Você está na página 1de 4

P a g e |1

Synthesis of 1-phenylazo-2-naphthol

ABSTRACT

The synthesis of 1-phenylazo-2-naphthol occurs through a diazotization reaction, which forms diazonium salts, as well as a coupling
reaction that results to the formation of coupling products.[1] These two reactions produced Sudan-1, a compound that may be used
for dyeing or as coloring agents. In this experiment, phenyldiazonium chloride and -naphthol were made to react in order to form
the red azo dye. This dye was then used to color a piece of fabric through ingrain dyeing which produced an orange hue on the cloth.
The solution was then recrystallized but was not able to give off any yield, resulting in a 100% error from the theoretical value of
0.54g.

1. Introduction Sudan-1 was then synthesized by slowly adding the remaining


phynyldiazonium chloride solution to the cold -naphthol solution
Sudan-1, also known as 1-phenylazo-2-naphthol, is a type of azo while continuously stirring. The mixture was ten left to stand for 1-
dye which is commonly used as an industrial coloring agent. It 5 minutes at 4C. The product was then filtered and thoroughly
contains chromophores which allow it to absorb light in the visible washed with small amounts of cold water. This was then
region and in turn reflect certain colors. The chromophore in azo recrystallized using 10 mL of hot ethanol in a steam bath. In the
dyes comes in the form of the functional group N=N that connect event that some of the solids do not dissolve after the addition of 20
two aromatic rings together, forming conjugated double bonds that mL hot ethanol, the undissolved solids were filtered off. The filtrate
allow for the absorption of light. The intensity of the color imparted was then left to cool in order to recrystallize. [1]
by the dye on the cloth may also be modified through the addition
of auxochrome groups on to the aryl ring. These are substituents 3. Results and Discussion
that have a lone pair of elections. [2]
The synthesis of 1-phenylazo-2-naphthol is typically done in a
Azo dyes are mainly synthesized in two reactions. It first two pot synthesis wherein two separate containers are used for the
undergoes a diazotization reaction where in aromatic amines are different components. A diazotization reaction occurs in the first
made to react with nitrous acid thus forming the intermediate in container which starts off with the production of nitrous acid
the form of the diazonium salt. It is then followed by a coupling through the combination of concentrated hydrochloric acid (HCl)
reaction where in the aryl diazonium ion that is positively charged and sodium nitrate (NaNO2). The nitrous acid was then protonated
acts as an electrophile towards activated aromatics, e.g. anilines and which caused the release of the water molecule and the production
phenol. This then leads to the production of the azo dye. [3] of the nitrosonium ion. The nitrosonium ion, which acts as the
diazotization ion, is then reacted with the aniline, creating the
In this experiment, 1-phenylazo-2-naphthol was synthesized by phenyldiazonium ion, whose reaction mechanism can be seen in
reacting phenyldiazonium chloride and -naphthol together. Figure 1. [4]
This was then used to color a fabric through ingrain dyeing,
giving it a light orange hue.

2. Materials and Methods

The phenyldiazonium chloride solution was prepared by mixing


0.2 mL aniline, 0.35 mL water and 0.5 mL concentrated HCl in a 50-
mL Erlenmeyer flask. This was then cooled to 4C by using an ice
bath whose temperature was maintained with the addition of rock
salt. One mL of ice-cold distilled water was then added to the
mixture followed by the gradual addition of a spatula-full of NaNO2
crystals. The temperature of the reaction mixture was maintained
below 5C in order to prevent it from decomposing. The -naphthol
solution was then prepared by dissolving 0.35 grams of -naphthol
in 4.5 mL 5% aqueous NaOH inside a 50-mL beakers and then
cooling the mixture to 4C. Fig. 1. Reaction mechanism of phenyldiazonium ion [5]

The ingrain dyeing procedure was done by placing the cotton The reaction mixtures were kept at temperatures below 5C in
fabric in a cold -naphthol solution that is submerged in an ice bath order to prevent the formation of side products such as phenol,
and was left for 2-3 minutes in order to soak up the solution. The which is of no use to its synthesis. If this reaction was done under
fabric was then removed and then patted dry in between two filter basic conditions, this would lead to the production of a pink N-
papers. The fabric was then immersed in the phenyldiazonium nitroso compound which is also not necessary for the synthesis of
chloride solution for several minutes then was rinsed well with the phenyldiazonium ion. [5]
running water.
P a g e |2

Fig. 2. Reaction mechanism of the side product Phenol [5]

Fig. 7. Resonance Structures of the Attack on C3 [5]

