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Synthesis of 1-Phenylazo-2-Naphthol
Maria Constancia Fretelin C. David*, Dominic Aquino
College of Social Sciences and Philosophy, Department of Psychology, University of the Philippines Diliman, Quezon City, Philippines

ABSTRACT

Dyeing is an ancient art which has been around since 2600 BC. Dyes are very useful in the successful coloration of various materials
such as fabrics, textiles, food, and hair. The experiment aim to synthesize the bright red-orange azo dye 1-Phenylazo-2-Napthtol or
commonly called Sudan-1. The synthesis of the dye occurred in two steps- diazotization and a coupling reaction. The crude product
was recrystallized to ensure purity. The pure product obtained was 0.06 g, giving a percent yield of 11%. The melting point of the
product was 129 C, giving a 3.73% deviance from the true melting of Sudan-1. Overall, the experiment was not very successful
because of the very low yield. In terms of purity, it can be said that the two-pot synthesis is successful in producing a product with
high purity.

*Corresponding author. Mobile: 09176363199

E-mail address: david.fretelin@gmail.com

1. Introduction
The process of dyeing cloth is an ancient art has
been around since around since 2600 BC. Before 1856,
dyes came from plant and animal sources. During 1856,
the first synthetic dye was produced by William Henry
Perkin by accidentally producing a purple dye side
product when he was synthesizing quinine from
allytoluidine. From then, the first dyeing company was
founded and is believed to be the dawn of organic
chemistry. In the present, dyes are ubiquitous in every
living. These are used colorize otherwise bland objects
such as cloths, food, oils, hair, and much more.
What makes dyes special from other organic
compounds is their ability to possess color through the
unique characteristics arising from their structure such
as presence of a chromophore, a color-bearing group
(N=N, N=O, C=O, C=S, C=C, C=NH), a conjugated
system of alternating single bond and double bonds (-=-
=), and the exhibition of resonance structures.
Dyes may be classified in several ways based on
their structures. Some examples would be anthraquinone
dyes, arylmethane dyes, pyronin dyes, and azo dyes. For
this experiment, the azo dye is the primary focus. Azo
dyes account for approximately 60-70% of all dyes used
in the food and textile manufacture. These dyes are
synthetic colours that contain the azo group -N=N- which
links two sp2 hybridised carbon atoms. Most azo dyes
contain only one azo group, but some contain two
(disazo) or more azo groups. The side groups around the
azo bond help stabilize the compound by extending the
delocalized system. Aromatic azo compounds are stable
and produce strong, vivid colors.
The synthesis of azo dyes require two reactions.
First is the diazotization of a primary aryl amine with a
nitrosonium ion to yield an arenediazonium salt, which
then undergoes a coupling reaction with an aromatic
compound coupling component such as phenols,
naphtols, and anilines to produce the final azo dye
compound.
Azo dyes is one of the most favoured dyes
because of its availability and low cost. Energy
requirements for the process are low since the reactions
have to occur at low temperatures. Additionally, the
environmental impact is quite minimal since the
reactions are done in water, which is cheap and easy to
clean and dispose of.
The successful dyeing of an objects depends on
both the structure of the dye and the fabric. Multiple
methods have been devised to address the proper
matching of materials. Some methods include direct
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dyeing, disazo dyeing, vat dyeing, and ingrain dyeing. In
ingrain dyeing, the dye is synthesized inside micro-
spaces in the fibers of the fabric. This technique is useful
when the textile to be dyed cannot undergo simple
adsorption.
In this experiment, the azo dye 1-phenylazo-2-
naphthol or more commonly known as Sudan-1 is
synthesized via the diazotization and coupling reactions
between phenyldiazonium chloride and -naphthol. Extra
precaution was done since the dye product is a known
carcinogen. A 2x3 fabric cloth with cellulose fibers is to
be colored with the Sudan-1 using the ingrain dyeing
technique. To assess the degree of success of the
experiment, the percent purity and percent recovery was
determined through melting point determination and
recrystallization.
2. Materials and Methods
Phenyldiazonium chloride solution and -
naphthol solution were prepared separately and
simultaneously. In a 50 mL Erlenmeyer flask, the
phenyldiazonium chloride solution was synthesized by
combining 0.2 mL aniline, 0.35 mL water, and 0.5 mL
concentrated HCl. The resulting solution was placed in a
rock salt ice bath and was cooled to 4 o C. After so, 1 mL
ice-cold distilled water was incorporated and a spatula-
full of NaNO2 crystals was gradually added. In a separate
50 mL beaker, the -naphthol solution was prepared by
dissolving 0.35g -naphthol in 4.5 mL 5% aqueous NaOH.
The solution was then cooled to 4o C in the same rock salt
water ice bath.
The 2x3 cm fabric to be dyed was immersed in
the cold -naphthol solution for 2-3 minutes. The fabric
was then dried by patting it in between filter papers.
Once dried, the fabric is soaked in the phenyldiazonium
chloride solution for approximately five minutes. The
fabric was then rinse with running distilled water for
cleansing.
The remaining phenyldiazonium chloride solution
was incorporated into and the -naphthol solution slowly
and while stirring. The reaction mixture was left to stand
for about 5 minutes at 4 o C. The product was filtered and
washed with small portions of cold distilled water. The
crude product was then recrystallized using a steam bath
with hot ethanol. The final pure product was then
weighed to determine the percent yield and its melting
point was determined. All results were recorded.
3. Results and Discussion
The first stage in the production of the azo dye
Sudan 1 is the formation of diazonium salts through a
process called diazotization. The first step of the process
is generation of a nitrous acid and nitric acid cation
(NO+). The primary amine, aniline, is to nitrous acid
(HNO2) prepared from sodium nitrite (NaNO2) and
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hydrochloric acid (HCl). The diagram below is the
detailed mechanism:
gas and carbocations, primary aromatic amines can form
stable diazonium salts when given the right conditions. In
aqueous solutions, the diazonium salts are unstable in
temperatures higher than 50 C, which is why the
temperature of the reaction mixture should always be
kept constantly lower than 5 0 C. If the temperature rises
above 50 C, the N+ N group becomes a nitrogen gas
leaving group and the resulting reaction would occur:

Diagram 1. Synthesis of nitric acid cation (NO+). Diagram 4. Degradation of amine

The second step of reaction is the diazotization of the
primary aromatic amine, aniline, with the nitric acid
cation formed. A detailed mechanism of the process is
shown below:
Acidity and basicity is a big factor in the
successful creation of Sudan-1. Phenyldiazonium chloride
should be reacted under an acidic medium to produce
the phenyldiazonium ion shown in diagram 2. If the
medium used was basic, there would be no protonation
of the OH- group and consequently no H 2O leaving group
producing a diazotate instead of the diazonium ion,
which cannot participate in a coupling reaction. The
mechanism is shown below:

+ N -
N - N OH -
N O
+ HO N + HO N

- H2O

Diagram 5. Creation of diazotate

Diagram 2. Diazotization of primary amine Additionally, the -naphthol should be

performed under a basic medium. If an acidic medium
Diazotization of aniline occurs in three steps. First was used, a side reaction where the acids in the solution
is the formation of the N-nitroso derivative by would protonate the -naphthol reagent and remove its
nucleophilic aromatic addition, with the lone pairs of the OH- substituent. The product would result in a positive
nitrogen of aniline attacking the electron deficient charged species that cannot participate in a coupling
nitrogen of the nitric acid. Next step is the reaction. The mechanism is seen below:
tautomerization of the N-nitroso derivative to a
H
hydroxydiazo which is then protonated by an H +, creating OH
H
+ +
O +
a good H2O leaving group. Once the H2O leaves, the C
H
+ H2O
hydrogen attached to the amine closest to the benzene
group donates its electrons to form a triple bond which
forms the phenyl diazonium ion, which then binds with
Diagram 6. Protonation of -naphthol
chloride to form phenyldiazonium chloride.
Since the preparation of the -naphthol and
phenyldiazoniumchloride entails different pH ranges,
After this process is the azo coupling reaction
they cannot be prepared together, that it why a two-pot
between the phenyldiazonium chloride and the -
synthesis is ideal. As demonstrated a while ago, an
naphthol through an electrophilic aromatic substitution
acidic medium would favour synthesis of
where the phenyldiazonium ion is the electrophile and
phenyldiazoniumchloride but would be unfavourable to
the activated -naphthol arene is the nucleophile. The
-naphthol and vice versa,
complete reaction is seen below:
In the figure below, the complete mechanism of
the coupling reaction is seen. The carbon of -naphthol
that is attacking the benzene diazonium ion is seen to
be at the C1 position.

