Dyes and Dyeing

A Closer Look at Dyes and their Colorful History

Although numerous colored compounds and, thus,

potential dyes have been produced since the 1850s, the
successful dyeing of a cloth sample depends both on the
chemical structure of the fibers in the cloth and the
chemical structure of the dye.
The structures of some common fibers are given below.
Wool, silk, and cotton are natural fibers. Wool and silk are
polypeptides, or polymers made of amino acid units. The
acidic and basic amino acids present in these polymers
provide many polar groups to which a dye can bind. Cotton, which is pure cellulose, has many hydroxyl
groups (–OH) which can form hydrogen bonds to dyes. Rayon (or acetate) is cellulose in which some of
the hydroxyl groups have been acetylated. Thus, rayon has fewer hydrogen bonding sites and is more
difficult to dye than cotton. Synthetic fibers such as nylon, dacron, and orlon contain have fewer polar
sites than the natural fibers. Nylon, a polyamide, is made by polymerizing a dicarboxylic acid and a
diamine. It can be synthesized so that either amino or carboxylate groups predominate at the ends of the
chains. Dacron is an example of polyester made by polymerizing ethylene glycol and terephthalic acid.
Orlon is a polymer of acrylonitrile.

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In order to dye the various types of fibers, numerous methods have been developed. Dyes have come to
be classified according to the dyeing method most commonly employed in their use. These
classifications are: direct dyes, disazo dyes, ingrain or developed dyes, mordant dyes, vat dyes, fiber
reactive dyes, disperse dyes, and optical brighteners. Some dyes fall into more than one of the above
classifications; dyes are sometimes also classified according to their structural class, e.g., azo,
triphenylmethane, anthraquinone, etc.

Direct Dyes
A direct dye forms a strong ionic bond with the fabric. The dye either contains or is capable of forming
a positive or negative charge which is electrostatically attracted to a negative or positive charge on the
fiber. For example, the direct dye picric acid is a strong acid and interacts with the basic side chains in
wool to form a salt linkage between itself and the fiber. On the other hand, malachite green bonds to the
acidic side chains in the wool fibers. Malachite green is a member of the important triphenylmethane
structural class of dyes.

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Disazo Dyes

so called substantive dyes, this type of dye contains two azo linkages. Disazo dyes link via hydrogen
bonding to the hydroxyl groups in a fabric. Cotton and sometimes rayon (depending on the amount of
acetylation of the hydroxyl groups) can be dyed directly with disazo dyes. Congo red (a benzidine dye) is
a disazo dye.

Ingrain Dyes
Also called developed dyes, these dyes are actually made inside the fibers of the fabric. The fabric is
treated with the two components used to synthesize the dye. These precursor molecules are small
enough to diffuse into the pores and spaces between the fibers in the fabric. They then react to form the
dye, which is trapped inside or “in the grain” of the fibers because of the large size of the dye molecule.
An example of an ingrain dye is para red (“American flag red”), an ingrain dye for cotton. The fabric is
soaked first in a solution of the coupling component ß-naphthol and then in a solution of diazotized p-
nitroaniline.

Para red is one member of a large structural group of synthetic dyes called “azo dyes”. Synthesized by
the coupling of aryl diazonium salts with various aromatic amines and phenols, azo dyes encompass a
broad range of colors, including yellows, oranges, reds, browns, and blues. It is the structure of each
particular dye that determines the color that will be exhibited. In general, the more conjugated the π-
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system of a molecule, the longer the wavelength of visible light it will absorb, and the observed color
will change accordingly. Azo dyes are discussed in Loudon (5th ed. section 23.10, pp. 1139-1144).

Mordant Dyes
Certain dyes form chelated complexes with heavy metals such as copper, chromium, tin, iron, and
aluminum. Cotton, wool, and silk can also coordinate with these metals. To dye a fabric with a mordant
dye, the fabric is first treated with a mordant, or the salt of a heavy metal. The fabric is then treated with
the dye, the dye complexes with the mordant, and is thus linked to the fabric. Different metals
(mordants) can lead to different colors with the same dye. Alizarin (an anthraquinone dye) is a typical
mordant dye, shown in a chelated complex with cotton using chromium as the mordant.
With some mordant dyes, especially the triphenylmethane dyes (e.g., malachite green and crystal violet,
cationic dyes) tannic acid is used as the mordant. Tannic acid is actually a mixture of tannin structures
and is isolated from the bark of different plants.

