Synthesis of Para Red Dye

Muhammad Hazim Tarar

Contribution from Department of Chemistry, LUMS Syed Babar Ali School of Science and
Engineering, Opposite U Block, 54792, DHA Lahore
Received 6th April 2020; Email: 22100053@lums.edu.pk

ABSTRACT : Para red dye was obtained from p-nitro analine, nitrous acid, and 2-naphthol and
purified by vacuum filtration and dried in oven. The product was obtained as a red crystalline
solid, in high yield.

INTRODUCTION their predation by other insects. Carmine is

Over the years there has been quite a lot of
use of dyes. A dye is a colored substance
that usually has an affinity to the substrate to
which it is being applied. Usually dyes are
aromatic compounds having delocalized
electron system. These compounds absorb
electromagnetic radiations of varying
wavelengths in UV-visible region,
depending on the difference in energy levels
of HOMO and LUMO. Dyes are generally
organic compounds applied in an aqueous
solution and require a mordant to improve
its fastness on the fiber. Dyes can be
classified into two groups- Natural Dyes and
Synthetic dyes. Natural dyes are mostly
extracted from plants and insects.
OH
N
N
NO2
f ig2.
Chemical Formula: C16H11N3O3
Well known natural dyes are cochineal dyes
that provide a variety of different colors for
example Carmine, a crimson- colored dye, is
extracted from Cochineal (Dactylopius
coccus), which is a scale insect. These
insects produce carminic acid that deters
primarily used as food coloring agent and
for cosmetics. Natural dyes may also be
found in minerals as well. Most of the
natural dyes are vegetable dyes from plant
sources – roots, berries, bark, leaves,
and wood — and other organic sources such
as fungi and lichens. Examples of plants
from which natural dyes can be extracted
include Catechu or Cutch tree (brown),
Larkspur plant (yellow), Indigofera plant
(blue) etc. Similarly, minerals such as
Arsenic (green), Cobalt (Blue), Copper
(Blue, Green, Purple) also act as sources of
natural dyes. The first human-made
(synthetic) organic dye, mauveine, was
discovered by William Henry Perkin in
1856. Many thousands of synthetic dyes
have since been prepared. After synthetic
pigments and dyes such as alizarin
production in the late 19th century, natural-
dye production gradually diminished.1
Traditional natural dyes were replaced by
synthetic dyes because synthetic dyes are
more economical, provide a wider range of
new dyes, and the dyed materials show
better properties in the case of synthetic
dyes. Food coloring are an example of
synthetic dyes. They are any dye or pigment
which shows a color when added to food or
drinks. Food colors can be found in liquid,
solid, paste or even in gel form. Around 60-
70% of dyes used in the food and textile

Muhammad Hazim Tarar, SBA school of science and engineering

industries are made up of azo dyes (a type of of para-nitroaniline at ice cold temperatures
synthetic dye). Disperse azo dyes are the which is then coupled with naphthol. The
largest category among disperse dyes that process begins by preparing an alkaline
accounts for more than 50% of the total solution of naphthol, followed by the
disperse dyes. These dyes are excellent preparation of diazonium salt using p-
colorants for synthetic fibers because of nitroaniline which is done by reacting p-
their outstanding properties, such as nitroaniline with nitrous acid to produce p-
complete color categories, high degree of nitrophenyl diazonium chloride which is a
exhaustion, and excellent color fastness.2 diazonium salt. The diazonium salt is then
Azo dyes acquired wide interest in coupled with naphthol to produce Para Red
application to biological system and Dye. The reaction scheme is shown in the
indicator in complexometric titration of figure below:
analytical chemistry. Azo dyes are the most
o
important group of synthetic colorants. They HCl + NaNO2 0-5 C NaCl + HNO2
are generally considered as xenobiotic
compounds that are very recalcitrant against
biodegradative processes. Aromatic azo
compounds especially are used as acid-base
O O
indicators, also used in biological strains and - N+ N+ -
O + HNO2 O
commercial colorants for clothing, plastics, + H2O
cosmetics and food beverages. Azo dyes NH2 N+
N -
contain at least one nitrogen-nitrogen double p-nitroaniline Cl
bond (N=N); however, many different p-nitrophenyldiazonium chloride
structures are possible. Monoazo dyes have
only one N=N double bond, while diazo and
triazo dyes contain two and three N=N O OH
8 1 3
double bonds, respectively. The azo groups 7 2 OH 2 4 N+ - N
are generally connected to benzene and 8a O N
6
4a
3
+ 1
5
naphthalene rings but can also be attached to N+ 6
5 4 N
aromatic heterocycles or enolizable aliphatic Cl-
groups. These side groups are necessary for p-nitrophenyldiazonium chloride
2-naphthol NO2
imparting the color of the dye, with many
different shades and intensities being Para Red
possible.3 Azo dyes are prepared by a
reaction known as azo coupling reaction. Fig 1. Reaction scheme of synthesis of
The anilines or phenols can be efficiently Para Red Dye
coupled with aromatic diazonium salts to
To obtain a dry sample of para red dye, the
give the proposed product with high yields.4
solid was separated from the mixture using
Para red dye is an orange-red dye was vacuum filtration and was dried by putting it
discovered in 1880 by von Gallois and in oven. UV Vis and FTIR were carried out
Ullrich and was the first azo-dye ever made. to characterize the compound.
It dyes cellulose fabrics a brilliant red.1 Para
Red Dye is synthesized by the diazotization EXPERIMENTAL SECTION

