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Synthesis of 1-phenylazo-2-naphthol

Jose Sandino A. Bandonil


Institute of Chemistry, University of the Philippines, Diliman, Quezon City
30 October 2014
13 November 2014

Abstract
1-phenylazo-2-naphthol, known by the common name Sudan I, is a red carcinogenic dye previously used in colouring
foodstuffs, plastics, and others; it is classified as an azo compound, a group characterised by the linkage of two arenes
by two double-bonded nitrogen atoms. These compounds may be produced through a diazo coupling reaction between
arenediazonium ions and highly reactive compounds; the arenediazonium ion may be prepared through the
diazotisation of an amine. In the study, aniline was converted to phenyldiazonium chloride in the presence of sodium
nitrite and strong acid, and subsequently reacted with phenolic compound -naphthol to produce Sudan I dye. The
melting point of the product was measured to obtain its qualitative purity. 2.97 grams of the dye was produced, with a
melting point between 129C -132 C.
I. Introduction
1-phenylazo-2-naphthol, also known by the common
name Sudan I (Figure 1), is a red dye used in the
colouring of several materials, including hydrocarbon
solvents, oils, waxes, plastics, and many others; it
was also used as a food colouring. However, it has
been classified as a potential human carcinogen, due
to its tendency to cause tumours in the liver and
urinary bladder of rats, mice and rabbits (Stiborova
et. al., 2002). Sudan I is classified as an azo
compound.
Azo compounds are a group of compounds
characterised by two arenes linked by two nitrogen
atoms in a double bond. These compounds are
notable for their use as textile dyes, due to their
intense colouration. This is caused by the extended
conjugated electron system, which allows the
absorption of light in the visible region of the
electromagnetic spectrum. Azo compounds are
formed through the diazo-coupling reaction, an
electrophilic aromatic substitution reactions
between an arenediazonium ion and a highly
reactive compound. (McMurry, 2008).

Figure 1. 1-phenylazo-2-naphthol. Notice the double


bonded N's linking the two arenes.
The quality of the dyes formed from the diazo
coupling reaction are judged by two qualities: its
fastness and its levelness. Levelness is the uniformity
of the dye upon its application on the surface of the
fabric, while fastness is the ability of the dye to stick
to maintain its colour.
Dyeing is the process of colouring objects, usually
textiles, with a designated colour through the
application of a dye on the surface to be coloured.
The process of dyeing depends on the ability of the
dye to gain access to the interior of the fibre, and its
subsequent ability to stay fixed in its substrate.
Several techniques are available in the application of
dyes, including pigment dyeing, ingrain dyeing, and
direct dyeing (Marshall Cavendish Corp.), among
which ingrain and direct dyeing are the primary
ones. Direct dyeing is the process involved for the
colouring of a fibre with several polar sites through a
polar dye; the process simply involves the immersion
of the fibre in a single solution. On the other hand,
ingrain dyeing, also known as developed dyeing,
involves the soaking of the fibre on an alkaline

phenol solution, subsequently followed by


immersion in a diazonium salt solution, letting the
diazo coupling reaction forming the dye take place in
the fibres (Seager & Slabaugh, 2013).
II. Methodology
To form the dye, the reagents phenyldiazonium
chloride (C6H5N2Cl) and -naphthol (C10H7OH) for the
diazo coupling reaction was prepared.
To prepare the phenyldiazonium chloride solution
(Figure 2), 0.2 mL aniline (C6H5NH2), 0.35 mL water,
and 0.5 mL concentrated hydrochloric acid (HCl) was
combined in an Erlenmeyer flask. The mixture was
cooled to 4C in an ice bath, and about 1 mL of cold
distilled water was added. A spatula of sodium nitrite
was gradually added to the flask, and the mixture
temperature kept below 5C. -naphthol (Figure 2)
was prepared through the dissolution of 0.35 g of
the compound in a 4.5 mL 5% sodium hydroxide
(NaOH) solution, and the resulting solution cooled to
4C.

