Synthesis of 1-phenylazo-2-naphthol

[1]
Busog, Bea and [2]Villarante, Angelo Ismael M.
[1]
Institute of Biology, College of Science, University of the Philippines, Diliman, Quezon City
[2]
Department of Food Science and Nutrition, College of Home Economics, University of the
Philippines, Diliman, Quezon City
Date Performed: October 30, 2014 November 04, 2014
Date Submitted: November 13, 2014
Abstract
Azo compounds are known for their functions as dyes and coloring reagents.
Formation of 1-phenylazo-2-naphthol, consists of two reactions: diazotization reactions and
coupling reactions. In diazotization reactions, a diazonium salt is formed from aniline and nitrous
acid (NaNO2 + HCl). While in coupling reactions, positively charged diazonium serves as the
electrophile to the -naphthol to give the coupling product. The experiment yielded 24.07% of
the 0.54 g theoretically calculated result. And a 4.48%-11.19% %error range was calculated for
the melting point determination. Possible errors are formation of side products and improper
preparation of reagents.

I. Introduction
Two reactions comprise the synthesis of 1phenylazo-2-naphthol. The first of these
reactions is called diazotization. This reaction
forms one of the most versatile intermediate in
organic synthesis, the diazonium salt. The
intermediate is formed from the reaction of
primary aromatic amines and nitrous acid.

Figure 1.Diazotization reaction

Diazo-compounds are the products formed
from the coupling reaction, the second and last
reaction of the synthesis, wherein the
positively charged aryl diazonium ion serves as
the electrophile towards the highly activated
aromatic substrates such as phenols and
anilines. Most of these diazo-compounds are
used as acid-base indicators like methyl orange
and methyl red and as food coloring agents
such as butter yellow but some are used as
staining agents and as textile dyes for fabric.

Figure 2.Coupling reaction

Textile dyes absorb light in the visible region
through
the
functional
group
called

augmenters
called
auxochromes.
These
includes the types NHR, -NR2, -OH, and OR.
The simple azo dyes that were synthesized in
1-phenylazo-2-naphthol are capable of dyeing
cotton as a developed or ingrain dye.
Dyes that adhere firmly to the fibers without
the aid of supplemental chemicals are within
the method of direct dyeing. These fibers, like
silk and wood, have many polar sites that bind
strongly to the polar dyes such as malachite
green, and methyl orange. In ingrain dyeing on
the other hand, fiber such as those in cotton is
impregnated with an amine, which is then
diazotized and then developed by immersion in
a phenol solution.
The method of dyeing used is such that the dye
is
synthesized
inside
the
fabric.
Two
components used in its synthesis will diffuse
into the spaces between the fibers inside the
fabric. Here, the component reacts within it
forming the azo dye. In this experiment, Sudan
1 will be synthesized through diazotization and
coupling reactions, its property as an ingrain
dye also examined. (Organic Chemistry Manual
2014.)
Levelness refers to how evenly distributed the
dye is throughout the substrate. It relies on the
use of the correct procedure based on the
substrate and the agitation provided by the
machinery being used. It is also derived from
level initial padding of dye for a continuous
dyeing. The resistance of a dye to removal or

chromophores, the color bearers. The

extended conjugation of the two aromatic
rings, the N=N- in azo dyes, causes the light
to
be
absorbed.
Aside
from
these
chromophores, textile dyes also contain color
fabric, thus making it have a few darkly stained
lines and blotches.
In the synthesis of Sudan-1, two-pot synthesis
was used. Two-pot synthesis is appropriate
because it incorporates faster separation
process and more efficient purification (Reusch,
2013).
II. Methodology
In the phenyldiazonium chloride solution, 0.2
mL aniline, 0.35 mL water, and 0.5 mL conc.
HCl were added in a 50-mL Erlenmeyer flask.
The mixture was cooled to 4C, after which 1
mL ice-cold distilled water was added. A
spatula-full NaNO2 crystal was added to the
resulting cold mixture, and maintained its
temperature at below 5C.

destruction is fastness. It is achieved mainly on

the selection of dyes. It also depends on the
removal of hydrolyzed reactive dye.
The synthesized dye that we had made
efficiently passed fastness since the red-orange
dye did not wash out after several washes with
water. In terms of levelness though, our dye
was not evenly distributed all throughout the
Figure 3. Diazotization of aniline with HCl and
NaNO2
Next, the diazonium ion was reacted with
prepared -naphthol solution. This is the
coupling reaction. The -naphthol couples with
the diazonium salt forming a resonance
stabilized intermediate. The figure below shows
the reaction.

-naphthol solution was prepared by dissolving

0.35 g -naphthol in 4.5 mL 5% NaOH (aq) in a
50-mL beaker, was cooled to 4C.
Prior to synthesis, dyeing was done. A fabric
was dyed in the -naphthol solution. After
soaking for 2-3 minutes, the fabric was
removed and pat dried. After which the fabric
was immersed in the phenyldiazonium chloride
solution, then rinsed with running water.
The remaining phenyldiazonium chloride
solution was added to the cold -naphthol
solution. The mixture was allowed to stand at
4C for 1-5 minutes. Filtering was done to the
product, as well as washing with portions of
cold water. Recrystallization was done using
minimal hot ethanol. After which weight
determination was done for the % yield, and
melting
point
determination
was
done
afterwards.
III. Results and Discussion
The
synthesis
of
1-phenylazo-2-naphthol
consists of two reactions, forming of the
diazonium salt intermediate and coupling
reactions. The formation of the diazonium salt
intermediate, or diazotization, was formed by
reacting aniline with HCl and NaNO 2. The
diazotization process starts when a proton and
N is exchanged, from which the Nitrogen lone

Figure 4. Coupling reaction of diazonium salt

with -naphthol.

pairs form triple bonds of N from NaNO 2 (DeTar

et al, 1955). The figure below shows the
detailed reaction mechanism.