Muhammad Hazim Tarar, SBA school of science and engineering

Chemicals and Materials 2-Naphthol, p-
nitro aniline, sodium nitrite, sodium
hydroxide, tri-sodium phosphate, HCl, and
ethanol.
Glassware and Equipment Three beakers
(a 250 mL and two 100 mL), a pipette, a
pipette sucker, a magnetic bar, a hot plate,
hardened filter paper, Buchner funnel, an
Erlenmeyer flask (100 mL), a glass rod, a
graduated cylinder, a spatula, an ice bath
and a water bath etc.
Procedure In a 500 mL beaker, 1 g (0.025
mol) of sodium hydroxide, 9.5 g (0.025 mol)
of commercial tri-sodium phosphate were
dissolved in 200 mL of water as a buffer
solution to maintain pH of reaction mixture
and finally 1.4 g (0.01 mol) of 2-naphthol
were added, in the same order. This solution
was stirred until all of the 2-naphthol was
completely dissolved. The solution was
chilled by allowing it to stand in an ice bath
for 5 minutes while it was stirred
intermittently. Meanwhile, a 100 mL beaker
was taken, and 3 mL of distilled water was
added in it. 3 mL of concentrated
hydrochloric acid was pipetted out and
added into the beaker containing water. 1.4
g of p-nitro aniline was dissolved in dilute
acidic solution in the beaker by gentle
warming on hot plate. Heating was
continued until all of the p-nitro aniline was
dissolved. The solution was cooled down to
room temperature and poured into a 100 mL
Erlenmeyer flask which contained about 10
g of chopped ice. The mixture was swirled
to obtain a fine suspension of the crystals of
p-nitro aniline hydrochloride, while the
temperature of the mixture was maintained
at 5–10 °C in the ice bath. 0.8 g (0.011
moles) of sodium nitrite were added in 3–4
mL of water and were poured into the cold
solution of p-nitro aniline hydrochloride as
quickly as possible. The mixture was
swirled until most of the hydrochloride
dissolved (2-3 min), it was allowed to stand
Muhammad Hazim Tarar, SBA school of science and engineering
for a few minutes to complete the
diazotization. The diazonium salt solution
was poured all at once into the chilled
alkaline solution of 2– naphthol. The
material was stirred vigorously for a few
minutes to ensure the completion of the
reaction and then, after adding 5 mL of
concentrated hydrochloric acid, the
temperature was raised to about 30 °C on a
water bath and stirred for 30 - 40 min with
the help of glass rod. The bright red dye was
collected after vacuum filtration, using a
hardened filter paper whose weight was
already measured. The solid was allowed to
dry completely and was then re-dispersed in
100 mL of water. The solid was collected by
vacuum filtration and was washed with
distilled water until the filtrate was
essentially free of chloride ion (filtrate
showed neutral pH). The crystals of azo dye
were washed finally with small portions of
ethanol. After the dye was dried it was taken
to oven where it was kept till 30 minutes.
Finally, the dye was weighed and
characterized by using UV Vis and FTIR.
RESULTS AND DISCUSSION
Percentage Yield Calculation
The percentage yield calculation involves
three steps:
1. Calculation of theoretical yield
Number of moles of naphthol=0.01
Mass of p-nitroaniline used=1.4g
Molecular mass of p-nitroaniline=
138.1g/mol
Number of moles of p-nitroaniline used=
1.4
=0.01
138.1
Molecular mass of Para Red=293.82g/mol
Theoretical Yield=0.01*293.82=2.938 g
2. Calculation of Experimental Yield
Mass of filter paper 1.068g
Mass of Para Red + 3.535g
filter paper
 Experimental Yield 2.467g
Table 1. Recordings of masses to calculate
the mass of para red dye produced

3. Percentage Yield Calculation

Percentage Yield=
Experimental Yield 2.467
∗100= ∗100=83.9 %
Theoretrical Yield 2.938

