DATE PERFORMED: SEPTEMBER 14, 2011

Synthesis of 1-Phenylazo-2-naphthol
R.J. Bitare2, M.C. Endico1, & D. D. Orbe2
Institute of Chemistry, University of the Philippines, Diliman, Quezon City 1101 Philippines
1
Department of Chemical Engineering, College of Engineering, & 2Department of Psychology, College of Social
Sciences and Philosophy, University of the Philippines, Diliman, Quezon City, 1101 Philippines

ABSTRACT

Synthesis of azo compounds can be achieved via the process of diazotization and subsequent azo
coupling. In order to verify this reaction, 1-phenylazo-2-naphthol, commonly known as Sudan I, was
synthesized via the reaction of a phenyldiazonium chloride solution with a basic β-naphthol solution. The
crude product obtained was then subjected to recrystallization and its melting point was obtained. Its
property as an ingrain dye was also examined.

Through the prescribed procedures, a 55.2 % experimental yield, presumed to be pure 1-

phenylazo-2-naphthol, was obtained. The melting range obtained for the product was 80–84 oC, far-off
from the theoretical value of 131 oC. Despite not being as close as theoretically predicted, the occurrence
of the said reaction is still confirmed by the obtained experimental results.

Introduction

Azo compounds are organic compounds
which bear the functional group R-N=N-R’ in
which the hydrocarbons can be either an aryl or
alkyl; they are formally defined as derivatives of
diazene (diimide), HN=NH, wherein both
hydrogens are substituted by hydrocarbon
groups. [8]
Azo compounds are often vividly
colored, mainly due to their highly conjugated
structure. Because of this property, azo
compounds are usually used as dyes. One such
example is 1-phenylazo-2-naphthol, more
commonly known as Sudan I, an orange-red
powdered substance. It was previously used as
dye for textiles and as food coloring but was
subsequently banned for such uses due to its
carcinogenicity.
Azo compounds are usually synthesized
through diazodium coupling reaction, a type of
electrophilic aromatic substitution.
In order to synthesize an azo compound,
arenediazonium salt is reacted with activated
aromatic rings like phenols and other amines.
The amine component of the compound must be
less activated the coupling component.
Meanwhile, the nitrogen in the salt serves as a
bridge between the two rings in the reaction.
The synthesis of 1-phenylazo-2-
naphthol utilizing aniline and β-naphthol is a
two-step process involving diazotization and azo
coupling, as shown by the following reaction
diagram:[4]
 NH2 + mixture was produced after 1-mL of cold
N
NaNO2/HCl/H2O N -
Cl
OH
N
N down and maintained at a temperature of about
NaOH/H2O
OH
Figure 1. General reaction to synthesize 1-
phenylazo-2-naphthol via azotization and
coupling reaction
This experiment aims to synthesize 1-
phenylazo-2-naphthol via the aforementioned
reaction.
Experimental Detail
Synthesis of 1-phenylazo-2-naphthol is
divided into two major procedural reactions: the
diazotization reaction and the coupling reaction.
As such, this experimental methodology follows
the same trend with the addition of ingrain
dyeing as an application procedure.
There are two main preparations that
were done during the course of this experiment:
1) preparation of the diazonium salt
(phenyldiazonium chloride) solution and 2)
preparation of the β-naphthol solution.
To prepare the diazonium salt solution,
0.2 mL aniline, 0.35 mL water and 0.5 mL
concentrated hydrochloric acid were combined
in a 50-mL Erlenmeyer flask strictly following
the sequence of introduction as stated here. The
solution was then subjected to a decrease in
temperature via an ice bath to about 4° C. A cold
distilled water was combined into the mixture.
To this resulting mixture, 0.3 g of NaNO2
crystals was gradually added while maintaining
the temperature below 5 °C.
A β-naphthol solution was prepared by
simply dissolving 0.35 g β-naphthol in 4.5 mL 5%
aqueous NaOH in a 50-mL beaker. As with the
diazonium solution, this preparation was cooled
4 °C.
To pre-test the synthesis reaction,
ingrain dyeing was done. Because of the nature
of the Sudan-1 (1-phenylazo-2-naphthol) dye, it
doesn’t react or bond well with cotton fabric
because of the lack of functional groups in the
fabric. As a counter method to this limitation,
ingrain dyeing was developed. Instead of
producing the dye independently then applying
it to the fabric, Sudan-1 is synthesized inside the
fabric so that it will be trapped in the individual
fabric components where it will be formed. To
do this, a 2 by 3 cm fabric was first soaked in the
cold β-naphthol solution for about 2-3 minutes.
It was then removed, patted dry with filter
papers and immersed in the phenyldiazonium
chloride solution. As a result, a prominent red-
orange dye formed within the fabric. After some
more minutes, it was removed from the solution
and rinsed well with running water. The red-
orange dye remained in the fabric.
After the ingrain dyeing, synthesis of
Sudan-1 using the combination of what
remained of the 2 preparations was set.
Phenyldiazonium chloride solution was added
into the β-naphthol solution slowly while stirring.
The mixture was still maintained at about 4° C
for 1-5 minutes before filtering the product and
washing it with small portions of cold water.
This crude product was recrystallized using
minimal portions of hot ethanol in a steam bath.
The resulting red crystals were collected, dried
and weighed along a pre-weighed filter paper to
determine the over-all yield in the synthesis
reaction. N
+ OH