Vat Dyes
Vat dyes can be used for all fibers, both natural and synthetic. Most vat dyes are soluble (and colorless)
in water in their reduced form, but become insoluble and colored when oxidized. They are introduced to
the fabric in their soluble form and then oxidized or “developed” to precipitate them both on the inside
and outside of the fabric fibers. The vat dye indigo (a quinonoid dye) is used to dye blue jeans. It is very
insoluble in all solvents, and thus is fast. However, since it is not covalently bound to the fabric, and
only adheres to the surface of the fiber, it is subject to removal by abrasion. This explains why the knees
and other parts of blue jeans are subject to wear and will gradually turn white. It also accounts for the
appearance of distressed jeans.

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Indigo has an interesting history. In ancient times, indigo was isolated from plant sources, such as
Indigofer. In India, it was used to dye cloth and in Egypt, mummies were sometimes wrapped with
indigo-dyed ribbons. It became known in Europe after the discovery of the sea route to India. It was
used for dyeing wool by the Gauls, and “their wives and daughters painted their bodies with it, when
they appeared naked at the sacred festivals. Caesar relates the same of the Britons, who however did it in
order to appear more terrible in battle”.1 In the sixth century in France and in Germany, indigo was
isolated from a plant known as “woad”. The first chemical synthesis of indigo wasn’t reported until 1880
by Adolf von Baeyer, and was initially met with violent opposition from growers of woad. Luckily for
these farmers both the first and second generation syntheses were not economically feasible; it wasn’t
until 1897 that BASF began producing indigo by the thousands of tons, ending isolation from natural
sources.

Disperse Dyes
Disperse dyes are similar to vat dyes in that they are applied to the fabric in soluble form and remain on
the fabric as a water-insoluble precipitate. These dyes are soluble in an organic solvent and insoluble in
water. They may be used to dye the fabrics like dacron and rayon that have few groups present to allow
any direct dye-fiber interactions. Many of the dyes used above can be used as a disperse dye: para red is
a common disperse dye.

Fiber-Reactive Dyes
This is the newest type of dye. These dyes attach to
the fiber by reacting with either an amino or a
hydroxyl group in the fiber to form a covalent
bond. The primary subclass of fiber-reactive dyes is

1
from The Rise and Development of Organic Chemistry, Carl Schorlemmer, p. 253, 1894.

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the procion dyes, which are based on cyanuric chloride. The dye molecule and the fiber molecule must
each contain either an –OH or an –NH2 group, each of which replaces one of the chlorines in cyanuric
chloride. The result is that the dye is covalently attached to the fiber through a triazine linkage.

Optical Brighteners
Many detergents contain a blue-white fluorescent dye that is adsorbed on the cloth during the washing
process. These dyes fluoresce, that is, absorb UV light and reemit light in the visible blue region of the
spectrum. This blue color counteracts the pale yellow color of white goods, which develops because of a
buildup of soil embedded in lipids.

Representative Dyes
The following compounds are dyes which represent the types discussed above:

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Supplemental: Dyes and Dyeing
Experiment 20
Synthesis of Azo Dyes
Reading: Organic Chemistry by Francis Carey, 7th edition, pp. 942-944 (22.18).Organic Chemistry by Marc Loudon, 5th ed.,
pp. 1139-1144 (23.10 A-B).

Suggested reading: Essay: “Dyes and Dyeing”, in this Lab Manual.