For the calculation of percentage yield, we

needed to first calculate the theoretical yield
which is done by using stoichiometry. The
number of moles used for naphthol and p-
nitroaniline were both 0.1. Since they react
in 1:1, the number of moles of Para Red dye
had to be 0.01. After this, the molecular
mass of para red was determined, and
theoretical yield was calculated. Next, the
Fig 2. UV Vis Spectrum of the product
experimental yield was calculated by
subtracting the mass of filter paper from the
The spectrum is studied using UV-Vis
total mass to obtain the mass of dry para red
Spectroscopy and it has been found that
dye produced. Finally, the percentage yield
Para-Red shows maximum absorption at
was calculated which came out to be 84%.
485nm with the highest absorption value
The percentage yield appeared to be
being 1.699. This region is also the visible
somewhat low due to reasons such as
region thus confirming the presence of a dye
material loss during the vigorous stirring in
formed.
the coupling reaction. Also, there might be a
n → π* 326 nm
possibility that the reagents provided were
not up to 100% pure. Other than that, no π → π* 485 nm
reasons were found which resulted in the
lowering of percentage yield. our values reconcile with the literature
values
Characterization of Product using UV Vis
Spectroscopy
Characterization of the product using
FTIR

Muhammad Hazim Tarar, SBA school of science and engineering

 90
80 70
Transmittance[%]
60 50
40

311 5.3 7
306 5.8 2

162 3.9 1
159 1.4 6
157 4.3 7

132 8.3 1

122 5.3 3
120 0.3 0
115 2.5 6
110 4.9 9
1554.44
1497.98
1454.00
1401.44

1258.12

858.56
834.46
746 .31
684 .27
4 00 0 3 50 0 30 00 25 00 20 00 1 50 0 10 00 5 00
Wa ve num ber c m -1

wavenumbers provided by the website of the

Department of Chemistry UCLA. The
standard values are quoted in Table 2.

Post Lab Questions

1. The effect on the rate of reaction if

p- methyl aniline is used instead of
p-nitro aniline. As p-methyl aniline
is an electron donating group, it will
decrease the electrophilicity of azo
group. Hence, will result in the
decrease in the rate of reaction

C:\PROGRAM FILES\OPUS_65\MEAS\Haniya-Mahnoor.1 Haniya-Mahnoor ATR platinum Diamond 1 Refl 13/03/2018 2. Why is it advised not to try taking
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melting point of the final product?
Fig 3. FTIR Spectrum of the product The dye might decompose before its
melting point (258-252’C). So, it is
Type of Standard Experiment not recommended to check the
Phenomen Wavenumb al melting point of the dye by capillary
on er (cm-1) Wavenumb method available in lab.
er (cm-1) 3. Why is necessary to keep the
Benzene 1600-1450 1591.46 & temperature below 5 °C during the
Ring (weak) 1574.37 diazotization reaction. At room
NO2 Stretch 1600-1500 1497.98 & temperature, the reaction of HCl
and 1400- 1328.31 and NaNO2 results in the production
1300(strong) of NO, NaCl and NaNO3. Hence,
OH 3115.37 3200-2700 HNO3 will not be produced which is
Stretching (weak) required diazotization.
(Alcohol)
Conjugated 1650-1600 1623.91
Alkene (medium)
Table 2. IR Spectrum of Para Red CONCLUSION

For confirming the presence of Para Red Para Red dye was synthesized in a multiple
dye, we first need to assign major peaks to step experimenting starting from the
the functional groups of Para Red Dye. Two preparation of an alkaline solution of
weak peaks (1591.46 and 1574.37) confirm naphthol, followed by the preparation of
the presence of two benzene rings. Two diazonium salt of p-nitroaniline (p-
strong peaks (1497.98 and 1328.31) confirm nitrophenyldiazonium chloride) and finally
the presence of NO2 group. A weak peak at the dye was produced by coupling the
3115.37 confirm the presence of the OH diazonium salt with naphthol. The dye was
group. A medium peak at 1623.91 indicates dried using vacuum filtration, weighed and
the presence of conjugated alkene. All these percentage yield (which came out to be
values were compared with the standard IR 84%) was calculated. The yield was
Muhammad Hazim Tarar, SBA school of science and engineering
somewhat lower due to loss of materials and
possibly due to impurity of the reactants
provided. The presence of the dye was
confirmed by using UV Vis and IR
spectroscopy by assigning major peaks.
Post Lab Questions

REFERENCES

1. Hussain, I.; Yameen, B.; Abbas, G.;

Farrukh, S. U. B., STUDENT'S MANUAL
FOR ORGANIC CHEMISTRY LAB 1.
2020, 91-94.
2. Qiu, J.; Tang, B.; Ju, B.; Zhang, S.;
Jin, X., Clean synthesis of disperse azo dyes
based on peculiar stable 2, 6-dibromo-4-
nitrophenyl diazonium sulfate. Dyes and
Pigments 2020, 173, 107920.
3. Al-Rubaie, L.; Mhessn, R. J.,
Synthesis and characterization of azo dye
para red and new derivatives. Journal of
Chemistry 2012, 9 (1), 465-470.
4. He, Y.; He, W.; Liu, D.; Gu, T.; Wei,
R.; Wang, X., Synthesis of block
copolymers via the combination of RAFT
and a macromolecular azo coupling reaction.
Polymer Chemistry 2013, 4 (2), 402-406.

Muhammad Hazim Tarar, SBA school of science and engineering