Diagram 3. Synthesis of Sudan 1

Unlike primary aliphatic amines that produce

highly unstable diazonium salts that decompose to N2
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Looking at the structure of Sudan 1, we can see it

O
- +
N
N satisfies all the conditions in order to possess colour.
+
a. It is able to absorb light in the visible spectrum
b. Has at least one chromophore (a colour-bearing
group) azo (N=N)
c. Has a conjugated system
N d. Exhibits resonance of electrons
N
H
O

N
N
OH

Diagram 10. Structure of Sudan-1

Diagram 7. Coupling Reaction for Sudan-1
The benzene ring has an OH- substituent
attached to it. OH is known to be an activator, and thus
is ortho, para directing. This means the attack could be
on 3 sights, at C1, C3 and C5. Carbon 5 has no free
hydrogen group which can undergo substitution, and so,
cannot react. Looking at the resonance structures
formed when the -naphthol, we see that C1 produces
seven resonance stabilized structures and C3 only
The azo group links the aromatic rings together
causing increased conjugation within the molecule. The
longer the extended conjugation system, the longer the
wavelength of light absorbed. Additionally, Sudan 1
contains an OH group which acts as auxochromes or a
colour helper.
Although auxochromes cannot in itself absorb light, it
can shift the color produced by the chromophore by
increasing or decreasing the wavelength it can absorb.
As mentioned before, the auxochrome of Sudan 1 is OH.
An OH group has electron donating ability, thus produces
a bathrochromic effect. A bathrochromic effect is the
change of spectral band position of a molecule to a
reflection of a longer wavelength. Furthermore, as the
auxochrome is placed in the ortho position, the
wavelength absorbed is even more elongated. As a result
of all these factors, the final wavelength this compound
absorbs is 490500 nm, or the wavelength corresponding
to blue-green.

The perception of a particular color is a tricky thing.

What the eyes actually see is the reflected color of an
object, and not the color absorbed by it. In essence, a
color is every color but the one you see. Ergo, a colored
object appears as the color complementary to the
wavelength it absorbs. In this case, the complementary
color of blue-green is red, the characteristic color of
produces six, one less than C1. Therefore, C1 is Sudan-1.
favoured.
Diagram 8. Resonance at C1 The table below summarizes the results of the
experiment:

Weight of 1-phenylazo-2- 0.06 g

naphthol, g

Theoretical yield, g 0.54 g

Percent yield 11%

Experimental Melting Point 129C

Theoretical Melting Point 134C

Diagram 9. Resonance at C3
Percent error 0-3.73%

Table 1. Results
After all the processes, the product yielded a
very low 11% percent yield. Although, the synthesis was
quite successful since the purity is high. A 129C melting
point was obtained during the melting point
determination, which is not so far off from the theoretical
melting point of 134C.
Possible sources of error that affected the yield
could have been the slight inaccuracy of the particular
amounts of reagents used and increased temperatures
due to the complications with the rock salt ice bath, and
miscalculated pH ranges which consequently might have
created side products. Unavoidable contaminated
reagents might have also been used that could have
possibly lead to other side unforeseeable reactions and
errors.
Specific side reactions are as follows:
1. Formation of diazoaminobenzene
If the amount of HCl used during
diazotization was too small, a coupling reaction
between the phenyldiazonium ion and the aniline
might have occurred producing a diazoamino
compound. Mechanism is shown below:
Diagram 11. Mechanism of diazoaminobenzene side
product
2. Protonation of aniline due to low pH in 2-naphthol
solution
(refer to diagram 6)
3. Formation of diazotate due to high pH in
phenoldiazonium solution
(refer to diagram 5)
4. Degradation of amine due to high temperatures
(refer to diagram 4)
In direct dying, the dye is dissolved in water and
is heated. The cloth is then immersed in the hot
solution. The molecules of the dye attach to the cloth
fibres through chemical interactions via strong ionic
bonds. The dye used either contains or can form
negative/positive charges and is attracted to the
negative/positive charges of the fibre. Direct dying does
not produce any permanent chemical bond with the
cellulosic fibres. This technique is widely used on paper,
leather, wool, and silk. Some disadvantages of this
technique are the production of bland and dull colours
and low fast washness.
On the other hand, ingrain dying entails a more
complex set of steps. Ingrain dyes are made inside the
fibres of the fabric itself. The fabric is first soaked in an
aromatic amine solution, the coupling component.
These molecules diffuse into the spaces between the
fibres. The fabric is then soaked in the diazonium
solution which reacts to the prior reagent, and forms the
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dye, which is trapped in the grain of the fibres, due to
the large molecule size.
Diagram 12. Ingrain dyeing method
Although direct dying is useful and pretty
simple, it is not always the best method to use. When
dyeing cotton with Sudan-1, direct dyeing cannot be
used due to the structure of cotton in comparison to
Sudan-1.
Cotton vs. Sudan-1
The effectivity of direct dyeing depends on the
strength and similarity of intermolecular forces of
attraction with the fabric. Cotton has an infinite number
of OH groups which are open to H-bonding, while Sudan-
1 only has a few sights for H-bonding. In addition,
molecules of Sudan-1 are quite large and would not
attach easily. Consequently, this will produce only a
weak attraction between the molecules which can be
easily broken by simple washing by water. Ingrain dying
is the better technique because the dye in formed inside
the fabric. This technique is very useful when the dye
and the fabric do not have similar IMFs as displayed
with the example.
The effectiveness of a dye does not depend only in
itself, but also on the type of fabric it reacts with. There
are different kinds of dye and of fabrics to make sure that
each would have a good affinity with each other.
Although, there are some characteristics that define
a good dye: fastness and levelness. Fastness refers to
the resistance of a materials colour to fading or running.
There should be a degree of permanence even when
exposed to extreme conditions such as bleaching and
extreme heat. Moreover, the dye should have a greater
affinity with the fabric than the solvent. Higher affinity for
the fabric makes the dye more resistant to solvent. On
the other hand, levelness refers to the dyes uniformity
on the fabric. There should be no weird blotches and
spots.
4. Conclusion and Recommendations
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The synthesis of 1-Phenylazo-2-Naphthol or Sudan-1