Dyes and humans have a long history with one another. Before the middle-nineteenth century, most of
the dyes used to dye fabric were extracted from natural sources such as plants or dirt. That is until 1856,
when, a then 18-year old William Henry Perkin, accidently synthesized the first dye while trying to
synthesize the anti-malarial drug Quinine. Within a year Perkin had patented the compound and opened
a dyeworks in London to manufacture it. The dye was called Perkin’s mauve or mauveine, and although
it fell out of fashion by the late 1860’s, it made Perkin a fortune and launched the synthetic chemical
industry.
In today’s lab, we are going to investigate another class of dyes known as azo dyes. Azo dyes form a
large structural group of synthetic dyes. The first commercially important azo dye was Bismarck Brown,
first manufactured in 1865. By the 1970s, over 60% of synthetic dyes were azo dyes. Azo dyes have the
general structure below:

In this experiment, you will synthesize one of eighteen azo dyes assigned according to a matrix of
reagents much as you did in the chalcone lab. Azo dyes, the mechanism of the synthetic reaction, and
the combinatorial scheme that you will follow are discussed in the following sections.

The Colors of Azo Dyes

Azo dyes come in a broad range of colors, including yellows, oranges, reds, browns, and blues. Each
compound has a slightly different color due to variation in the substitution patterns of the aromatic
rings. The different substituents contribute varying electronic and conjugation effects resulting in
changes to the dyes π-system.
Extensively conjugated π-systems absorb light at particular wavelengths in the visible portion of the
spectrum. In general, the more extensive the conjugated π-system of a molecule, the longer the
wavelength of visible light it will absorb and the observed color from the reflected light will change
accordingly.
white (least extensive π-system) » yellow » orange » red » green » blue (most extensive π-system)
Whenever a compound absorbs a particular wavelength (color) from white light, the combination of the
reflected wavelengths (colors) makes the compound appear colored. For example, if a compound
absorbs in the visible region at 5000 Å, which is green, the combination of all the other wavelengths
which are reflected makes the compound appear red.

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Experiment 20: Synthesis of Azo Dyes
Mechanism of Azo Dye Formation
Azo dyes are formed by the coupling of an aryldiazonium salt with an aromatic amine or a phenol. Aryl
diazonium salts are prepared by treating an acidic solution of an aryl amine with sodium nitrite:

Aryl diazonium salts are stable for several hours if kept in an aqueous solution at 0–5°. They are
relatively weak electrophiles but have sufficient reactivity to attack highly activated aromatic rings such
as anilines and phenols. The ensuing reaction, called “azo coupling”, results in molecules that have the –
N=N– system linking two aromatic rings (Figure 20.1).

Figure 20.1 » Mechanism for the reaction of aromatic amines or phenols with a diazonium ion.
In an azo coupling, a naphthol is often used and is usually dissolved in a base such as NaOH. This
deprotonates the OH and makes the phenol group highly nucleophilic. The aryl diazonium ion adds para
to the electron releasing group (X) unless that position is occupied, in which case it adds ortho. For
reference, the numbering convention for naphthalene is shown below. The 1-position is often referred
to as α, and the 2-position as β.

In this experiment, you will synthesize the dyes from an aminobenzenesulfonic acid (the aryl amine that
will form an aryl diazonium salt) and an aromatic coupling agent (the compound with an electron-
releasing group). The generalized scheme is shown in Figure 20.2. Note the extensive conjugation that
will lend each dye its characteristic color.
1
R
R2
ERG
+ - ERG N
NH2 NaNO2 N Cl
N N
R 1 HCl, H2O R
NaOH, H2O R2
diazonium salt azo dye

Figure 20.2 » Generalized scheme of the azo-dye synthesis you will perform in lab.

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Experiment 20: Synthesis of Azo Dyes
Your goal is to determine if the dye that you are assigned can be made, if it is a relatively efficient
synthesis, what color it is, and how well it dyes fabric. The possible coupling agents and their structures
are given in Table 20.1.

Table 20.1
Coupling agents for the azo dye experiment.

Designation Name of compound Structure

A sulfanilic acid (4-aminobenzenesulfonic acid)

B metanilic acid (3-aminobenzenesulfonic acid)

C aniline-2-sulfonic acid (2-aminobenzenesulfonic acid)

1 2-naphthol (β-naphthol)

2 1-naphthol (α-naphthol)

3 salicylic acid

4 8-anilino-1-naphthalenesulfonic acid

5 6-amino-4-hydroxy-2-naphthalenesulfonic acid

6 7-amino-4-hydroxy-2-naphthalenesulfonic acid

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Experiment 20: Synthesis of Azo Dyes
Safety Notes
The naphthol derivatives and the azo dyes are irritants; 1-naphthol is toxic. Sodium hydroxide and
hydrochloric acid are corrosive and sodium nitrite is a toxic oxidizer. Avoid skin contact with all the
chemicals and wear gloves throughout the experiment.

