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Synthesis of 1-phenylazo-2-naphthol
Caitlin Bridgette G. Castro
aNational Institute of Molecular Biology and Biotechnology, University of the Philippines Diliman

ABSTRACT
1-phenylazo-2naphthol or Sudan-1 is an orange-red azo dye that was commonly used in enhancing the color of foodstuff,
but is now mostly used in coloring oils, waxes, and polishes. The experiment aims to synthesize Sudan-1 via two-pot
synthesis wherein phenyldiazonium solution and beta-naphthoxide solution will each be prepared separately in two “pots”
or containers and eventually mixed together in one container. The finished product was a shiny red powder that had a
37.40% yield with a 61.07% error. The Sudan-1 dye produced also successfully stained a piece of cotton cloth with high
fastness and low levelness.

1. Introduction Aside from producing Sudan-1, a small piece of

1-phenylazo-2-naphthol or Sudan-1 is an orange
red azo dye. Azo dyes contain the functional group
R−N=N−R’, with R usually being aryl. Because of their
conjugation, delocalization takes place and allows
them to have vibrant colors. This is further enhanced
by the N=N which increases the delocalization. The
system is called the chromophore as this is
responsible for its color. Additionally, dyes have
auxochromes which adjust the wavelength that the
dye could absorb and thus control how vibrant the
color dyes would produce [1].
Azo dyes are prepared by coupling. Azo coupling is
the electrophilic substitution reaction of an aryl
diazonium cation with its coupling partner [1]. In the
case of Sudan-1, phenyldiazonium ion was coupled
with beta-naphthoxide, as seen in figure 1.
cotton cloth was dyed via ingrain dyeing. Ingrain
dyeing is the synthesis of the dye within the fabric.
Because of dissimilar intermolecular forces between
the fabric and the dye, the starting substrate for the
dye will first seep into the fabric and only then will the
subsequent reagent be added. This is to ensure that
the dye is trapped within the cloth fibers[3].
The direct dyeing process is characterized by first
synthesizing the dye then subsequently dyeing the
fabric with it. This process would work if the fabric
and the dye have similar intermolecular forces[3].

Figure 2: Structure of cotton

As seen from the structure of cotton in figure 2

Phenyldiazonium beta- Sudan-1 above, it is shown to have many H-bonding groups.
Ion naphthoxide
Sudan-1, on the other hand, as seen in figure 1, has
Figure 1: Synthesis of 1-phenylazo-2-naphthol
only one H-bonding group (-OH) which is not enough
to bind with cotton. Therefore, ingrain dyeing is the
Via electrophilic aromatic substitution, the
most optimal process to dye cotton with Sudan-1[4].
electrophile, phenyldiazonium ion, attacks the beta-
The quality of a dye is determined by its fastness,
naphthoxide ion. The aromatic rings and diazo group
how well the dye stains the fabric, and its levelness,
are the chromophore while the hydroxide group is the
how evenly the dye stains the fabric.
auxochrome.
Two-pot synthesis was needed for the experiment
2. Materials and Methods
because of the low pH environment of
phenyldiazonium and the high pH environment of
In one container, 0.2mL aniline, 0.35mL water, and
naphthoxide. Preparing them together would not
0.5mL concentrated HCl were combined and cooled to 4
allow these environments to occur [2].
deg C. 1mL of ice-cold distilled water was added.

