3

ABSTRACT

Sudan I commonly known as CI Solvent Yellow 14 and Solvent Orange R and

its IUPAC name is 1-phenylazo-2-naphthol will be synthesized by diazo
coupling reaction. The diazo component is aniline, a primary aromatic amine
and the coupling component is 2-naphthol, a phenol. The diazo coupling
reaction yields a bright red powdered Sudan I, with a determined melting point
127-130°C. Using the prepared solutions a cotton cloth was dyed using the
Ingrain process of dyeing. The cloth is immersed first in the coupling
component, allowed to dry, and then immersed in diazo component to develop
the color. The dyed cloth exhibits a red-orange color.

I. Introduction

Since prehistoric times man has been dyeing cloth. The "wearing of the purple" has long
been synonymous with royalty, attesting to the cost and rarity of Tyrian purple, a dye derived
from the sea snail Murex brandaris. Indigo, a pigment extracted from a plant, was used to dye
burial cloths for Egyptian mummies over 4,000 years ago. Indigo is used today to dye blue jeans.
American Indians used cochineal, a scarlet dye extracted from the dried bodies of insects, to
color their baskets and clothing. The red dye alizarin, extracted from madder root, was known to
the ancient Egyptians and Persians. Alizarin was used to dye the red coats of British soldiers in
the American Revolution, the red caps and trousers of French soldiers in the French Revolution,
and the violins of Antonio Stradivari. The organic chemical industry originated with William
Henry Perkin's discovery of the first synthetic dye, Perkin's Mauve, in 1856 (Fieser and Fieser,
1963).

Figure 1.
Examples
of dyes
used since
prehistoric
times.
The
most
common
dyes are
the azo
dyes,
formed by
coupling
diazotized
amines to
phenols.
The dye
can be
made in
bulk, or, as we shall see, the dye molecule can be developed on and in the fiber by combining the
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reactants in the presence of the fiber (Fieser and Williamson, 1992 ). Azo dyes are usually
intensely colored because the azo (diazenediyl) linkage, -N=N- , brings the
two aromatic rings into conjugation. This gives an extended system of
delocalized π electrons and allows absorption of light in the visible region.
Azo dyes are used in dyeing industry because of their intense colors and
because they can be synthesized from relatively inexpensive compounds
(Solomon and Fryhle, 2011).

Azo dyes are made in two steps. First, a primary aromatic amine is reacted to give a
diazonium salt, as shown in Figure 2. Second, the diazonium salt is reacted or coupled with a
strongly activated aromatic system, such as phenoxide, as shown in Figure 3 (David and
Blangey, 1949).

Figure 2. The primary aromatic amine reaction yielding diazonium salt.

Figure 3. Coupling of diazonium salt.

The first step, the formation of diazonium salts, is called diazotization. The reaction was
discovered in 1858 by Peter Griess, who subsequently discovered several reactions of this new
compound. The most important method for the preparation of diazonium salts is treatment of
primary amines such as aniline with nitrous acid (HNO 2) prepared from sodium nitrite (NaNO2)
and a mineral acid (e.g. HCl). The reaction mechanism is shown in Figure 4 (David and Blangey,
1949).
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Figure 4. Mechanism for diazotization of primary amine and generation of nitrous acid and nitric
oxide cation (NO+).
Primary aliphatic amines react with nitrous acid to give highly unstable diazonium salts
which spontaneously decompose to N2 gas and carbocations as shown in Figure 5. The
carbocations react further to produce a mixture of alkenes, alcohols or alkyl halides, with
alcohols as the major product. This reaction is of little synthetic importance because the
diazonium salt is too unstable, even under cold conditions (David and Blangey, 1949).

Figure 5. Degradation of aliphatic diazonium salt.

