be dyed with pigments, the choice of the
colour type depending on the nature of finish.
• When basic dyes are used for dyeing leather, they give powerful,
rich and full shades on leather.
• Although these dyes produce surface dyeing, they withstand
perspiration (‫ َع َر ْق‬.‫)پَ ِﺳيﻧَہ‬.
• However, the main drawback of these dyes is that they are not fast
to light and when deep shades are dyed, a reddening of the shades
takes place.
• Whenever light shades on dye are desired, acid dyes are used in the
presence of formic acid.
• The dyes used for leather may not have the fastness properties but
the dye used should not be highly sensitive to variations in the
leather and, thus there should be uniform dyeing.
• In some leather dyes, alkyl sulphonic groups are present in one of
the components and they improve the penetration.
• The chemical class of dyes used is mostly azo dyes.
• However some acridine and aniline dyes are also used e.g.,
chrysoidine Y is basic mono azo dye used for dyeing leather.

Chrysoidine Y Base
• Basic dyes produce deep and rich shades.
• They are resistant to perspiration so leather dyed with these dyes are used for
making gloves and clothings.
• Nigrosines are bluish-black to black dyes.
• These are water-soluble dyes which are used chiefly for the dyeing of the leather.
• These are prepared by the oxidation of aniline hydrochloride with nitrobenzene
in the presence of ferric chloride at 160-180oC.
• Nigrosines are also useful in the preparation of boot polishes.
 Nigrosine
Paper Dyes
• Paper is a non-woven material made up primarily from cellulose
of varying degrees of refining.
• Dyes are adsorbed on the pulp by their affinity for the cellulose.
• Paper is colored by either dyeing or be pigmentation.
• Direct dyes are mostly commonly used.
• Dyes used for dyeing leather are also used for dyeing paper.
• Example of these are:
• The coloured materials for pigmentation must be finely divided.
• Most of carbon papers contain elemental carbon in finely divided
form and wax with small amount of oil-soluble dye to counteract
the reddish tone carbon black.
• In some cases a basic dye methyl violet 10 BNS is employed.
• Vat dyes are very suitable for colouring paper pulp because of their
fastness to alkalies.
• Carbon papers are made by coating the paper with a composition
containing waxes, oils and oil soluble dyes.
• Most of the carbon papers contain carbon black and a small amount
of a blue dye soluble in oil.
• The blue dye is used to counteract the slight-reddish tone of carbon
black.
• The paper may be coloured in the pulp or by dipping or by
impregnation.
• Acid dyes are used for internal colouring of paper but such papers
will bleed in water.
• Coloured papers and paper boards are manufactured for a
multiplicity of end uses, which in turn demand certain degrees of
fastness e.g., light, alkali, acid, chlorine, ink eradicators, and wet
rubbing.
• A coloured sheet used in plastic laminates requires the utmost in
fastness to light since this may be exposed to light over quite
extended periods of time.
• Fastness to alkali is of importance for paper subjected to gluing or
pasting operations where adhesives may be alkaline.
• Papers used for packaging alkaline materials such as soap must not
change shade on storage.
• Fastness to acid is important in writing papers where acid inks may
be used, acidic glues and adhesives may be encountered also.
• Napkin papers, paper towels, facial tissues, and papers employed for
packaging wet materials should be fast to bleeding in water. e.g.,
chrysophenine G, a direct dye.

Food Colours
• Food is mainly used for nutrition.
• However, it may be made more acceptable by colouration.
• Originally, the substances used for colouration of food were naturally
colouring matters like chlorophyll, cochineal, saffron and turmeric.
• However, they are still used to a great extent.
• These days synthetic dyes find extensive use due to the following
reasons:
– They offer a variety of shades.
– They are cheap.
– They can be handled easily.
• The criteria for selecting a synthetic dye for dyeing food are as
follows:
– They should be stable to light and heat.
– They should not interact with other ingredients.
– They should not interfere the taste and flavour of the food.
– They must be made free from harmful constituents such as lead
and arsenic.
– They must be totally harmless to human beings.
• In order to achieve the above properties, the food colours are to be
certified and permitted.
• These are certified on the basis of their complete analysis.
• Thus, there is legislative control for restricting the use of food
colours to certain permitted items which have been found to be
harmless after rigorous examination.
• The dyes used for colouring food are orange I, tartazine, amaranth,
erythrosine, naphthol yellow, crystal red F, fast red E, victoria
scarlet 3R, etc.
Solvent Dyes
• These dyes are not soluble in water but soluble in organic solvents.
• These dyes are derived from azo, anthraquinone, phthalocyanine
and xanthene dyes.
• These dyes find uses in varnishes, polish, printing inks, blue pen
inks, polymers, fats, oils, waxes. etc.