is possible through the diazotization of aniline and
nitrous acid and the coupling reaction of the
phenyldiazonium chloride and -naphthol. The low 11%
yield showed that the experiment was a failure. The
process used proved that the final product can achieve
purity, but not high yield.

The dyeing technique used with Sudan-1 was

appropriate with the fabric used. The ingrain dyeing
method effectively colored the fabric. When run under
water, no dye was washed away, ensuring the good
fastness of the product. Additionally, the fabric was
colored evenly meaning there is also high levelness.

The low percent yield may be accounted by the

creation of multiple side products caused by the
difference in amounts of reagents used, temperature of
the solutions, and the fluctuating pH. It is really
important that the experimenters work fast and
cautiously to avoid any errors.

References

Kolorjet (n.d.). Direct dyes. Retrieved from http://www.dyes-

pigments.com/direct-dyes.html. Appendices
MyTeacherPages. (2002). Essay: Dyes and dying. Retrieved from
http://www.myteacherpages.com/webpages/CCPHS/files/article 1.0217 g aniline 1mol aniline 1000 mmol
%20-%20essay%20dyes%20and%20dyeing.pdf.
2 mL aniline x x x
mL 93.13 g aniline 1 mol
Wikipedia. (2016). Bathochromic shift. Retrieved from
https://en.wikipedia.org/wiki/Bathochromic_shift.
1 mol naphthol 1000 mmol
Monographics (n.d.) General introduction to chemistry of dyes. 0.35 g naphthol x x =2.4
Retrieved from 144.17 g naphthol 1 mol
http://monographs.iarc.fr/ENG/Monographs/vol99/mono99-7.pdf

ChemistrySC. (n.d). Synthesis of sudan. Retrieved from

1 mmol Sudan1 1 mol 248.28 g
http://www.chemistry.sc.chula.ac.th/bsac/Org%20Chem 2.19 mmol aniline x x x
%20Lab_2012/Exp.11[1].pdf 1 mmol aniline 1000 mmol mol
Clark, J. (2004). Reaction of diazonium salts. Retrieved from:
http://www.chemguide.co.uk/organicprops/aniline/propsdiazo.ht
ml Anilin - 1-
e naphth phenylazo-
Institute of Chemisty, University of the Philippines. Organic
chemistry laboratory manual, 2008 ed.; University of the ol 2-naphthol
Philippines: Manila, 2013
WEIGHT/VOLU 0.2ml 0.35g 0.54 g
General introduction to the chemistry of dyes. Retrieved from ME
http://monographs.iarc.fr/ENG/Monographs/vol99/mono99-7.pdf
MOLECULAR 93.13 144.17 248.279
Food Info. (2014). Azo dyes. Retrieved from http://www.food-
WEIGHT g/mol g/mol g/mol
info.net/uk/colour/azo.htm

DENSITY 1.021 1.20 1.219 g/ml

7 g/ml
g/ml

MMOL 2.19 2.43 2.19 mmol

mmol mmol
Percent Yield
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0.06 g
x 100=11
0.54 g

Percent Error

129 134
x 100
134