Fig. 3. Reaction mechanism of the side product N-Nitroso [5] The theoretical color of the Sudan-1 that is to be obtained was
red due to the conjugated double bonds present in its structure
In the second container, the -naphthol solution is then which allowed for the absorption of light in the visible region. The
prepared by dissolving it in NaOH, a basic solution, which forms a red color of the crystals is attributed to the presence of the OH
resonance-stabilized naphthoxide ion. If the reaction was done in auxochrome. This intensifies and enhances the color of the dye as it
an acidic medium, the -naphthol will be protonated and thus will increases the wavelength of absorption. [2]
form a carbocation. The carbocations tend to be very reactive so
they can react with the nucleophiles present in the solution which A 0% yield was obtained during the synthesis of 1-phenylazo-2-
will lead to the production of side products. [6] naphthol which may have been caused by several sources of error.
One of the most prominent errors would be the temperature at
which the experiment was done in. It was important that the
reaction mixture was done at temperatures below 5C in order to
prevent to formation of side products and in order to ensure that
the synthesis of the two components undergoes completion, but
due to the extremely hot temperature of the current season, the
Fig. 4. Reaction mechanism of the -naphthol solution [6] temperature of the reaction was harder to maintain. The purity of
the reagents used may also have played a part as the aniline used
The use of the two-pot synthesis method for the synthesis of 1- was already brown indicating its low purity.
phenylazo-2-naphthol was necessary as the two components were
prepared in different pH levels, with the phenyldiazodium chloride There are several types of dyeing, one of which is direct dyeing.
done in an acidic medium and the -naphthol solution done in a Direct dyeing is composed of the fabric and the dye and is mainly
basic medium. The phynyldiazonium chloride solution is then used for fabrics and dyes of the same IMFA. Ingrain dyeing on the
added to the -naphthol solution to start the coupling reaction other hand uses the fabric as well as the components of the dye,
which causes the diazonium ion to attack the carbon of the - also known as dye precursors. This is used when the fabric and dye
naphthol. [3] There are two possible carbons for the diazonium ion have different IMFAs so the smaller dye precursors are used so that
to attack but the attack on C1 is more favored than C3 since it is they are able to seep into the fabric. The synthesis of the dye is then
more stable as it has 7 resonance structures, with 4 that are done within the fabric itself, creating a dye molecule that is big
aromatic, while C3 has 6 with 2 that are aromatic. which will then in turn be trapped inside the fabric. The two
properties used in order to assess the quality of the dye are fastness
and levelness. Fastness consists of retention factor of the dye as
well as its resistance to fading. Levelness on the other hand refers
to the uniformity of the color that the dye imparts on the fabric. [7]

The second part of the experiment consists of the dyeing of the


cotton fabric through ingrain dyeing. Ingrain dyeing is the more
Fig. 5. Coupling Reaction of Sudan-1 [5] appropriate choice for cotton and Sudan-1 rather than direct
dyeing. Since cotton consists of many OH molecules while Sudan-1
has only 1 OH molecule, the H-bonding that occurs under direct
dyeing will not be effective resulting in a lower fastness and
levelness than in ingrain dyeing. Their opposing IMFAs on the other
hand favor ingrain dyeing more which is why it is the more
appropriate technique.

Fig. 6. Resonance Structures of the Attack on C1 [5]

Fig. 8. Chemical Structure of Cotton [8]


P a g e |3

[8] Vision Learning. http://www.visionlearning.com/en/library/


4. Conclusion and Recommendations Inside-Science/58/Ruth-Benerito/205 (Accessed April 26, 2016).

The synthesis of 1-phenylazo-2-naphthol from phenyldiazonium [9] National Institute of Standards and Technology. http://webbook
chloride and -naphthol did not give any yield leading to a 100% .nist.gov/cgi/cbook.cgi?ID=C842079&Mask=400 (Accessed April 26,
error from the theoretical value of 0.54 g. The experimental melting 2016).
point in turn could not be determined from its theoretical value of
133-134 C [9] thus the purity of the dye could not be assessed. The
filter paper used exhibited a red orange color indicating that the
Sudan-1 had been produced but due to the extremely low yield, it
could not be weighed. Despite not obtaining any 1-phenylazo-2-
naphthol, the fabric was still successfully dyed through ingrain
dyeing as it was able to produce an orange hue.

In order to obtain a higher yield it would be recommended to do


the entire experiment in a much cooler room or during a cooler
season as it is imperative that the temperature of the reaction is
kept below 5C. The solutions should also never leave the ice bath
as the momentary exposure to a slightly higher temperature may
greatly affect the yield. It would be best if the solutions used were
fresh and of high purity as well. Proper recrystallization method
should also be followed in order to properly obtain the Sudan-1
crystals.

References

[1] Organic Chemistry Lab Manual. (2008). Institute of Chemistry:


UP Diliman.

[2] Essential Chemical Industry. http://www.essentialchemical


industry.org/materials-and-applications/colorants.html (Accessed
April 24, 2016).

[3] Azo Coupling http://www.organic-chemistry.org/named


reactions/azo-coupling.shtm (Accessed April 24, 2016).

[4] McMurry, J.E. Organic Chemistry, 8th ed. Cengage Learning,


2013.

[5] R.O.C. Norman and C. M. Coxon, Principles of Organic Synthesis,


CRC Press, New York, 2009.

[6] Williamson Ether Synthesis. http://www.mendelset.com/arti


cles/694/williamson_ether_synthesis (Accessed April 25, 2016).

[7] Solomons, T.W; Fryhle, C. Organic Chemistry, 10th ed. John


Wiley and Sons, Inc., US 2011.
P a g e |4

Appendix I

Table 1. Properties of Aniline, -naphthol and Sudan-1


Property Aniline -naphthol Sudan-1
Weight, g 0.204 0.35 0.54
Volume, mL 0.2 0.29 0.43
Molecular Weight, g/mol 93.13 1454.17 248.29
Density , g/mL 1.02 1.22 1.119
Mmol 2.19 2.43 2.17

1.02 g mol 1 mol Sudan1


0.2 mL Aniline = 0.0022 mol Sudan-1
mol 93.13 g 1 mol Aniline

248.29 g
0.0022 mol Sudan 1 = 0.54 grams Sudan- 1
mol