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Synthesis of 1-Phenylazo-2-Naphthol (Sudan-1)

Konrad Frederick Magboo
Department of Food Science and Nutrition, College of Home Economics, University of the Philippines Diliman, Quezon City, Philippines

ABSTRACT

Sudan-I was synthesized via a 2-pot synthesis reaction by preparing a solution of phenyldiazonium chloride with β-naphthol at a temperature below 5˚C. The
phenyldiazonium chloride was prepared by reacting aniline with Nitrous Acid (HONO) below 5˚C. β-naphthol was placed in NaOH solution also below 5˚C. To
test for the effectivity of the produced dye, two sets were prepared. One set was used to test for the effectivity via ingrain dyeing while the other will be used
to synthesize the azo dye. After the ingrain dyeing, the dye produced was shown to be effective and possessed levelness and fastness. The other sets were then
reacted to synthesize the dye. The synthesized dye was then recrystallized via a hot ethanol solution. After recrystallization, the 0.15g of recrystallized dye
was formed. This gave a 27.54% yield. This recrystallized dye had a measured melting point of 130-137˚C. Similar to the other set used for ingrain dyeing, the
recrystallized dye also possessed levelness and fastness.

1. Introduction

Azo dyes are made from primary arylamines since alkylamines
are highly unstable and simply decompose and release the
diazonium group as N2 gas and produce a carbocation which will
react with a nucleophile. The arylamines; however, are more stable
and can be isolated, although at a cold temperature. (McMurry,
2004).
2. Materials and Methods
2.1. Preparation of phenyldiazonium chloride solution
To prepare the coupling reactant of phenyldiazonium ion, 0.2 mL
Aniline, 0.35 mL Water, and 0.5 mL concentrated (6 M) HCl were
combined in a 50-mL Erlenmeyer flask.

Azo dyes are made from primary arylamines since alkylamines
are highly unstable and simply decompose and release the
diazonium group as N2 gas and produce a carbocation which will
react with a nucleophile. The arylamines; however, are more stable
and can be isolated, although at a cold temperature. (McMurry,
2004).
Azo dyes are synthetic dyes used for coloring consumer goods
such as carpets, cosmetics, etc. (Encyclopedia Brittanica, 2016).
Some Azo dyes can also be used as biological dyes since they are fat
soluble. They also exhibit geometric isomerism which determines
the resulting color of the dye. (“Chem 322: Azo Dyes: Combinatorial
Synthesis of Dyes”, n.d.)
Azo dyes can also be used as titration indicators. An example of
this is methyl orange which is red at an acidic solution while yellow
at a basic medium. Aside from geometric isomerism, a shift in the
electron delocalization of the aromatic rings will absorb different
wavelengths of light. (Clark, n.d.)
In this experiment, Sudan-1, an azo dye will be synthesized
through a two-pot synthesis reaction with aniline and β-naphthol
being the main reactants.
Nitrous Acid (HONO), was prepared by reacting Sodium Nitrite
with concentrated HCl. This was done at below 5˚C. This was also
combined with aniline and to prepare the coupling reagent,
phenyldiazonium ion.
Two sets of these solutions were prepared. One will be used for
ingrain dyeing. The other will be used to synthesize the dye.
2.2. Preparation of the β-naphthol solution
To prepare the coupling reactant of β-naphthol, 0.35 grams β-
naphthol and 4.5 mL of 5% aqueous NaOH (1.25M) were dissolved
in a 50-mL beaker. Two sets of this solution were also prepared
with one set to be used for ingrain dyeing while the other to be used
to synthesize the dye.
2.3. Ingrain dyeing to test for effectivity
The fabric to be dyed was placed in the β-naphthol solution in an
ice bath for 2-3 minutes. It was then removed from the solution and
was pat dry with filter paper. After drying, it was placed in the
phenyldiazonium chloride solution. After which, the cloth was
rinsed with running water.

This process was done in order to test whether the

phenyldiazonium chloride and β-naphthol form a successful
coupling reaction. Also, this was done in order to see if the color of
the resulting solution will be bright since dyes have a bright color.

2.4. Synthesis of Sudan-1 by Two-Pot Synthesis and Determination of

Product Yield and Purity

The remaining sets of the phenyldiazonium chloride and β-

naphthol, still in the ice bath were reacted slowly, while stirring.
The product was filtered then washed with small portions of cold
water. It was then recrystallized with hot ethanol and stored in a
pre-weighed vial to determine the % yield of the reaction. A small
portion of the recrystallized product was also determined its
Figure 1: Structure of Sudan-1, the azo dye to be synthesized. melting point to test for purity.
E-mail address: legendaryboykonrad@gmail.com
BS Community Nutrition, UP Diliman

