EXPERIMENT 16- SYNTHESIS OF 1-PHENYLAZO-2-NAPHTHOL

HONEYLYN A. HERBIETO
Department of Mining, Metallurgical and Materials Engineering, University of the Philippines, Diliman, Quezon City
FEBRUARY 14 AND 19, 2014
MARCH 5, 2014


Abstract
Azo dyes, one of the most common dyes can be synthesized by diazonization followed by coupling reaction. In
this experiment, 1-Phenylazo-2-Naphthol, also known as sudan-I an azo dye was synthesized from phenyldiazonium
chloride and -naphthol. The amount of sudan-I obtained was 0.29g which is 52.73% of the theoretical yield of 0.55g.
Error could be accounted by the decomposition of phenyldiazonium chloride which at temperature above 4C could result
in the formation of side products. Ingrain dying was also done in the experiment to observe how sudan-I dyes a cotton
fiber.
Keywords: Azo dye, 1-phenylazo-2-naphthol, ingrain dying


I. Introduction

Dyes have functional groups called
chromophores that absorb light in the visible region,
giving the dye a colour. Chromophores have conjugated
double bonds system that consist of an alternating
double and single bond structure, this allows some
delocalization of electron to occur, absorbing the
energy in light and consequently reflecting colour.
[1]

Auxochromes are groups attached to the
chromophores that influence dye solubility
[2]
; they
deepen the colour of the dye and provide sites where
the dye can chemically bond with the fabric
[1]
. Few
examples of auxochromes are of the type NHR, -NHR
2
,
-OH and OR.
Azo dyes, one of the most common dyes
contain N=N- which links two aromatic rings together,
this conjugation allows visible light to be absorbed
[3]
.
Azo dyes can be synthesized by converting a primary
amine to a diazonium ion and reacting the product with
an aryl compound through electrophilic aromatic
substitution reaction.
The main objective of this experiment is to
synthesize 1-phenylazo-2-naphthol or sudan-1, an azo
dye, orange in colour from -naphthol and
phenyldiazonium chloride. Ingrain dying will also be
observed in the experiment.

II. Methodology

Phenyldiazonium chloride solution was first
prepared at the start of the experiment. 0.2 mL aniline
was added with 0.35 mL water and 0.5 mL concentrated
HCl in 50-mL Erlenmeyer flask. The solution was cooled
to 4C and afterwards, 1-mL of ice cold distilled water
was added. 0.3 g of NaNO
2
crystals were added
gradually to the solution keeping the temperature of
the reaction below 5C.
-naphthol was then prepared next in a 50-mL
beaker by dissolving 0.35 -naphthol in 4.5 mL 5% aq.
NaOH. This was then cooled to 4C.
To observe ingrain dying, a cotton fabric of 2X3
cm was dyed in cold -naphthol solution that was still
immersed in an ice bath, soaking the fabric for 2-3
minutes. After soaking the fabric, remove from the bath
and pat dry between filter papers. The fabric was then
immersed in the phenyldiazonium chloride solution and
after several minutes was removed from the solutions
and was rinsed well with running water.
In order to synthesize sudan-1, the remaining
phenyldiazonium chloride solution was added to the
cold -naphthol solution. Allow solution to stand for 1-5
minutes at 4C. Product was filtered and washed
thoroughly with small portions of cold water. Crude
product was recrystallized using minimal amount of hot
ethanol in a steam bath, melting point was determined
using the recrystallized product.

III. Results and Discussion

In synthesis of sudan-1, it involves two
reaction, diazotization and coupling reaction.
Phenyldiazonium chloride, a diazonium salt is
formed from the diazotization of aniline. This was
then added with phenol to for 1-phenylazo-2-naphthol.
The obtained data are as follows:

Weight filter paper 0.73 g
Weight Sudan-1 obtained 0.29 g
% yield 52.73%
Melting point 131-133C

In the diazotization reaction, the aniline was
reacted with acid and NaNO
2
. The NaNO
2
added with
the acid would produce NO
+
ions that would react with
the nitrogen in aniline forming the intermediate, it then
tautumerizes and with HCl forms the diazonium ion.
After forming the intermediate, coupling reaction is
then done by the addition of phenol. Diazonium ions
are weak electrophile, and can react with aromatic
compounds such as phenols.
For this experiment, -naphthol was added to
the diazonium ion formed. -naphthol was prepared in
basic solution because it reacts more readily in a couple
reaction, although excessive base in the solution could
lead to the formation of another ion (diazotate ion)
instead.


Diazonium ion was supposed to attack the para
of the arylamine, however, since it is already occupied,
it attacks the ortho position instead which is readily
available.
Fig 1. Resonance structure of intermediate diazonium
ion
In the experiment, the phenyldiazonium
chloride was maintained to a temperature below 5C,
this is because at higher temperature, the salt is
unstable and tends to decompose. The water can react
with the diazonium salt and could replace the N
2
, a
good leaving group, with OH from the water.


Dyes are known to be used to colour their
substrate, so they must be designed to have a good
affinity with the substrate and that afterwards, it would
be permanent, not easily fading under water or sunlight
[2]
. In the experiment, ingrain dying was done for the
cotton with sudan-1. The cloth was first immersed in -
naphthol, pat dried and then added to the
phenyldiazonium chloride (diazonium salt) and again
pat dried. After the process, it was then observe that
the cotton cloth now had the permanent colour of
sudan-1, an orange-brown compound. Direct dying
cannot be done on the cotton cloth because cotton is
made up of cellulose which is not reactive to cations or
anions, lacking the polarizing group. In order for
effective dying to occur, sudan-1 is synthesized in the
spaces between the fabric making the colour
permanent.

IV. IV. Conclusion

The main objective of the experiment was to
synthesize sudan-1. Only 0.29g of sudan-1 was obtained
from the theoretical of 0.55g, which was only 52.73%.
synthesizing sudan-1 involved multi-steps that needed
the temperature below 5C, error could have been
made and some side products formed decreasing the
total yield of sudan-1. Human errors could also be
accounted for throught the experiment, such as not
keeping temp low, contamination of solutions,
contamination in recrystallization and others.


V. Reference

[1] "Experiment #1, Synthesis of an Azo Dye for Incorporation
Into Crystals". pages 14-16
[2] "General Introductions to the Chemistry of Dyes,
Principles of colour chemistry". pages 57-58.Accessed at
http://monographs.iarc.fr/ENG/Monographs/vol99/mono99-
7.pdf on March 1, 2014.
[3] "Experiment 11, Synthesis of Sudan-I".
Department of Chemistry, Chulalongkorn
University.2012.
[4] Solomons, T. W. (1996). Organic Chemistry (6th
Edition). New York: John Wiley & Sons, Inc.
[5] Organic Chemistry Laboratory Manual:
Experiment 16: Synthesis of 1-Phenylazo-2-
Naphthol, 2008 ed. Institute of Chemistry,
University of the Philippines Diliman, Quezon City 1101

VI. Appendices