Primary aromatic amines can form diazonium salts which are stable at low temperature.
In aqueous solution these salts are unstable at temperatures higher than 5°C; the -N+≡N group
tends to leave as N2, i.e. nitrogen gas. One can isolate diazonium compounds as tetrafluoroborate
(BF4-) salts, which are relatively stable at room temperature. In general, diazonium compounds
are not isolated and once prepared, used immediately in further reactions (David and Blangey,
1949).
An azo coupling is a reaction between a diazonium compound and aniline, phenol or
other aromatic compound which produces an azo compound. In this reaction the diazonium salt
is an electrophile and the activated arene is a nucleophile in an electrophilic aromatic
substitution. In most cases, including the example in Figure 3, the diazonium compound is also
aromatic. The product absorbs longer wavelengths of light than the reactants because of
increased conjugation (David and Blangey, 1949).

In this experiment, azo dye will be synthesized from aniline and 2-naphthol. This azo dye
is Sudan I in which the IUPAC name is 1-phenylazo-2-naphthol. Its structural formula is shown
in Figure 6.

Figure 6. Structural formula of Sudan I, an azo dye.

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Sudan I is commonly known as CI Solvent Yellow 14 and Solvent Orange R. This dye is
a powdered substance with a red-orange appearance. The additive is mainly used to
color waxes, oils, petrol, solvents and polishes. The dye has reportedly been used in
Worcestershire sauce in United Kingdom last February 2005. The origin of contamination is
traced back to the adulterated chili powder used as the raw material for Worcestershire sauce.
Some countries now ban the use of Sudan I because of the toxicity of the dye. Sudan I is
classified as carcinogenic by the International Agency for Research on Cancer (David and
Blangey, 1949).

II. Objectives

The main objective of the experiment is preparation of an azo dye which is Sudan I.
Specifically, it is aimed to:

1. synthesize Sudan I by diazotization and coupling; and

2. recrystallize and characterize the product by measuring its melting point.

III. Methodology

No major revisions in the procedure of the experiment. Refer to Organic Chemistry

Laboratory Manual for the set of procedures and reagents to be used.

IV. Presentation of Results

Table 1. Properties of the crude Sudan I.

Mass of filter paper 0.56 g

Mass filter paper + crude product 0.98 g
Mass crude product 0.42 g
Melting point of crude product* °C Ref:
Observations of the crude product Red precipitate; bright red powder
*The melting point of the crude Sudan I was not determined due to the small amount such compound.

Table 2. Properties of the recrystallized Sudan I.

Mass of filter paper 0.53 g

Mass of filter paper + recrystallized product 0.56 g
Mass recrystallized product 0.03 g
Melting point of recrystallized product 127-130°C Ref: 131-132°C

V. Discussion of Results

Sodium 2-naphtholate was the coupling component in the azo dye and was prepared by
mixing 2-naphthol in sodium hydroxide. The 2-naphthol was dissolved in sodium hydroxide
because it is a phenol. The solution was cooled before adding to the diazonium salt.

The benzene diazonium chloride was prepared by dissolving aniline in concentrated

hydrochloric acid. The former solution was reacted with nitrous acid (HONO) to form the
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diazonium salt. Nitrous acid was generated in situ from sodium nitrite and mineral acid (in this
case HCl from the reaction of aniline and HCl). The reaction is carried out at low temperatures
(0-5°C) because diazonium salts reacts with water to form phenols and other by-products at
higher temperatures. The excess nitrous acid was determined by touching a small drop of the
resultant solution on the tip of the stirring rod to a piece of KI/starch solution. An immediate
purple color indicates excess nitrous acid and addition of urea with cooling and agitation is
necessary. The procedure was continued until there was no immediate purple color was seen on
KI/starch solution. There was a need for determining excess nitrous acid since the coupling
component is a phenol and phenol couple readily in mildly alkaline solutions. However, it must
also be noted that too low pH will prevent an amine from reacting by causing protonation of
amino group, whereas too high pH prevent amine will cause diazonium salt to change to a
diazotate ion, which is incapable of coupling (Fieser and Williamson, 1992; avid and Blangey,
1949).

Figure 7. Formation of unreactive species at high and low pH.