*Corresponding author. Mobile: 09198212087

E-mail address: cbgcastro@gmail.com

Gradually, 0.04g NaNO2 crystals were added. The
solution was kept below 5 deg C
In another container, 0.35g of beta-naphthol was
dissolved in 4.5mL 5% aqueous NaOH. The solution was
cooled to 4 deg C.
While stirring, the phenyldiazonium chloride
solution was slowly added to the beta-naphthoxide
solution. The mixture was left to stand at 4 deg C for 1-5
minutes. The product was filtered, washed with cold
water, recrystallized using hot ethanol, and dried. The
product was weighed, and a small portion was used to
determine its melting point.
The phenyldiazonium chloride solution and the beta-
naphthoxide solution were prepared again using half
the volumes. A small piece of white cotton fabric was
soaked in cold beta-naphthoxide solution for 2-3
minutes. The fabric was pat dried before immersing it in
the phenyldiazonium chloride solution for several
minutes. The cloth was then rinsed in running water.
3. Results and Discussion
3.1. Preparation of phenyldiazonium solution
Diazotization is the conversion of a primary amine, R-
NH2, to a diazonium, R−N=N−R’[3], as seen in the
reaction mechanism figure 3.
Figure 3: Synthesis of phenyldiazonium ion
Sodium nitrite is converted to nitrous acid to later
form a nitrosyl ion. It is important to perform the
synthesis of phenyldiazonium in acidic conditions to
convert the sodium nitrite to nitrous acid, to protonate
nitrous acid to eventually produce the nitrosyl ion, and
to prevent the formation of side products: N-nitroso and
its deprotonated form [5] as seen in figure 4.
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Figure 4: Formation of N-nitroso side products in
basic conditions
The solution was prepared at low temperatures to
prevent the formation of phenol [5] as seen in figure 5.
Figure 5: Formation of phenol side product in high
temperature
The presence of side products decreases the yield of
Sudan-1 formed as the side products cannot be coupled
with beta-naphthoxide to produce Sudan-1.
3.2. Preparation of beta-naphthoxide solution
When beta-naphthol, an acidic reagent, reacts with
NaOH, it neutralizes and forms a naphthoxide ion as
seen in figure 6. Oxide ions are very reactive and donate
electrons easily, making it susceptible towards
electrophilic aromatic substitution [6].
Figure 6: Formation of beta-naphthoxide
It was important to form beta-naphthoxide in a basic
solution because otherwise, a side product would be
formed as seen in figure 7 [5].
Figure 7: Formation of side products in acidic
conditions
The presence of side products decreases the yield of
Sudan-1 formed as the side products cannot be coupled
with phenyldiazonium to produce Sudan-1.
The solution was cooled to 4 deg C to prevent the
temperature of the solution from increasing once the
two solutions are mixed together.
3.3. Synthesis of Sudan I by Two-Pot Synthesis

Phenyldiazonium can attack beta-naphthoxide on
either carbon 1 or carbon 2 as seen in figures 8 and 9,
respectively[7].
Figure 8: Resonance structures for C1 attack
Figure 9: Resonance structures for C3 attack
In the C1 attack, however, there are more stable
resonance structures that can be formed. Thus, attack on
C1 is favored.
The synthesized Sudan-1 was bright red, as seen in
figure 10, and weighed 0.21g against a theoretical yield
of 0.55g (37.40% yield). Possible sources of error
include incomplete synthesis of either the
phenyldiazonium ion or the beta-naphthoxide ion.
Figure 10: Synthesized sudan-1 after drying
The melting point determined was 80 deg C against
the theoretical melting point of 131 deg C (61.07%
error). This indicates that the synthesized Sudan-1 was
not pure. This could be attributed to high temperature
of the solution and thus the formation of side products.
3.4. Ingrain dyeing
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Figure 11 shows the fabric dyed in Sudan-1.
Because of the uneven distribution of pigment, it can be
said that the dye was not very level. However, when it
was washed with running water, barely any of the dye
seeped out. This is an indication that the dye was fast.
Figure 11: Cloth ingrain dyed with Sudan-1
4. Conclusion and Recommendations
The Sudan-1 produced, although bright red as
mentioned by theoretical studies, had low purity and
yield. It was, however, able to dye fabric.
The two-pot method is simple enough to warrant
hardly any error. However, the conditions needed to
produce the phenyldiazonium ion are difficult to
replicate in hot climates. It is recommended that the
experiment would be performed in a cooler room.
References
[1] Allen, R. L. (2013). Colour chemistry. Springer
Science & Business Media.
[2] Nesmeyanov, A. N. (2013). Selected works in organic
chemistry. Elsevier.
[3] Lehman, J. W., & Lehman, J. W. (2002). Multiscale
Operational Organic Chemistry (pp. 213-222). Prentice-
Hall: Upper Saddle River, NJ.
[4] McMurry, J. E. (2010). Fundamentals of organic
chemistry. Cengage Learning.
[5] Penn State. (n.d.) Synthesis of dye, Sudan I – Chemistry
courses. Retrieved from
http://courses.chem.psu.edu/chem36/Web%20Syn06
/Exp31Syn06.pdf
[6] University of Calgary. (n.d.). Reactions of arenes.
Electrophilic aromatic substitution. Retrieved from
http://www.chem.ucalgary.ca/courses/350/Carey5th/
Ch12/ch12-8b.html
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[7] National Center for Biotechnology Information.

PubChem Database. 2-Naphthol, CID=8663,
https://pubchem.ncbi.nlm.nih.gov/compound/2-
Naphthol (accessed on July 3, 2019)

Appendices

Hot filtration set-up