N
Finally, the melting point of the product -
Cl
was determined using the common hot oil
immersion technique. OH
+
N
Results and Discussions
N
-
Table 1. Experimental Results Cl Coupling

Weight of Sudan I 0.30 g

Theoretical Yield 0.54 g
Percent Yield 55.2%
Melting Point 80-84 oC

The red-orange azo dye 1-phenylazo-2-

naphthol was obtained through the reaction of a
diazonium salt intermediate formed from aniline
with β-naphthol. 0.2 mL of aniline and 0.35 g of
β-naphthol produced 0.3 g of 1-phenylazo-2-
naphthol upon experimentation. The expected
yield was .54 g or 2.19 mmol. Therefore, the
experimental yield is just 55% of what could
have been produced in a total and perfect
synthesis.
Of a very conspicuous note would be the
discrepancy of the experimentally-determined
melting point and that of what was theoretically
proposed. The experimenters posit 2 possible
sources of error for this inconsistency: 1) a large
amount of impurity in the final product and 2) a
self-imposed miscalculation during the actual
melting point determination. The latter may have
been caused by an inefficient set-up while the
former is being attributed to potential lapses
during the filtration phases.
For the particular method of
synthesizing 1-phenylazo-2-naphthol perfomed
in the experiment, the reaction mechanism is as
follows:
-
Cl N - HCl
N
H N N
+
O OH
H
Diazonium coupling of aromatic
diazonium ions normally happen only with
active substrates such as amines and phenols,
both of which are strongly activating ortho-para
directors. Considering the size of the attacking
species (in this aromatic electrophilic
substitution), substitution occurs mostly in the
para position relative to the activating group.
The ability of amines to give ortho and para
products shows that even in acidic medium, they
are reacting in un-ionized forms. However, at
very highly acidic concentrations, no reactions
occur because the concentration of free amines
becomes too small. This is the reason why
concentrations of acidity are controlled in this
experiment. However, this may also be a source
of error as the pH levels weren’t monitored in
the entire experiment. [7]

+
NH2 NH3
HCl NaNO2 + HCl
-
Cl Diazotization

N N
H N H N
+
O + OH
H C
Figure 2. Resonance structure of the attack of
the diazonium ion on carbon 1 of β-naphthol.
As shown in the figure above, there are
2 possible ways of coupling with the β-naphthol.
However, of these 2, the attack on carbon 1 is
preferred because it favors retaining the
resonance-stabilized structure of the ring and
sets the positive charge at a position favorable to
the entire synthesis.
In addition to our product of interest,
there are also 2 possible side reactions that may
result into 2 unwanted product formations. The
first one is the direct substitution of a
nucleophile present in the interacting solution.
The nucleophile may substitute the nitrogen in
the diazonium salt and may form other aromatic
compounds like phenol. The second one is the
possibility for a decomposition reaction due to
heightened temperatures. In this case, the
product reverts back to aniline (the reverse
reaction of what is in Figure 1).
+
N Nuc
acid
N
+ Nuc
Figure 3. Side reaction wherein a nucleophilic
substitution involving nucleophiles such as –OH
occurs.
Practical applications for the main
product of this synthesis reaction was said to be
in the field of dyeing. A dye is considered ideal
if it is absorbed by the target fibers efficiently.
For this to happen, the dye must be perfectly
bonded with the material of the cloth. The
functional groups present in the dye determine
the strength of adhesion between the dye and the
textile. The best dye is the one which is capable
of being absorbed by most fibers. This dye may
have a structure ideal for bonding with the
material of mostly used textiles. As discussed
earlier, Sudan 1 is not an efficient dye because
its particle sizes and its reactivities are not
efficient for use with certain textiles (i.e. cotton).
This is particularly due to unmatched structures
that inhibit direct bonding. Consequently, it was
classified as a category 3 carcinogen[10].
Meaning, the substance is potentially harmful
and may cause cancer in humans.
Aside from 1-phenylazo-2-naphthol,
which can be prepared by using aniline as the
amine and β-naphthol as the coupling
component, other dyes that can be prepared via a
similar format include:
O
OH CH3
N N
N CH3
1. ,
O
OH
which can be prepared by using NH2
CH3
N
CH3
as the amine and as coupling
component;
 N N reaction. This, in correspondence, tells us that
the primary objective of this experiment to prove
that an azo dye synthesis exists via the said
reactions has been satisfactorily reached.