Note that the process is called “two-pot synthesis” because the
reactants were first reacted in two separate containers or “pots”
and then synthesized in one pot; on the other hand, in one-pot
synthesis, all the reactants and products are synthesized in one
container or “pot” only.
3. Results and Discussion
3.1. Reagent Analysis and Use in the Reaction
Aniline was chosen because it is the simplest primary arylamine.
It will be used as the source of the phenyldiazonium ion.
Concentrated HCl was used because it will function as the source of
the Chloride ion and its strong acid characteristic which denotes
complete dissociation.
Figure 1: Reaction Mechanism of the synthesis of Phenyldiazonium
chloride from Aniline, concentrated HCl, and Sodium Nitrite
(Solomons and Frhyle, 2008).
NaNO2 provided the source of the Nitrite ion which will react
with the concentrated HCl to form the Nitrous acid (HONO) which
will react with Aniline to form the phenyldiazonium ion at a low
temperature. (Solomons and Frhyle, 2008).
HCl(aq) + NaNO2(aq) -> HONO(aq) + NaCl(aq)
Equation 1: NaNO2 reacts with HCl to form Nitrous Acid (HONO)
(Solomons and Frhyle, 2008).
NaOH, on the other hand, catalyzed β-naphthol’s conversion into
β-napthoxide because of β-Naphthol being a weak acid. Therefore,
they will react with bases such as NaOH in a neutralization reaction.
(Solomons and Frhyle, 2008).
Equation 2: Conversion of β-Naphthol to a Naphthoxide anion
(Solomons and Frhyle, 2008).
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Ethanol was used as the recrystallization solvent because Sudan-
I is sparingly soluble in ethanol at room temperature.
3.2. Mechanism of the reaction
Figure 2: Reaction mechanism between β-naphthol and
phenyldiazonium ion follows the Electrophilic Aromatic
Substitution Mechanism (Solomons and Frhyle, 2008).
As shown in the reaction mechanism, the attack on Carbon-1 by
the phenyldiazonium ion is favoured since carbon-1 is in the ortho
position while carbon-3 is in the meta position. The para position
cannot be the site of the attack of the phenyldiazonium ion because
it is already occupied by naphthol’s second aromatic ring. Carbon-1
is also prepared because the if the resonance is to be consulted,
when the site of the attack is carbon-3, the positive charge is not
delocalized to the –OH group which is more electronegative and can
handle the positive charge better than Carbon. (McMurry, 2004).
Figure 3: The attack on carbon-3 by the phenyldiazonium ion does
not give the positive charge to the OH group
3.3. Precautionary measures to increase the product yield
To ensure the formation of the desired product, the process was
done in a two-pot synthesis. The first pot being the
phenyldiazonium chloride solution, which, as stated earlier, cannot
be prepared in a basic medium because of the need for a
concentrated amount of acid to form HONO. (Solomons and Frhyle,
2008). The second pot was the basic β-naphthol solution, which as
stated earlier needs to be present as the β-naphthoxide anion in
order to be more reactive with the phenyldiazonium cation.
To increase the product yield, the NaOH added was slightly in
excess in order to hasten the coupling reaction of β-naphthol
(equation 2) and phenyldiazonium chloride. An ice bath and and ice
were made readily available to the solution to foster a cold
temperature below 5˚C. to prevent the phenyldiazonium ion from
decomposing to form a phenol and nitrogen gas. NaOH was not
added in a large excessive amount because it will convert the
phenyldiazonium ion to a Diazohydroxide or a diazotate anion (The
diazonium ion is converted into the diazotate anion when NaOH is