Wood Dyes
• These are applied to wood in water, alcohol or other solvents.
• These are used for staining wood in various shades for matching the same with
other parts of building.
• When the wood is painted with or soaked m the dye solution, the solvent
evaporates.
Medicinal Dyes
• The application of dyes in pathology was first of all discovered by Ehrlich who
found that the staining of nerve cells by methylene blue is selective.
• Later on, several dyes were found to stain and paralyse specific micro-
organisms.
• These discovires gave a clue to the use of dyes as antibacterial and
chemotherapeutic agents.
• However, their use in chemotherapy has considerably diminished because more
effective drugs like penicillin, streptomycin, sulphamilamides have been
discovered.
• Mercurochrome and acriflavine still find use as antiseptics in medicine.
• Other dyes having limited application as bactericides are brilliant green, crystal
violet, malachite green, methyl violet, gention violet.
Photography
• An ordinary photographic plate or film is sensitive only to violet
and blue in the visible region and to ultraviolet light.
• It is found that if certain dyes are added to the photographic
emulsion, it is interested to note that the coated plate becomes
sensitive to the whole visible spectrum and also sensitive to the
near infrared.
• The dyes added to the photographic emulsion are known as
photographic sensitizers.
• All dyes cannot act as photographic sensitizers.
• If the complete effect is to be achieved, the sensitizer added should
be highly pure and must be employed in very diluted form.
• The discovery of colour photography could be attributed to the
synthesis of efficient sensitizing dyes.
• Cyanine is one of the oldest synthetic dyes but its sensitizing
properties were discovered many years later.
• However, its use as a photographic sensitizer is limited because it
causes fogging of the plates.
• The sensitizing property of a cyanine dye can be enhanced by
adding ammonium or alkali aurous thiocyanate to the emulsion.
• Carbocyanine and isocyanines have been found to be much more
effective sensitizers in colour photography.
• Aqueous solutions of certain acid dyes are employed for hand
colouring and retouching of black and white photographs.