The coupling reaction is carried out by adding the diazo component, benzene diazonium
chloride, with cooling and stiring, to a solution of coupling component previously prepared. The
coupling reaction is an electrophilic aromatic substitution reaction, with benzene diazonium
chloride acting as electrophile. Because the diazo group of benzene diazonium chloride, -N 2+, is
only a weakly electrophilic, the coupling component must contain one or more strongly activated
groups, in this case OH from 2-naphthol, for coupling to occur. Throughout the coupling
reaction, there was constant agitation to ensure complete mixing of the diazonium salt in the
coupling component. Furthermore, slight adjustment of pH was done by adding small amount of
hydrochloric acid and cooled in an ice bath before filtering to obtain a better yield of dye (David
and Blangey, 1949).

Bright red solid precipitate was formed after the coupling reaction. This precipitate is the
Sudan I (1-phenylazo-2-naphthol). The precipitate was washed with cold distilled water twice.
The washing of precipitate with cold distilled will washed off the impurities brought by the
mother liquor without dissolving the Sudan I. The crude product was air-dried. The dried crude
Sudan I was further recrsytallized to attain a purer product. The recrystallization solvent used
was ethanol. Ethanol is considered as a good recrystallization solvent for Sudan I. The dye was
dissolved in hot ethanol, not too hot since the dye will turn to black-brown mess. The mass of
recrystallized product is 30 mg, a typical yield for recrystallized Sudan I. The determined
melting point of Sudan I is 127-130°C. This shows that the synthesized Sudan I is slightly pure
because the theoretical melting point of the dye is 131-132°C. The large temperature range of
Sudan I can be attributed to the following: incomplete washing, insufficient recrystallization
solvent and incomplete drying of the product (Fieser and Williamson, 1992).

Before the coupling the product to form bright red precipitate of Sudan I, a cotton cloth
was dyed by the process of Ingrain dyeing. Generally, cloth can be dyed by several different
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processes. It can be a direct process, dispersed process or Ingrain process. The experiment
focuses more in Ingrain dyeing process in which the dye is synthesized in the cloth itself, usually
by the combination of a diazonium salt and coupling component. The cloth is immersed first in
the cold sodium 2-naphtholate, allowed to dry, and then immersed in benzene diazonium
chloride to develop the color. The comparatively small molecules of the separate components can
diffuse in the space between the fibers; after they combine to form the dye, the larger dye
molecules are trapped there. In the dyeing process a cotton cloth (Figure 8) was used because do
not have the anionic and cationic carboxyl and amine groups like that of wool and silk and they
are best dyed with an azo dye, like Sudan I, due to its high molecular weight that shows colloidal
properties. The dyes probably become fixed to the fiber by hydrogen bonding (Fieser and
Williamson, 1992).

Figure 8. Structural formula of cotton (R=H).

After the cloth has been dyed, the color is bright red-orange. The color of the dye in the cloth
depends on the wavelengths of light it absorbs. If a dye absorbs light at certain wavelength, the
color perceived by the human eye arises from the wavelengths that are not absorbed and are
therefore reflected to the human eye. The light absorbing portion of the dye molecule is called
chromophore, a conjugated system of delocalized electrons (David and Blangey, 1949).
.
VI. Conclusion

The azo dye Sudan I was prepared by diazo coupling reaction which is electrophilic
aromatic substitution. The diazo component of Sudan I is aniline, a primary aromatic aniline and
the coupling component is 2-naphthol. The diazotization reaction involves aniline reacted with
hydrochloric acid and the resultant solution was added with nitrous acid yielding benzene
diazonium chloride. Excess nitrous acid was determined by touching a small drop of the solution
on the tip of the stirring rod to a piece of KI/starch solution. Immediate purple color indicates
excess nitrous acid. Addition of urea was done to remove excess nitrous acid. . There was a need
for determining excess nitrous acid since the coupling component is a phenol and phenol couple
readily in mildly alkaline solutions. However, it must also be noted that too low pH will prevent
an amine from reacting by causing protonation of amino group, whereas too high pH prevent
amine will cause diazonium salt to change to a diazotate ion, which is incapable of coupling.
Sodium 2-naphtholate was the coupling component in the azo dye and was prepared by mixing
2-naphthol in sodium hydroxide and cooled. The coupling reaction is carried out by adding the
diazo component, benzene diazonium chloride, with cooling and stirring, to a solution of
coupling component previously prepared. The coupling reaction is an electrophilic aromatic
substitution reaction, with benzene diazonium chloride acting as electrophile.