in excess) which will not couple with the β-naphthol. (Solomons
and Frhyle, 2008).
Figure 4: Conversion of the Phenyldiazonium ion to a
Diazohydroxide then a diazotate anion, respectively, in excess
amounts of NaOH (Solomons and Frhyle, 2008).
Rock salt was added to the ice bath in order to reduce the
temperature of the ice bath. Salt solution will reduce the
temperature of the ice bath which will help in cooling the reactants.
This is because of Freezing point depression where ice can be
melted at a lower temperature when added with solute. Also,
melting is an endothermic process which therefore absorbs heat
and cools its surroundings. (Petrucci, et.al., 2011).
3.4. Ingrain dyeing and the use of cotton
Ingrain dyeing forms azo dyes directly from the precursors
through an irreversible reaction. The dyes they produce also exhibit
color fastness. On the other hand, direct dyeing forms azo dyes
outside the precursors. The dyes they produce are water soluble,
and have an affinity to fibres. They do not have washfastness,
however. (Encyclopedia Brittanica, 2016.)
Cotton fibers are composed mostly of cellulose. Since cellulose is
a very polar compound, unlike that of Sudan-1, it will have a low
affinity with the dye. Therefore, it must be produced through
ingrain dyeing. The reactants, phenyldiazonium chloride a polar
molecule, will have an affinity to the cotton fibers and bind to its
cellulose component. Once the phenyldiazonium chloride has
reacted with β-naphthol in the cellulose fiber, it will be trapped
between the fibers.
Figure 5: The structure of cellulose consists of numerous –OH
groups which contribute to its polarity.
3.5. Results and Interpretations
The measured melting point of the recrystallized Sudan-1 was
measured at 130-137˚C. Since the theoretical melting point of
Sudan-1 is 131˚C, it can be concluded that the recrystallized
product has a relatively high amount of purity. The experiment
produced a low yield of product, although with a high amount of
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purity. A possible reason for this low yield is the temperature of the
laboratory when the experiment was conducted. The time when the
experiment was conducted was during the summer season which
therefore could have converted some phenyldiazonium ion to a
phenol despite being in an ice bath. Despite these losses, the
recrystallized dye still produced fastness and levelness which
indicates the experiment’s success.
Sudan-1 gives off a bright color because it contains numerous
chromophores. Chromophores are functional groups that absorb
light. Some chromophores are conjugated double bonds and azo
groups. Both of these groups can be found in Sudan-1. Therefore,
Since Sudan-1 has numerous chromophores, it can absorb a higher
amount of wavelength of light. (“Experiment 11: Synthesis of
Sudan-1”., n.d.). Sudan-1 is also known to absorb 480-516 nm of
light. (National Center for Biotechnology Information., n.d.).
Therefore, the possible colors it can reflect are Orange, Red, or
Purple. (Skoog, et. al., 2004.).
4. Conclusion and Recommendations
The two-pot synthesis reaction of Sudan-I was done by first
preparing two sets of the coupling reagents phenyldiazonium
chloride and β-naphthol below 5˚C. Phenyldiazonium chloride was
prepared from HONO and Aniline while β-naphthol was prepared
by immersing it in NaOH solution.
One set of the coupling reagents were first tested for
effectiveness via ingrain dyeing which determined the effectiveness
and the fastness of the dye.
After ingrain dyeing, the remaining set of the coupling reagents
were then reacted to produce the dye. The produced dye was then
recrystallized with hot ethanol as the recrystallization solvent and
its melting point was determined. The measured melting point was
130-137˚C. Since the theoretical melting point of Sudan-I is 131˚C,
the measured melting point has a 0.76 to 4.58% error. This % error
value reflects that the experiment has produced a high-purity
product; though, with a low yield of 27.54%. The product produced
also possessed fastness and levelness. These characteristics of the
synthesized product already reflect that the experiment was very
successful since it has produced a quality product, despite the low
yield.
If the experiment were to be repeated, it is recommended that
rock salt is added into the ice bath in order to reduce the
temperature. It is also recommended that numerous sets of the dye
is prepared in order to have a set that can be used for extra trial
runs.
The dye produced was colorfast and had levelness. To become
colorfast, the dye must retain its color without fading or running.
(Encyclopedia Brittanica, 2016.) To have levelness, the dye must
have an affinity with the substrate being dyed. (Encyclopedia
Brittanica, 2016.). The dye was colorfast since its color did not fade
easily. It also had levelness since the substrate (fabric) being dyed
had affinity with the dye and that it absorbed the dye’s color. These
two properties, along with the assessed purity justify that the
experiment was a success, despite the small yield.
Some possible sources for a reduced yield is the temperature of
the experiment not being at ideal conditions. When the solution is
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not below 5˚C, the phenyldiazonium ion will decompose to become

a phenol and expel the diazonium group as nitrogen gas.

Another possible source of error is when the phenyldiazonium

ion was reacted immediately with NaOH before it was reacted with
HONO. When the aniline is reacted with NaOH before Sodium
Nitrite, HONO will not form and Aniline will just form an immiscible
layer with NaOH and water. If, NaOH was in excess amounts when
reacted with the phenyldiazonium ion, it will form the
diazohydroxide and eventually the diazotate anion which will not
couple with the β-naphthol solution. (Figure 4). The low yield is
probably a result of an excess of NaOH in the solution which could
have converted some of the reactant into diazohydroxide or the
diazotate anion.

References

Encyclopedia Brittanica. “Azo Dye.” Accessed: May 1, 2016, 22:43

http://www.britannica.com/science/azo-dye

Encyclopedia Brittanica. “Direct Dye.” Accessed May 1, 2016, 22:45

http://www.britannica.com/technology/direct-dye

Encyclopedia Brittanica. “Ingrain Dye.” Accessed: May 1, 2016,

22:44
http://www.britannica.com/technology/ingrain-dye

Merriam-webster. “Colorfast.” Accessed: May 1, 2016, 22:39

http://www.merriam-webster.com/dictionary/colorfast

McMurry, “Organic Chemistry 6th edition.” International Student

Edition. 2004. Print.

National Center for Biotechnology Information. “Sudan-I.” n.d.

Accessed: May 1, 2016, 23:28
https://pubchem.ncbi.nlm.nih.gov/compound/Sudan_I#section=To
p

Petrucci, et. al. “General Chemistry Principles and Modern

Applications 10th edition.” Pearson. 2011. Print.

Skoog, et. al. “Fundamentals of Analytical Chemistry.” International

Student Edition. 2004. Print.

Solomons, Graham, T.W. and Fryhle, Craig. “Organic Chemistry 9th

edition”. Van Hoffman Press. 2008. Print.