Silava, Nash Daniel E.

2009-05789

Experiment 16: synthesis of 1-phenylazo-2-
naphthol

Phenyldiazonium chloride solution was
prepared by combining aniline, water and HCl in
an Erlenmeyer flask while keeping the
temperature below 5C and adding a few
NaNO
2
crystals. -naphthol solution was
prepared by dissolving a few grams of -
naphthol in aqueous NaOH and kept cool.
The 2 x 3 cm fabric was then placed in
the -naphthol solution and was allowed to
soak for a 2-3 minutes and it was removed and
pat dry between filter papers. It was then
immersed in the phenyldiazonium chloride
solution. After several minutes, it was removed
and rinsed with water.
After completing the ingrain dying, the
remaining phenyldiazonium chloride solution
was added to the -naphthol solution while
keeping it at 4C. The product was filtered and
recrystalized using ethanol in a steam bath. The
melting point of the product was determined.
The method in synthesizing 1-
Phenylazo-2-naphthol consists of two reactions
the diazotization and coupling reactions.
These are typical electrophilic aromatic
substitutions in which the positive diazonium
ion is the electrophile that reacts with the
electron rich ring of a phenol or arylamine. The
reaction occurs at the para position.
Aniline reacted with NaNO
2
under acidic
condition. That was why HCl was introduced.
The reaction was maintained at 4C to prevent
the decomposition of the diazonium salt into
aniline. The reaction for the diazotization
process is

Figure 1: Diazotization reaction
In the coupling reaction, the charged
diazonium ion reacts with the -naphthol to
give the coupling product.


Figure 2: Coupling reaction

Figure 3: resonance structures of the
intermediate
As discussed previously, the reaction
occurs usually at the para postion but in this
case the ortho position to OH, an ortho & para
director, is favoured since the para position is
blocked by another aromatic ring.
Two possible conditions that would lead
to side products would be (1) the solution is not
kept cold at 4C and (2) conversion to a phenol
by the OH present.

Figure 4: side reaction due to nucleophilic
substitution of nucleophile.
A good dye should mix well with the
cloth fibers. Some dyes are capable of direct
dyeing via chemical interactions called salt
linkages. One must know the properties of the
fabric to be used so one can choose a good dye.
Another property is that the dye should have a
good color. The groups responsible for the
absorption of light are called chromophores. A
dye with a good color is aesthetically pleasing.
Cotton fibers are made up of cellulose and
contain numerous OH functional groups.
These make the cotton fiber very polar. Sudan
1, on the other hand is a non-polar compound,
making its adhesion with cloth fibers very weak.
That was why ingrain dyeing was used, which
involved reacting the components of the dye
inside the cotton fibers, trapping the dye within
the fibers.

References:
(1) Mcmurry, John. Organic Chemistry 5
th
edition,
Brooks/Cole
(2) Organic Chemistry Laboratory manual 2008
edition, Institute of Chemistry, University of the
Philippines Diliman.
(3) http://www.dyespigments.com/what-is-dye.html
(accessed on feb 22)
(4) Salvador, Ruben and Junio, J.D. FR for experiment
16. (2010)