Figure 5. Diazonium ion resonance forms.

From the figure above, delocalization of ions
causes the salt to be a weak electrophile. Thus
it would only react with strongly activated
compounds, in this case naphthol, having OH
as the strong activator (as seen from the
intermediate). The diazonium salt attacks the
carbons at para- and ortho- positions with
respect to activating substituent of benzene
(McMurry, 2012). Carbon 1 was

attacked because the OH is in the para- and

ortho- positions. However, the para- position is
unstable due to unavailability of Hydrogen for
substitution, thus the product is formed by the
ortho- position.
Throughout the reaction process, the reaction
mixtures temperature was maintained at
below 5C to prevent decomposition. When
done at higher temperatures a possible side
reaction may occur. -naphthol was prepared
under basic conditions because as a phenol, it
reacts readily at weakly basic conditions. If it
was prepared under acidic conditions, the naphthol will be protonated to form a salt, as
explained on the Chemistry Department of the
Northern Virginia Community College. As
explained on Chemistry Section of the National
Programme on Technology Enhanced Learning,
if the phenyldiazonium chloride was done in a
basic medium, the diazonium salt is reduced to
an aryl radical, which reacts with the benzene
ring. The figure below shows the reaction under
basic conditions.

Figure 6. Diazotization under basic conditions.

Afterwards, ingrain dyeing was done. After the
fabric was soaked in the -naphthol solution
and pat dried, the fabric was immersed in the
phenyldiazonium
chloride
solution.
Upon
immersion, the fabrics color turned to orange.
This indicated the synthesis of desired azo dye.
When the fabric was washed, the color was not
washed off, indicating the dye was trapped
between the fibers of the fabric. Cotton lacks in
strong polarized groups, thus it cannot produce
strong interactions with anions or cations
(Department
of
Textile
and
Apparel

Figure 7. Sudan-1
The table below shows Experimental Results
and Melting Point Determination (See Data
Sheet for Calculations).
Table 1. Experimental Results
1-phenylazo-2naphthol, g
Theoretical Yield
%yield

0.13 g
0.54g
24.07%

Table 2. Melting Point Determination

Experimental Melting
115%-120%
Point, C
Theoretical Melting
134%
Point, C
%error
4.48%-11.9%
In the experiment, we were able to obtain the
melting point of the pure Sudan 1 within the
range of 115-120oC and the crude, ranging
from 119-140oC as oppose to the theoretical
melting point of 134o C. The purity of the
synthesized dye that we obtained theoretically
was accurate and close enough to the
theoretical yield. Using the crude melting point
range, the percent error ranges from 4.48% to
11.19%.
The percent yield we had obtained in the
experiment was unexpectedly low, having it at
only 24.07% with an actual yield of 0.13 grams
and a theoretical yield of 0.54 grams. Possible
sources of error in the experiment could come
from the preparation of the reagents used

Management, University of Missouri, 2008).

From the aforementioned statement, cotton
cannot produce interactions with 1-phenylazo2-naphthol. By using ingrain dyeing instead of
direct dyeing, 1-phenylazo-2-naphthol (an azo
dye) with big molecules can permanently
diffuse the color into the fibers.

itself, the purity of it, or in the preparation of

the 1-phenylazo-2-naphthol. Another thing to
be taken into account would be the formation
of side products that may have formed during
the reactions in the experiment. These side
products are the result of not being able to
prevent keeping the temperature at 4oC.

The red-colored appearance of Sudan 1 with

the
structure
below
is
because
of
delocalization. The light is absorbed in the
visible region once it has synthesized in the
fabric through the functional group called
chromatophore and color deepeners called
auxochromes (Department of Chemistry,
University of Washington).

IV. Conclusion
The experiment was successful in synthesizing
Sudan-1 from the diazotization of aniline.
However, only 0.13 grams of Sudan-1 was
recovered, which yielded a 24.07% from the
0.54 grams of the calculated theoretical yield.
The calculated results could have deviated
from the aforementioned discrepancies in the
previous paragraph.

V. References
[1] McMurry, J. Organic Chemistry. Belmont,
California: Brooks/Cole CENGAGE Learning,
2012.
[2] DeTar, D.F and Turetzky, M.N. 1955. The
Mechanisms of Diazonium Salt Reactions.
Journal of the American Chemical Society.,
77(7), p1745-p1750.
[3] Reusch, W. 2013. Reaction of Amines.
Department of Chemistry, Michigan State
University. < http://www.chemistry.msu.edu/ >
Acessed on November 10, 2014.
[4] Chemistry Section, National Programme on
Technology
Enhanced
Learning.
<
http://nptel.ac.in/ > Accessed on November 11,
2014
[5] Synthesis of an Azo Dye. Department of
Chemistry, University of Washington. <
http://depts.washington.edu/ > Accessed on
November 11, 2014.
[6] Department of Chemistry, North Virginia
Community
College.
<
http://www.nvcc.edu/index.html > Accessed on
November 12, 2014.
[7] Project Cotton. 2008. Department of Textile
and Apparel Management, University of
Missouri. <
http://cotton.missouri.edu/ > Accessed on
November 12, 2014.
[8] Organic Chemistry Laboratory Manual.
Organic Chemistry Academic Group, Institute of
Chemistry. University of the Philippines
Diliman, Quezon City.