Figure 2. Structure of the reagents phenyl diazonium


chloride and -naphthol involved in the diazo
coupling reaction.
After the preparation of the reagents, a piece of
cotton fabric was dyed through soaking in the
prepared solutions. The fabric was first immersed in
the -naphthol solution for 3 minutes, and dried
through filter paper. The dried cloth was submerged
in the phenyldiazonium chloride solution for 5
minutes, and then rinsed with running water.
The remaining reagents were reacted to produce the
Sudan I dye. The phenyldiazonium chloride solution
was slowly added to the -naphthol solution while
stirring, and allowed to stand for 3 minutes. The
product was filtered and washed with cold water,
and the filtrant air-dried. The weight of the resulting
dye was measured, and its melting point range
determined.
III. Results and Discussion

The formation of 1-phenylazo-2-naphthol is


performed through a diazo coupling reaction (Figure
3) between phenyldiazonium chloride and the naphtholate anion. The coupling reaction involves an
attack of the phenyldiazonium ion on the phenol ring
of the -naphtholate anion, forming a ketonic
aromatic ring on the naphthol side of the azo
intermediate. Resonance stabilisation protonates the
oxygen of the ketonic aromatic ring, forming the final
product, the Sudan I dye (Christie, 2001).

Figure 3. The diazo coupling reaction between


phenyldiazonium chloride and -naphthol, forming
1-phenylazo-2-naphthol.
During the reaction, two possible intermediates may
form, as the phenyldiazonium ion may attack either
the ortho sites, as shown in Figure 3, or the para site
of the -naphthol phenolate ring. However, an attack
on the ortho sites are more favoured, due to the
large steric hindrance by the attached benzene ring
on the para position. Also, a comparison of the
resonance structures (Figure 4) between the orthoattached and para-attached intermediates show that
there is a larger resonance in the ortho position, thus
making the said position more stable and thus the
more favoured reaction.

Figure 4. A comparison between the resonance


structures of the ortho and the para coupling
intermediates.
To produce the Sudan I dye, phenyldiazonium
chloride was prepared through a three step
diazotisation reaction (Figure 5) with aniline in the
presence of sodium nitrite and hydrochloric acid. In
the first step, nitrous acid dissociates into the

nitrosonium ion (NO+) through the protonation of


nitrous acid. The nitrosonium ion reacts with aniline
in a nucleophilic attack by the arene, to produce an
N-nitrosoamine, in the process forming an Nnitrosoaminium ion intermediate. The third step
involves the tautomerisation of the N-nitrosoamine
to a diazohydroxide, later forming the
phenyldiazonium ion through water loss in the
presence of hydrochloric acid (Solomons et. al.,
2014).

Figure 5. The diazotization reaction for aniline,


forming the phenyldiazonium ion, in the presence of
sodium nitrite and hydrochloric acid.
The reaction was done in temperatures below 5C,
due to the inherent instability of the reaction
product. Arenediazonium salts, as a rule, are only
relatively stable at temperatures below 10 C, as
higher temperatures force its decomposition (Figure
6) into the highly stable nitrogen molecule and
carbocations. The instability of the salts also provide
the molecules needed for the Sandmeyer reactions
(Wade, 1987).

Figure 6. The decomposition of phenyldiazonium


chloride into nitrogen and a benzene carbocation.
The reaction mixture was subjected to an acidic
environment to generate nitrous acid from sodium
nitrite (Wade, 1987). Subjecting the said mixture in a
basic solution, on the other hand, achieves the
formation of anilines conjugate base, with aniline
forced to act as an acid in a neutralisation (Figure 7)
reaction, where B stands for the base (Vollhardt &
Schore, 2011). The resulting conjugate base of
aniline may form a salt with the sodium ions from
the dissolved sodium nitrite.