H3C N Despite all this, a complementary test

CH3 (melting point determination), seem to be a
2. ,
problematic issue in this experiment. Not that
NH2 this only severs an empirically tested and
theorized physical property of Sudan 1 (melting
which can be prepared by using as point), but it also opens up concerns about sound
CH3 experimental techniques used by the
N experimenters during the course of the
CH3
experiment. With this at hand, the experimenters
the amine and as coupling recommend further investigation on more
component; and efficient ways of a total organic synthesis for 1-
phenylazo-2-naphthol. ‘

OH NH2HO
O
N S
OH NH2 OH O N
O O
S N
N
O
O HO S O
CH3
O
O S OH

3. O

which can be prepared by using

OH NH2 OH
O
S NH2
O

HO S O
O as the amine and

H3C O O CH3 as coupling

component.

Conclusion

The final results show that the

experiment was able to give a 55.2% yield of a
probably still impure sample of Sudan-1.

Regardless of the percent yield, the fact

that 1-phenylazo-2-naphthol was produced and
had given a positive qualitative result (red-
orange dye) validates the theoretical reaction of
diazotization and its corresponding coupling
References Appendix

[1] Bristol, T. S.-U. (2002). Azo Dyes. Retrieved Calculations:

September 19, 2011, from Chemistry of Dyes:
http://www.chm.bris.ac.uk/webprojects2002/pric 1 cm3 1.019 g
0.2 mL Aniline × ×
e/azo.htm mL cm3
1 mol C6 H5 CH2 OH
×
[2] Brown, W. H., Foote, C. S., Iverson, B. L., & 93.1265 g
Anslyn, E. V. (2005). Organic Chemistry (5th = 2.19 mmol Aniline
ed.). United States of America: Brooks/Cole
Cengage Learning. 1 mol β − naphthol
0.35 g β − naphthol ×
144.17 g
[3] Carey, F. A. (1996). Organic Chemistry (3rd = 2.43 mmol β − naphthol
ed.). USA: McGraw-Hill.
∴ Aniline is the limiting reagent.
[4] Chemistry, P. S. (n.d.). Synthesis of the Dye
Sudan I. Retrieved September 20, 2011, from Theoretical yield:
http://courses.chem.psu.edu/chem36/Web%20Sy 1 mmol Sudan I
n06/Exp31Syn06.pdf 2.19 mmol Aniline ×
1 mmol Aniline
= 2.19 mmol Sudan I
[5] Georgia, U. o. (n.d.). Diazotization reactions.
Retrieved September 19, 2011, from 0.24828 g
http://asmehta.myweb.uga.edu/diazotization.htm 2.19 mmol Sudan I ×
1 mmol Sudan I
l = 0.54 g Sudan I

[6] Institute of Chemistry, University of the Actual Yield:

Philippines, Diliman. (2008). Organic
Chemistry Laboratory Manual. Quezon City: 1 mol Sudan I
0.30 g Sudan I ×
Institute of Chemistry, UP Diliman. 248.28 g
= 1.21 mmol Sudan I
[7] March, J. Advanced Organic Chemistry,
McGraw-Hill, 1968, 398-400. Percent Yield:

[8] McMurry, J. E., Organic Chemistry (7th ed.). 1.21 mmol Sudan I
% Yield = = 𝟓𝟓. 𝟐%
Singapore: Thomson Learning, 2008, 941-945. 2.19 mmol Sudan I

[9] Mohrig, J.R., Hammond, C. N., Morrill, T.

C., Neckers, D.C., Experimental Organic
Chemistry. W.H. Freeman, 1998, 719-720, 289-
291.

[10] Refat N.A., Ibrahim Z.S., Moustafa G.G.,

Sakamoto K.Q., Ishizuka M, Fujita S. (2008).
"The induction of cytochrome P450 1A1 by
sudan dyes". J. Biochem. Mol. Toxicol. 22 (2):
77–84.