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Synthesis of 1-Phenylazo-2-Naphthol
Natalie B. Nisce
College of Home Economics, University of the Philippines, Diliman, Quezon City
Date Performed: February 14, 2014
Date Submitted: March 5, 2014


Abstract
The objective of the experiment was to synthesize 1-phenylazo-2-naphthol, or Sudan 1, from
phenyldiazonium chloride solution and -naphthol solution. The general reaction patterns for Sudan 1
involve diazotization and then coupling reaction with highly activated aromatic compounds. The
experiment yielded 1.26g crude Sudan 1 dye which is 217% of the 0.58g theoretical yield. This
discrepancy in yield can be accounted for by the possible presence of contaminants in the
unrecrystallized crude product. The melting point of the product was determined to be within 118-
125, not too far from the theoretical range which is 131-133 ensuring that our results are
somehow accurate.

I. Introduction

Azo compounds have the functional group R-
N=N-R', where R can be either an aryl or an alkyl
group. In the synthesis of an azo dye, the
diazotization and the coupling reactions are
employed. In diazotization reaction, a primary
aromatic amine reacts with nitrous acid to form
a diazonium salt. For the coupling reaction, the
diazonium salt becomes electrophilic towards
the activated aromatic substrates to produce the
coupling product.


Figure 1. General mechanism of diazotization and
coupling reactions

Azo dyes are often brightly colored and have
been used commercially due to its simple
preparation and cheap large-scale manufacture
cost. Azo dyes are suitable for cotton, rayon, silk,
and other cellulose-based fibers. The specific
combination of the diazo salt and naphthol
determines the color obtained. An advantage of
this dye is that it does not bleed and mix with
other contrasting colors when placed side by
side.

People from India, Australia, and Indonesia have
been using azo dye in their crafts for thousands
of years. However, in the United States, azo dyes
have been banned for commercial use as food
additives and in crafts supplies due to its
possible carcinogenic effects.

Despite its diminishing use, the synthesis of
Sudan 1 is still a beneficial procedure to perform
in the laboratory because the mechanisms
behind the experiment are relevant in the study,
understanding and application of organic
chemistry. One example is the synthesis of
butter yellow, the artificial color additive for
butter. Butter yellow is also produced through
the diazotization and coupling reactions. Today,
butter yellow is primarily used to study
carcinogens and other medical chemical
reactions.

The purpose of this experiment is to synthesize
Sudan 1, a bright red azo dye, using aniline as the
primary aromatic amine reacted with -naphthol
solution. The melting point of the crude product
was also used determined.

II. Methodology

To prepare the phenyldiazonium solution, 0.2mL
aniline was added into a 50mL Erlenmeyer flask
2
along with 0.35mL distilled water and 0.5mL
concentrated hydrochloric acid. The mixture was
cooled in an ice bath until its temperature
reached 4. Adding rock salt into the ice bath
induces freezing point lowering to make the
required temperature attainable. Once the
mixture was at the required temperature, 1mL
ice-cold distilled water was added into the
mixture. Then, 0.33g of sodium nitrite crystals
were gradually added. The temperature of the
mixture was kept below 5.

The -naphthol solution was prepared by
dissolving 0.38g of -naphthol in 4.5mL 5%
sodium hydroxide. The solution was cooled to
4 an ice bath.

Still in the ice bath, a piece of fabric was dipped
into the -naphthol solution for 2-3 minutes. The
fabric was then retrieved from the solution and
dried between filter paper.


Figure 2. Fabric in -naphthol solution

Then, the fabric was again immersed, this time in
the phenyldiazonium chloride solution and
instantly, the fabric turned bright red. After
several minutes, the fabric was removed and
rinsed in running water. Gloves were worn
throughout this process due to the possible
carcinogenic effects of the product compound.


Figure 3. Fabric in phenyldiazonium chloride
solution

The remaining phenyldiazonium chloride
solution was slowly added to the -naphthol
solution. After 5 minutes, the product was
filtered, washed with cold distilled water and
then dried.