Figure 7. The neutralisation reaction between aniline


and a base.
The preparation of -naphthol, on the other hand,
was done through dissolution of the phenolic
compound in a basic environment. This allows the
phenol ring of the compound to be converted to a
phenolate ion (Ar-O-); this facilitates the coupling
reaction, due to its higher solubility in water as
compared to its unionised form. In addition to this,
the more electron releasing character of the Ogroup as compared to the hydroxyl group more
strongly activates the system towards electrophilic
substitution (Christie, 2001). The dissolution of naphthol on acidic solution, however, may be
subjected to sulfonation, if sulphuric acid was used in
the acidification of the solution.
While the mixing of the reagents for the coupling
reaction was done in a single container, two pot
synthesis was necessary for the formation of the
reaction reagents. This is caused by the contrasting
pH requirements for the preparation of the said
reagents, as mentioned earlier. The adverse effects
of preparing the reagents in a single container, or
one pot synthesis, also necessitate the performance
of the two pot synthesis for the diazo coupling
reaction.
The ingrain process was used in dyeing the cotton
fabric, due to the characteristically weak H-bonding
of the dye molecules polar groups to cottons
hydroxyl groups. This caused by the lack of highly
electronegative groups in the structure of cotton
(Figure 8), and thus the lack of polar sites that Sudan
I can bind to (Landgrebe, 1993). The colouration of
the cotton fabric after the process was dark red
orange. The dye formed is of low quality, deviating
from the normal dark red colour of the pure dye. The
levelness of the dye is low, with some parts of the
fabric having a darker colouration than others; the
dye fastness is relatively good, with the dye not
washing away after rinsing the fabric with water.

Figure 8. A three-ring fragment of the polysaccharide


cellulose.
The colour of the dye was similar to that of the
cotton fabric. 2.97 g of Sudan I, equivalent to 11.96
mmol, was produced from the reaction between
0.35 g (2.43 mmol) -naphthol and 2.19 mmol
phenyldiazonium chloride. The theoretical product
was computed to be 0.60 g of the dye, putting the
reaction at a percent yield of 495%.
The very high percent yield may be explained by the
presence of impurities in the final product. This is
confirmed by the boiling point range of the product,
at 3 C (129-132 C); in comparison with the
theoretical boiling point of the Sudan I (134 C), the
experimental boiling point has a 1.49-3.73% error.
The impurities may be traced to the instability of
arenediazonium salts at temperatures above 5 C, as
stated earlier; periods when the phenyldiazonium
chloride solution was withdrawn from its water bath
likely contributed to this.
IV. Conclusion
The study shows that azo compounds are produced
from an electrophilic aromatic substitution reaction
between a phenol and a diazonium salt, called the
diazo coupling reaction. The diazonium salt may be
prepared through the nucleophilic attack of an
amine on the nitrosonium ion formed from the
dissociation of nitrous acid, through the diazotisation
reaction.

Seager, S.L., & Slabaugh, M.R. (2013). Safety-scale


laboratory experiments for chemistry for
today (8th ed.). Belmont, CA: Brooks/Cole.
Solomons, G., Fryhle, C., & Snyder, S. (2014). Organic
chemistry (11th ed.). Hoboken, NJ: John
Wiley & Sons.
Stiborova, M., Martinek, V., Rydlova, H. Hodek, P., &
Frei, E. (2002). Sudan I is a potential
carcinogen for humans: evidence for its
metabolic activation and detoxication by
human recombinant cytochrome P450 1A1
and liver microsomes. Cancer Research,
62(5678).
Vollhardt, P., &
Schore, N. (2011). Organic
chemistry: structure and function (6th ed.).
NY: W.H. Freeman & Co.
Wade, L.G. Jr. (1987). Organic chemistry. Englewood
Cliffs, NJ: Prentice Hall.
VI. Appendix
Bnap = -naphthol
S1 = 1-phenylazo-2-naphthol
Theoretical Sudan 1 yield:

Percent yield:

Temperature % error:
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The purity of the final product may be improved


through purification of the crude azo dye, either
through recrystallization or sublimation.
V. References
Christie, R.M. (2001). Colour chemistry. Cambridge,
UK: Royal Society of Chemistry.
Landgrebe, J.A. (1993). Theory and practice in the
organic laboratory: with microscale and
standard scale experiments (4th ed.).
Belmont, CA: Brooks/Cole.
Marshall Cavendish Corporation. (2003). How it
works: science and technology, volume 5 (3rd
ed.). Tarrytown, NY: Marshall Cavendish.
McMurry, J. (2008). Organic chemistry (7th ed.).
Belmont, CA: Thomson Learning.

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