Procedure
There is no official prelab for this experiment and there will not be a prelab quiz. You will be graded on
your technique, data/observations, and write-up, together worth a total of 20 pts. Before you come to
lab, write a brief, general procedure. Your TA will assign you the synthesis of one of the 18 azo dyes.
You will need to calculate the number of grams of reactants when you get to lab; for your convenience,
these physical data are summarized in Table 20.1.
1) Diazonium salt preparation
Put 2 mL of 15% HCl in a small Erlenmeyer and set it in an ice bath to chill. In another flask,
put 1.4 mmol of an aminobenzenesulfonic acid (A–C series) and 2.5 mL of 2.5% sodium
carbonate. Warm this flask until all of the sulfonic acid is in solution, then remove the flask from
the heat source and add 10 drops of 40% sodium nitrite solution using a Pasteur pipet. Now,
slowly drip the aminobenzenesulfonic acid solution into the chilled HCl solution, keeping the
mixture on ice and swirling occasionally during the addition. Keep the resulting mixture in the
ice bath until you are ready to use it. (It will likely be a suspension.)

2) Coupling reaction
In a small Erlenmeyer flask, place 1.3 mmol of the phenol (1–6 series) and 1 mL of 2.5 N
NaOH. Once the naphthol has gone into solution, chill the flask in an ice bath.
Swirling occasionally, add the suspension of diazonium salt prepared in the previous step
portion wise with a Pasteur pipet to the flask of dissolved naphthol, swirling. The color of the
solution will begin to change; let the reaction proceed for about 10 min with occasional stirring,
then heat on a hot plate for a few minutes until all (or at least some) of the solid dissolves. Add
0.5 g of solid NaCl and continue heating for 5 min.

3) Dying a fabric strip

Pour the solution of dye from the previous step into a beaker. Put a strip of the multi-fiber
fabric in the solution and keep it immersed while you boil the solution for about 5 min. Remove
from heat and use forceps to take the fabric out of the solution. Rinse the fabric with tap water.
Pat dry and compare the color with the fabric dyed by your lab mates.
The key to the fibers in the multi-fiber strip is in Table 20.3.

4) Write-up
Hand a copy of your data and observations as well as the dyed fabric strip in to your TA.

Wastes
Aqueous Waste: The used dye solutions.

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Experiment 20: Synthesis of Azo Dyes
 Table 20.2
Physical data for the reactants in the azo dye experiment.

Compound M.W. m.p. °C b.p. °C

sulfanilic acid (4-aminobenzenesulfonic acid) 173.19 >300 …

metanilic acid (3-aminobenzenesulfonic acid) 173.19 >300 …

aniline-2-sulfonic acid (2-aminobenzenesulfonic acid) 173.19 >300 …

2-naphthol (b-naphthol) 144.17 120-2 285-6

1-naphthol (a-naphthol) 144.17 94-6 278-80

salicylic acid 138.12 158-61 211

8-anilino-1-naphthalenesulfonic acid 299.34 215-7 …

6-amino-4-hydroxy-2-naphthalenesulfonic acid • H2O 257.26 … …

7-amino-4-hydroxy-2-naphthalene sulfonic acid • H2O 257.26 … …

Table 20.3
13-Fabric Key: 6-Fabric Key:
Black thread 1 Acetate Rayon

1 Acetate Rayon 2 Bleached Cotton

2 SEF (acrilan) 3 Nylon

3 Arnel 4 Silk

4 Cotton 5 Viscose Rayon

5 Creslan 61 6 Wool (yellowish)

6 Dacron 54

7 Dacron 64

8 Nylon 6.6

9 Orlon 75

10 Silk

11 Polypropylene

12 Viscose Rayon

13 Wool

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Experiment 20: Synthesis of Azo Dyes
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Experiment 20: Synthesis of Azo Dyes