The product is a bright red solid and imparts a red-orange color when dyed on cloth.
Sudan I was recrystallized to obtain a pure product. Ethanol was used a recrytallization solvent
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because it satisfies the requirement of a good recrystallization to Sudan I. The recrystallized

product was subjected to melting point determination, and the determined melting point is 127-
130°C which is nearer to the reference value of 131-132°C.

VII. Questions and Answers

Prelaboratory Question

1. What are azo dyes? Why are azo dyes colored?

Azo dyes are artificial dyes that contain an azo group. These are dyes that results from the
reaction of a diazo component and a coupling component by diazo coupling reaction. Also, azo
dyes always contain one or more –SO3- Na+ groups to confer water solubility on the dye ad assist
in binding to the surfaces of polar fibers (wool, cotton, nylon).

2. What type of reaction is involved in the preparation of azo dyes?

The preparation of azo dyes involves diazo coupling reaction which is electrophilic aromatic
substitution.

Postlaboratory Questions:

1. Give the diazo component and coupling component that can be used as starting materials
for the preparation of the following synthetic dyes:

Para red

Diazo component: ρ-nitroaniline

Coupling component: β-naphthol

Bismarck brown

Diazo component: m-phenylenediamine

Coupling component: m-toluidine
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Congo red

Diazo component: benzidine

Coupling component: sodium naphthionate

2. Show why the reaction between the diazonium ion and 2-naphthol occur primarily on the
1 and not the 3 position as shown in the equation above. (Hint: Draw the initially-formed
carbonium ion for attack at each position placing + charge on the C atom at 2 and look
at the conjugation in the distribution of the remaining C-C double bonds).

The carbocation intermediate in the attack in C-1 has better resonance structure than the
intermediate attack on C-3.

3. Give two possible side reactions that can occur if conditions in preparing the dye are not
met.

The side effects can be the dye is not formed because of the protonation of amino group, or
diazonium salt was changed to a diazotate ion which is incapable of coupling. The second one is
that instead of a bright red Sudan I, the product is a black-brown mess.

4. Explain how ingrain dyeing works. Why is Sudan I applied this way?

Ingrain dyeing is a process in which the dye is synthesized in the cloth itself, usually by the
combination of a diazonium salt and coupling component. The cloth is immersed first in the
coupling component, allowed to dry, and then immersed in diazo component to develop the
color. The comparatively small molecules of the separate components can diffuse in the space
between the fibers; after they combine to form the dye, the larger dye molecules are trapped
there. Sudan I was applied in this way because the cotton cloth does not have the anionic and
cationic carboxyl and amine groups that are like that of wool and silk and they are best dyed with
an azo dye, like Sudan I, due to its high molecular weight that shows colloidal properties. The
dyes probably become fixed to the fiber by hydrogen bonding.

VIII. References

David, H. D. F. and L. Blangey. (1949). Fundamental Processes of Dye Chemistry. New York:
Interscience Publishers, Inc.

Fieser, L. F. and M. Fieser. (1963). Topics in Organic Chemistry. New York: Reinhold
Publishing Corp.
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Fieser, L. F. and K. L. Williamson. (1992). Organic Experiments (7th ed.). Lexington,

Massachusetts, Toronto: D.C Heath and Company.

Solomon, T. and C.B. Fryhle. (2011). Organic Chemistry (10th ed.). United States of America:
John Wiley and Sons.