Figure 4. Crude Sudan 1 dye

The melting point of the product was
determined by crushing a sample of dried
crude Sudan 1 dye and pressing it into a
capillary tube. The capillary tube was then
attached to a thermometer and both were
submerged partially in a beaker of oil. The
beaker was heated over a hot plate. As the
Sudan sample began to disappear inside the
capillary tube, the temperature was noted.
Once the Sudan sample disappeared
completely, the temperature was noted again.


III. Results and Discussion

The reaction between aniline and sodium
nitrite crystals in the presence of
concentrated hydrochloric acid needed to
take place inside an ice bath because the
3
phenyldiazonium intermediate may convert
back into aniline at higher temperatures.


Figure 5. Formation of diazonium salt

The diazotization reaction begins with the
bimolecular exchange of a proton and
nitrogen. As a result, the nitrogen lone pairs
create triple bonds with the nitrogen from
sodium nitrite.


Figure 6. Formation of diazonium ion

In coupling reaction, the diazonium salt reacts
with carbon 1 of -naphthol to form a
resonance stabilized intermediate. OH
donates its lone pair to Carbon 1 making it
more electron rich. The diazonium salt
attacks at carbon 1 of -naphthol since the
intermediate formed is the most stable.


Figure 7. Coupling reaction

Possible side reactions include the production
of phenol by the direct substitution of OH
from the solution to the diazonium salt. -

can also attach the diazonium salt and
substitute the azo-group to form side
products.

Figure 8. Side reaction when a nucleophile
substitutes the azo-group

A good dye must be safe for humans. It is
unacceptable to use dyes that may be toxic or
have hazardous effects on humans. A good
dye must be able to adhere completely to the
fiber of the product being dyed. The dye must
not bleed when washed nor fade from wear
and tear. To ensure this, a good dye must
contain functional groups that bond
intermolecularly with many surfaces. Sudan 1
is generally non-polar. It does not have
functional groups that are compatible with
the functional groups in cotton, which is
generally polar due to its OH groups. For
Sudan 1 to be an effective dye on cotton, the
ingrain dyeing process must be used. In
ingrain dyeing, Sudan 1 is synthesized right in
the presence of the cotton, as was done in
the experiment, and so the dye is
permanently trapped within the fibers of
cotton.

Theoretically, 0.58g of 1-phenylazo-2-
naphthol should have been produced.
However, because the recrystallization
procedure was omitted, the total product
after the experiment came out to 1.26g,
which is 217% yield. The over amount of yield
may be due to contaminants and impurities
present in the crude Sudan 1 product. The
determined boiling point, 118-125 further
supports that the product was not pure
because the theoretical boiling point of 1-
phenylazo-2-naphthol is 131-133.

IV. Conclusion

The objectives of the experiment were met
since 1-phenylazo-2-naphthol or Sudan 1 dye
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was successfully produced from
phenyldiazonium chloride solution and -
naphthol solution.

The final result is a yield of 1.26g Sudan 1, a
bright red azo dye. The actual yield is 217% of
the theoretical yield, 0.58g.

If the experiment were to be performed again,
I suggest that the recrystallization of the
crude Sudan 1 be performed to ensure a pure
final product.


V. References

Brown, W. H. et al. (2005). Introduction to
Organic Chemistry, 3
rd
ed. New Jersey:
John Wiley and Sons, Inc.

Chang, R. (2010). Chemistry, 10
th
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York: Mc Graw Hill International.

Curtin, D. Y., Fuson, R. C., Hermann, C. K. F.,
Morill, T. C., & Shriner, R. L. (1998). The
systematic identification of organic
compounds, 7
th
ed. New York: John Wiley
& sons, Inc.

Eaton, D.C. (1989). Laboratory Investigations
in Organic Chemistry. McGraw Hill Book
Co., USA.

Mc Murry, J. (2004). Organic Chemistry, 6
th
ed.
New York: Brookes/Cole Thomson.

Zubrick, J. W. (1997). The organic chem lab
survival manual, 4
th
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