Dyes used in cosmetics

• A number of dyes are used in the preparations of various beauty
aids such as face powders, lipsticks, nail polishes, hair darkening
formulations etc.
• The dyes and pigments used in cosmetics require to have certain
properties.
 – They should have brightness and attractiveness.
– They should have resistance to perspiration.
– They should be non-toxic.
– They should be water soluble or oil soluble.
– They should not affect skin.
• Face powders and lipsticks are coloured with organic or mineral
pigments.
• The dyes used for nail and lipstick are derivatives of fluorescein.
• Dibromoderivative of fluorescein i.e., eosin dispersed in oil is used as
nail polish while tetrabromo derivative of fluorescein gives coloured
lakes with transition metal salts which are oil soluble and are used in
lipsticks.
• Melanin and p-aminodiphenyl sulphonic acid are used as black dye in
hair dye formulation.
Indicators and reagents
• In analytical chemistry, a number of dyes find valid applications
which are as follow:
• As pH indicators, in volumetric analysis e.g., phenolphthalein,
methyl orange, methyl red, congo red, etc.
• As oxidation-reduction indicators, in volumetric analysis e.g.,
methylene blue, indigo carmine, etc.
• As adsorption indicators in volumetric analysis in the titration of
halides with silver nitrate, etc., dichlorofluorescein, eosin, etc.
• As precipitants for the determination of metals listed as below:
• Certain dyes are known which change colour at specific temperatures.
• Such dyes are used in observing the variations in temperature in
different parts of machinery.
Flourescent dyes
• In our daily life, luminescence is desired.
• For this purpose, fluorescent dyes are used for dyeing and printing
theatrical fabrics, carpets in cinemas and other purposes.
• Certain fluorescent dyes, which are activated by ultraviolet light but
do not have after-glow, are used for night marking of streets and
direction signs.
• An example of fluorescent dyes is fluorescein.
• This emits an intense green fluorescence.
• This is mainly used for the detection of leaks in drains.
• During the war, airmen are provided with a pack of fluorescein.
• If they are forced down into sea, the dye is released into the water and
this produces a green patch which can be seen from a great distance.
• Thus, the rescue operations can then be easily guided.
Coloured smokes
• During the wartime, coloured smokes are produced for giving signals.
• These are produced by igniting a mixture of the pigment, potassium
chlorate and sugar.
• The pigment used must have the properties like colour, volatility and
thermal stability.
• The pigments used in producing coloured smokes are 1,5- and 1,3-bis
m-toluidino anthraquinone (violet), 2-bromo-1-amino-4-toluidino
anthraquinone (blue), l-amino-4-hydroxy anthraquinone (wine red)
and 1,2,4-trihydroxy anthraquinone (brown).
Camouflage colours
• During war times, precautionary steps are required to prevent the
detection of targets by infrared photography.
• For this purpose, the dispersions of the phthalocyanines and of the
pigment green (iron complex of 1-nitroso-2-naphthol) are used.
Recent applications of dyes
Dyes for lasers
• Laser is an acronym stands for Light Amplification by Stimulated
Emission of Radiation.
• Laser are used in a variety of application of medicine e.g., for eye
surgery therapy, for carpel tunnel syndrome and for photocoagulation,
• Laser light is monochromatic, directional and coherent, while ordinary
white light is a combination of many colours of light, emitted in many
directions away from source.
• Laser consist of lasting medium which is either gaseous or liquid or
solid.
• Semiconductor material is also used which may be in liquid solution
or in suspension form.
• Dyelaser in which complex organic dyes in solution are the laser
material can be tuned to produce light of any chosen wavelength
over a range of a sizable fraction of visible spectrum.
• One of major sources of chemical hazards from lasers is from the
organic dyes used in dyelasers.
• Rhodamine CG is used as dyelaser.
Bio-medical applications of dyes
• Methylene blue, a thiazine dye is useful as a vital stain, since it deeply
colours parts of the living tissues, such as peripheral nervous system,
leaving other parts unstained. Methylene Blue is one of the most common
stains used in bacteriological technique for examination of pathogenic
organisms such as tuberculosis and cholera bacilli.
• Malachite green free from zinc is used as bacteriological and histological
stain.
• Phenolphthalein, a triphenylmethane dye is a mild tasteless purgative
while disodium salts of tetraiodophenolphthalein and phenoltetraodo
phthalein are used for X-ray examination of gall bladder. Disodium
phenoltetrabromophthalein disulphate is used in the examination of liver
function.
• The opacity of 3-iodo and 4-iodoalizarin is used in X-ray visualisation.
• Erythrosine A and erythrosine B are used as microscopical stains.
• Ethoxazene, pyridium and neotropin are mono azo dyes which are useful
staining media for tumors.
• Riboflavin (vitamin B2) is a fluorescent yellow, water soluble pigment.
• Nile Blue 2B is an oxazine dye used as a stain and inhibits the growth of
cancer cells.
Dyes for synthetic fibres,
Toners, Lakes, Food
colours, Food dyes, Dye
fixer.
Dyes for synthetic fibres
Disperse dyes
• Disperse dyes include water insoluble dyes which could be applied
on synthetic fibres.
• None of the other classes of dyes had been good for dyeing
cellulose acetate.
• Some dyes were reported which did not possess the solubilizing
groups like SO3Na.
• These had been found to dye the cellulose acetate from a water
dispersion.
• Green and Sanders in 1923 prepared temporarily solubilized dyes
having -N-CH2SO3Na groups.
• These dyes were sold as ionamines e.g., ionamine orange CB.
• This dye got hydrolyzed in the dye-bath giving a finely divided insoluble
dye which got dissolved in the fibre yielding a solid-solid solution.
• These dyes lost the solubilising CH2SO3Na group on hydrolysis.
• These dyes were later replaced by acetate dyes which were aqueous
disperse ions of insoluble dyes in a finely divided state (1 to 4 μ) and
could be able to dye the fibre from aqueous dispersion.
• Several dyes manufactures produced these dyes which were named
disperse dyes by C.M. Whittaker in 1953.
• These dyes had been dispersed by several techniques such as precipitation,
milling with surface active agent, or milling with special kind of sand or
glass.
• The disperse dyes should possess a slight solubility in water for proper
dyeing.
• Dispersing agents are added to the dye to disallow aggregation but to
enhance solubility.
• Several kinds of dispersing agents like alkyl sulphates, alkylaryl
sulphonates.
• Fatty alcohol or amine + ethylene oxide condensation products,
naphthalene sulphonic acid + formaldehyde condensation products, lignin
sulphonate etc. have been used with disperse dyes.
• Some of these dyes get sublimed during ironing.
• Hence a sublimation fastness rating has to be introduced.
• Some of these dyes with NH2, N-alkyl group are influenced by traces
of nitrogen oxides in the city atmosphere resulting in change of shade.
• Fastness to burnt gas fumes provides rating of this capacity.
• With the introduction of polyester fibres in 1950 there occurs the rapid
development in this field to make dyes suitable for polyester fibers and
several modifications have been carried out.
• The chemical constitution of many of the new disperse dyes is
unknown.
• However, most of the disperse dyes belong to azo and anthraquinone
class which will be described as following:
Azo dyes
• The monoazo disperse dyes have been reported to give almost a
complete range of shades.
• These dyes are largely used for cellulose acetate (CA) and polyester
(PE) fibers and their blends with cotton, polyamides (PA),
polyacrylonitriles (PAN) and cellulose triacetate (CTA).
 Cibacet yellow GBA, C.I. Cibacet diazo black B
disperse yellow 3, 11855. disperse black 2, 11255

