Synthesis of 1-phenylazo-2-naphthol

Abstract
Azo dyes are a varied class of colored synthetic dyes characterized by a N=Nor azo functional
group. The dyes non polar nature make it capable of a special type of dyeing called ingrain
dyeing. In this experiment, the azo dye 1-phenylazo-2-naphthol, also known as Sudan 1, was
synthetized by a diazotization reaction followed by a coupling reaction; ingrain dyeing of Sudan 1
on a cotton fabric was also performed. Phenyldiazonium chloride was synthesized in situ by a
reaction between aniline, NaNO 2, water and an excess of HCl in low temperatures. A fabric
dipped in cold basic -naphthol solution was soaked in the diazonium salt solution, where the
dye was ingrained in the cloth. A fresh phenyldiazonium chloride solution was mixed with a new
-naphthol solution, filtered, and recrystalized to extract Sudan 1. The experiment resulted
I. Introduction
Amines (Fig. 1) are organic compounds
characterized by having a nitrogen atom with
a lone pair. The lone pair in the nitrogen is
the reason that amines can undergo
reactions, serving as a site for nucleophilic
attack by electrophiles

Preparation of azo dyes is initiated by first

synthesizing a diazonium salt by reacting a
primary amine with nitrous acid in a process
called diazotization (Fig. 3). The salt is highly
unstable and will easily decompose unless it
was synthesized in specific conditions.
Following diazotization is an electrophilic
aromatic substitution by the salt to a usually
aryl nucleophile in a process called a
coupling reaction. The substitution concludes
with two substituents bonded by an azo
group.

Figure 1. A generalized structure of a

primary amine. Secondary and tertiary
amines are possible as well
Commercial applications are widespread in
amine compounds. Amines are used as
starting material in many commercial
products, such as azo dyes

Figure 3. A general scheme of the

diazotization reaction. In most cases an
Arylamine (Ar) is used for its stability and
delocalized electrons

Azo dyes (Fig. 2) are common names for azo

compounds; it is characterized by a R-N=N-R
structure where R is usually an aryl group.
The N=N is called an azo group, formed by
reacting primary amines with nitrous acid. As
a common characteristic of dyes, azo dyes
are also heavily colored owing to their
conjugated structure.

High colorization is a property of azo dyes

due to their conjugated structure. The
conjugated molecular structure resulting in
color is called a chromophore. The electrons
in chromophores are excited by light in an
energy level contained inside the visible
spectrum (390-700 nm). In most situations,
the chromophore may absorb light in high
wavelengths. In these cases auxochromes
are used to lower the wavelength absorb to
the visible spectrum. Auxochromes such as
OH and NH2 contain free electrons which
add to the conjugation, making the
compound more easily excited and thus
require only less energy. It must be noted
that alone, auxochromes will not result in

Figure 2. Azobenzene is a simple example

of an azo compound. It is also used as a dye.

color;
they
must
be
present
with
chromophores for a visible color observation.

A notable characteristic of azo dyes is their

lack of ability to bond with protein based
fabrics such as wool or silk. The structure of
azo dyes show its predominantly non polar, a
hindrance when bonding with protein based
fibers with their polar amino group. For this
reason acid dyes are used for protein-based
fibers due to their acidic groups that can link
with the relatively basic amino group on the
external of the fabric. To circumvent this,
ingrain dyeing is performed.
Ingrain dyeing is performed inside the fabric
as opposed to direct dyeing by acid dyes.
Usually, the cloth is soaked in the
nucleophile
component
before
being
transferred to the diazonium solution. The
reaction happens inside the fibers of the
fabric and the dye is trapped within, coloring
the fabric.
In this experiment the concepts discussed
will be performed. The azo dye 1-phenylazo2-naphthol, also known as Sudan 1, was
synthesized by a diazotization reaction with
Aniline, NaNO2, HCl, and water followed by a
coupling reaction with -naphthol in a basic
solution. Purification and recrystallization will
be performed to ensure purity of Sudan 1. In
addition, ingrain dyeing of Sudan 1 to a
cotton fabric was performed. The experiment
gauged the purity and yield of the
synthesized Sudan 1 as well as the fastness
and levelness of the dye based on
observations on the cloth dyed.
Add fastness and levelness
II. Methodology
The synthesis of Sudan 1 required a two pot
synthesis
for
each
of
its
coupling

components: the phenyldiazonium chloride

solution and the -naphthol solution.
The phenyldiazonium chloride was prepared
in situ by mixing 0.2 ml phenylamine
(aniline), 0.35 ml water, and 0.5 ml
concentrated hydrochloric acid inside a 50 ml
beaker. The solution was cooled in an ice
bath to 4 C and added with 5 ml of ice cold
distilled water. One spatula full of NaNO 2
crystals was added and the solution was left
to cool.
The -naphthol solution was prepared by
dissolving 0.35 g -naphthol crystals with 5%
aqueous NaOH inside a 50 ml beaker and
cooled in an ice bath to 4 C.
In ingrain dyeing, a small cotton cloth was
dipped inside the -naphthol solution for
about 2-3 minutes. The cloth was taken out
and patted dry with filter paper. The cotton
cloth was soaked with the phenyldiazonium
chloride solution where it was dyed a deep
red color. The resulting dyed cloth was
washed with water.
The synthesis of Sudan 1 was done by
preparing a fresh batch of both cold
phenyldiazonium chloride and -naphthol
solution. The diazonium salt was slowly
added to the -naphthol solution while
stirring. The solution was left standing for 4
minutes after which it was filtered. The
residue was mixed in a new beaker with hot
ethanol until boiling. The boiling solution was
filtered using a fluted filter paper and the
recrystallized Sudan 1 was gathered and left
to dry. It was placed inside a pre-weighed vial
to determine the percent yield. A few amount
of Sudan 1 was taken in order to determine
its melting point and purity.