Synthesis of 1-Phenylazo-2-Naphthol

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 -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 1phenylazo-2-naphthol, was obtained. The melting range obtained for the product was 8084 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-2naphthol utilizing aniline and -naphthol is a
two-step process involving diazotization and azo
coupling, as shown by the following reaction
diagram:[4]
NH2
N a N O 2 /H C l/H 2 O
Cl
OH
N
N a O H /H 2 O
N
OH
Figure 1. General reaction to synthesize 1phenylazo-2-naphthol via azotization and

coupling reaction
This experiment aims to synthesize 1phenylazo-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 -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

mixture was produced after 1-mL of 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 -naphthol solution was prepared by
simply dissolving 0.35 g -naphthol in 4.5 mL
5% aqueous NaOH in a 50-mL beaker. As with
the diazonium solution, this preparation was
cooled down and maintained at a temperature of
about 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
doesnt 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 -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 -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.
NH2
NH3
H Cl
Finally, the melting point of the product

was determined using the common hot oil
immersion technique.
Cl
N aN O
+ H C l
D ia z o t iz a t io n
OH
N
Cl
Results and Discussions

Table 1. Experimental Results
OH
Weight of Sudan I
Theoretical Yield
Percent Yield
Melting Point
0.30 g
0.54 g
55.2%
80-84 oC
The red-orange azo dye 1-phenylazo-2naphthol was obtained through the reaction of a
diazonium salt intermediate formed from aniline
with -naphthol. 0.2 mL of aniline and 0.35 g of
-naphthol produced 0.3 g of 1-phenylazo-2naphthol 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:
N
Cl
Cl
N
H
C o u p lin g
- H Cl
N
O
N
OH
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 werent monitored in
the entire experiment. [7]
H
O
+
+
N
OH
Figure 2. Resonance structure of the attack of

the diazonium ion on carbon 1 of -naphthol.
As shown in the figure above, there are
2 possible ways of coupling with the -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).
+
Nuc
Nuc
a c id
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 -naphthol as the coupling
component, other dyes that can be prepared via a
similar format include:
O
OH
N
N
1.
CH3
N
CH3
which can be prepared by using

OH
O
NH2
CH3
NH2
HO
CH3
as the amine and

component;
OH

N
OH NH2
S
as the amine and

as coupling
H3C
CH3
as coupling
component.
Conclusion
H3C
The final results show that the

experiment was able to give a 55.2% yield of a
probably still impure sample of Sudan-1.
N
CH3
2.
,
NH2
as
CH3
N
CH3
the amine and

component; and
as coupling
3.
OH
OH NH2
OH
S
O
OH
CH3
O
O
N
O
NH2HO
HO
S
O
Regardless of the percent yield, the fact

that 1-phenylazo-2-naphthol was produced and
had given a positive qualitative result (redorange dye) validates the theoretical reaction of
diazotization and its corresponding coupling
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.
Despite all this, a complementary test
(melting point determination), seem to be a
problematic issue in this experiment. Not that
this only severs an empirically tested and
theorized physical property of Sudan 1 (melting
point), but it also opens up concerns about sound
experimental
techniques
used
by the
experimenters during the course of the
experiment. With this at hand, the experimenters
recommend further investigation on more
efficient ways of a total organic synthesis for 1phenylazo-2-naphthol.
References
[1] Bristol, T. S.-U. (2002). Azo Dyes. Retrieved
September 19, 2011, from Chemistry of Dyes:
http://www.chm.bris.ac.uk/webprojects2002/pric
e/azo.htm
[2] Brown, W. H., Foote, C. S., Iverson, B. L., &
Anslyn, E. V. (2005). Organic Chemistry (5th
ed.). United States of America: Brooks/Cole
Cengage Learning.
[3] Carey, F. A. (1996). Organic Chemistry (3rd
ed.). USA: McGraw-Hill.
[4] Chemistry, P. S. (n.d.). Synthesis of the Dye
Sudan I. Retrieved September 20, 2011, from
http://courses.chem.psu.edu/chem36/Web
%20Syn06/Exp31Syn06.pdf
[5] Georgia, U. o. (n.d.). Diazotization reactions.
Retrieved
September
19,
2011,
from
http://asmehta.myweb.uga.edu/diazotization.htm
l
[6] Institute of Chemistry, University of the
Philippines,
Diliman.
(2008).
Organic
Chemistry Laboratory Manual. Quezon City:
Institute of Chemistry, UP Diliman.
[7] March, J. Advanced Organic Chemistry,
McGraw-Hill, 1968, 398-400.
[8] McMurry, J. E., Organic Chemistry (7th ed.).
Singapore: Thomson Learning, 2008, 941-945.
[9] Mohrig, J.R., Hammond, C. N., Morrill, T.
C., Neckers, D.C., Experimental Organic
Chemistry. W.H. Freeman, 1998, 719-720, 289291.
[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):
7784.
Appendix
Calculations:
0.2 mL Aniline
1cm3 1.019 g 1 mol C 6 H 5 CH 2 OH
=2
mL
93.1265 g
cm 3
0.35 g naphthol
1mol naphthol
=2.43 mmol na
144.17 g
Aniline is thelimiting reagent .

Theoretical yield:
2.19 mmol Aniline
1 mmol Sudan I
=2.19 mmol Sudan I
1 mmol Aniline
2.19 mmol Sudan I
0.24828 g
=0.54 g Sudan I
1mmol Sudan I
Actual Yield:
0.30 g Sudan I
1 mol Sudan I
=1.21mmol Sudan I
248.28 g
Percent Yield:
Yield=
1.21mmol Sudan I
=55.2
2.19 mmol Sudan I

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DATE PERFORMED: SEPTEMBER 14, 2011

Azo compounds are usually synthesized

Figure 1. General reaction to synthesize 1phenylazo-2-naphthol via azotization and

temperature via an ice bath to about 4 C. A cold

using minimal portions of hot ethanol in a steam

Finally, the melting point of the product

Results and Discussions

Diazonium coupling of aromatic

concentrations of acidity are controlled in this

Figure 2. Resonance structure of the attack of

Figure 3. Side reaction wherein a nucleophilic

which can be prepared by using

as the amine and

which can be prepared by using

as the amine and

The final results show that the

which can be prepared by using

the amine and

Regardless of the percent yield, the fact

"The induction of cytochrome P450 1A1 by

1cm3 1.019 g 1 mol C 6 H 5 CH 2 OH

Aniline is thelimiting reagent .

2.19 mmol Aniline

2.19 mmol Sudan I

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