Disazo dyes
• The disazo dyes find use in dyeing CTA and PE fibres.
Anthraquinone disperse dyes
• This group largely provides blue and violet dyes.
• The earliest known dye was Duranol Red 2B, C.I. Disperse Red
1560710.

Methine or styryl dyes

• Methine dyes provide yellow shades e.g., Celhton Fast Yellow 76,
naphthostyril dyes

Naphthostyril dye
Coumarin dyes
• These dyes are used for polyester fibres and give fluorescent yellow
shade.
Formazin dyes
• These give blue disperse dyes which are suitable for nylon.
Cationic dyes for synthetic fibres
• These dyes are used specially for acrylonitrile fibres.
• These dyes possess azo, anthraqumone or triarylmethane or cyanine
as the chromophoric system.
• Most of the basic dyes can act as cationic dyes.
• Some of the basic dyes possess good fastness properties for
polyacrylonitrile (PAN) fibres.
Anthraqninone based dyes
• An example of anthraquinone based cationic pendant dye is as
follows:
Cyanine dyes (Methine and Polymethine Dyes)
• This group of dyes is termed as cyanine dyes.
• The molecules of dyes have a methane -CH= or a chain of
conjugated methine groups.
• The terminal groups and the number of conjugated methine groups
ascertain the colour and properties of the dyes.
• A number of these dyes find use as photographic sensitisers in
colour photography.
• Some of these dyes also find use as cationic dyes.
• The cationic dyes of this class have at least one of the terminal
groups as a quaternary nitrogen group.
 Astrazone Yellow, 3GL
C.I. Basic Yellow 11
48055

Triarylmethane cationic dyes

• Two of the dyes belonging to this class have been Astrazone Blue G
or Rhoduline 6G C.I. Basic Blue 1, 42025 and Astrazone Blue B,
C.I. Basic Blue 5 42140 which posses the following structure:

Astrazone Blue B Astrazone Blue G

Oxazine cationic dyes
• An oxazine dye for PAN fibres has been Astrazone Blue BG C.I.
Basic Blue 351004 whose structure is as follows:

Naphthostyrilc cationic dyes

• These are blue dyes having good fastness.
• One example from BP 1353983 is as follows :
Toners
• These are chemical compounds which are used to change the colour of the
fabrics before applying the main dye itself.
• This is specially applied for synthetic fibres where disperse dyes are used.
• They are the salts of the dyes which arc precipitated without usmg any
substrate.
• They were initially used for toning printing inks and hence they arc called
toners.
• The toners have better colour strength compared to lakes.
Lakes
• These are chelate compounds formed between the metal and dye.
• They are
• formed when the dye is applied by mordant dyeing where the metal hydroxides
are usually used as mordants.
• They are soluble organic dyes which are precipitated on an inorganic substrate.
• The inorganic substances are colourless compounds like hydrated alumina or
barium sulphate.
• Lake can also be the insoluble metal complex of an organic dye. The lakes have
• higher brightness and better transparency when used in oil paint.
Food colours
• Food is mainly used for nutrition.
• However, it may be made more acceptable by colouration.
• Originally, the substances used for colouration of food were naturally
colouring matters like chlorophyll, cochineal, saffron and turmeric.
• However, they are still used to a great extent.
• These days synthetic dyes find extensive use due to the following
reasons:
– They offer a variety of shades.
– They are cheap.
– They can be handled easily.
• The criteria for selecting a synthetic dye for dyeing food are as
follows:
– They should be stable to light and heat.
– They should not interact with other ingredients.
– They should not interfere the taste and flavour of the food.
– They must be made free from harmful constituents such as lead
and arsenic.
– They must be totally harmless to human beings.
• In order to achieve the above properties, the food colours are to be
certified and permitted.
• These are certified on the basis of their complete analysis.
• Thus, there is legislative control for restricting the use of food
colours to certain permitted items which have been found to be
harmless after rigorous examination.
• The dyes used for colouring food are orange I, tartazine, amaranth,
erythrosine, naphthol yellow, crystal red F, fast red E, victoria
scarlet 3R, etc.
Food dyes
• Most synthetic and natural dyes commonly used in food, drugs, and
cosmetics are carefully controlled materials, regulated by the
government agencies in the EEC, the United States, and Japan.
• These currently consist of very few (under 100) dyes and are listed
in the approved list.
• Regulations list the approved color additives and conditions under
which they may be safely used, including the amounts that may be
used.
• The most frequently used synthetic dyes for food, drugs, and
cosmetics belong to azo, anthraquinone, carotenoid, and
triarylmethane chemical types.
• The following two azo series food dyes are good examples.
 Dye fixer (Mordant)
• Dye fixer is the most essential chemical (sodium carbonate or soda
ash) in our dyeing process, because it causes the chemical reaction
that makes these dyes become part of the fabric.
• These dyes will not work without the use of dye fixer.
• In direct application dyeing, the fabric is first soaked in a solution
of dye fixer dissolved in water.
• When used for solid color dyeing, the dye fixer is added to the dye
bath near the end of the dyeing process.
Cationic fixing agents
• Various pretreatment and after treatments system have been
developed but at the moment most widely used are cationic fixing
agents.
• These chemicals function by forming a complex of high molecular
weight and low aqueous solubility and therefore high wet fastness,
amines, quaternary ammonium, phosphonium, and tertiary
sulphonium compounds and dicyanidiamide, formaldehyde can be
used as dye fixing agents to improve there wet fastness properties.
Mordant
• The term mordant is used for chemicals which usually have a metal
with a valency of at least two or more, they can also be other types
of compound as well.
• Natural dyes also referred as mordant dyes; do not readily adhere to
cotton so mordants are used.
• Mordants are needed to set the color when using natural dyes.
• Different mordants will give different hue color with the same dye.
• A mordant is thus a chemical agent which allows a reaction to occur
between the dye and the fabric.
• In textiles, mordants are used to fix the color in dyeing or fabric
printing, especially for fabrics of plant origin (cotton).
• Mordant is added to the dye source to influence it, it does not serve
as a color source on its own.
• The fabric is impregnated with the mordant, then during the dyeing
process the dye reacts with the mordant, forming a chemical bond
and attaching it firmly to the fabric.
• The choice of mordant depends upon the fabric.
• An alkali mordant, such as soda ash, works well with cotton, and
acid mordant such as vinegar works well with wool.
Metal mordants
• Metal mordants can be defined as a polyvalent metal ion which
forms coordination complexes with certain dyes.
• Two types of bonds are involved in the fundamental reaction
between a mordant dye and a mordant.
• One is a covalent bond with usually hydroxyl oxygen and the metal
atom.
• The other is a coordinate bond with the metal with the double
bonded other oxygen also referred as “chelation”.
• It is possible, however that the formation of dye‐mordant
complexes involving several molecules of dye can also form.
• Varying the amount of mordant with the dye is a way to exert some
control over the change in hue color.
• The two commonest metals used in natural dyeing are aluminium
and ferric ions both having valencies of three.
Different types of mordants
• Mordants are commercially available, commonly in the form of salts
from metals such as chrome, copper, tin, iron and aluminium.
• These mordants are listed in descending order of relative toxicity.
• Other types of mordants which are not metal mordants are tannins,
cream of tartar, baking soda and vinegar.
• The later two serve to change the alkalinity and acidity, respectively,
of the dye, another property that influences the final color.
• Besides metallic salts, tannins and other inorganic compounds,
sometimes oils such as oil of turkey and its type are also used as
mordants
Enhancement by mordant
• It is often remarked that the addition of a mordant to an appropriate
dye solution results in a very sudden, dramatic change in color.
• This is due to the incorporation of the metal atom into the
delocalized electron system of the dye.
• Metals have relatively low energy levels, so their incorporation into
a delocalized system results in lowering of the overall energy.
• The absorbance of the hue and thus its color is related to this
phenomenon.
Use of mordant
• Most dyers mordant the cloth and then apply the dyes as two
separate steps.
• The advantage is that the mordant has a chance to “bite” into the
fiber, so that when the color is applied, maximum amount of
bonding takes place.
• Many dyers turned to natural dyes because they are safe and
non‐toxic, so it is imperative to ascertain whether the mordants that
are used to fix the dyes are safe or not.
• Most of the mordants that are used for natural dyeing are not
seriously toxic.
• The better results obtained in case of pre‐mordanting with stannous
chloride and ferrous sulphateare attributed to the empty d‐orbitals of
ferrous and stannic ions.
• The mode of binding of dye seems different with iron and
aluminium ions.
Binding with ferrous ion
• The pre‐mordanting with ferrous sulphate showed least color discharge
after washing because of the pretreatment of fabric with tannic acid which
shows 100% iron binding efficiency in terms of tannic acid equivalents.
• The iron binding by phenolicsincreases with increasing number of -OH
groups.
• A flavonoidring B and a 3’,4’‐dihydroxy group is required for Fe‐binding
(I) and in case of aluminiumion binding, the 3‐hydroxychromane groups
are required as shown in the structure (II) below.
Mechanism of fixation of natural dyes through mordants
• Most of the natural dyes have no substantivity on cellulose or other
textile fibres without the use of a mordant.
• The majority of natural dyes need a mordanting chemical
(preferably metal salt or suitably coordinating complex forming
agents) to create an affinity between the fibre and dye or the
pigment molecules of natural colourant.
• These metallic salts as mordant form metal complexes with the
fibres and the dyes.
• After mordanting, the metal salts anchoring to the fibres, attracts the
dye/organic pigment molecules to be anchored to the fibres and
finally creates the bridging link between the dye molecules and the
fibre by forming coordinating complexes.
• Aluminium sulphate or other metallic mordants anchored to any
fibre, chemically combine with certain mordantable functional
groups present in the natural dyes and bound by
coordinated/covelent bonds or hydrogen bonds and other
interactional forces as shown below:
• Thus, for proper fixation of natural dyes on any textile fibre,
mordanting is essential in most of the cases.
• The said mordanting can be accomplished either before dyeing
(premordanting), or during dyeing (simultaneous mordanting) or
after dyeing (postmordanting).