Synthesis of Azo Dye

Kristine Alvina1 and Ria Mikaella Ladrera2

1, 2
College of Public Health, University of the Philippines Manila

Ermita, 1000 Manila

Abstract

Dyes are organic solids with prominent colors used in coloring food, fabrics, and waxes,

most of which are azo dyes. This experiment makes use of diazotization and azo coupling

mechanisms to synthesize 1-phenyazo-2-naphthol dye. The researchers synthesized the

compound with a percent yield of 1052.06%.

I. Introduction

Organic synthesis is a branch of chemical synthesis and is concerned with the construction of organic

compounds. Basically, it takes pre-existing molecules to make new materials. In the experiment, 1-phenylazo-2-

naphthol dye, also known as Sudan I, was one of the organic compounds synthesized.

Dyes are colored organic substances that show affinity towards the substrates they are being applied to.

Dyes may either be natural or synthetic. Natural dyes are available and are obtained from plants, animals, or

minerals while synthetic dyes must be made by combining different compounds and initiating a reaction between

them. A dyes effectiveness depends on the affinity between the substrate and the dye. For this reason, dyes

must be designed to have a greater affinity for the substrate than the medium from which it is applied, which is

usually water, and it must have a high degree of permanence.

The synthesized dye in the experiment is an azo dye. This type of dye has an azo group (R-N=N-R) and

contains aromatic carbons. Azo groups, along with nitro grous (-NO2) and carbonyl grous (>C=O) are

chromophores, functional groups that absorb light. The synthesis of azo dyes involve two general steps: (1)

diazotization and (2) diazo coupling. The Sudan I dye is a red-orange substance classified as an azo dye. It is

used to colorize waxes, oils, polishes, and even food. The linear chemical formula for this compound is

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C6H5N=NC10H6OH. Because of the azo functional group present (R-N=N-R), it is classified as an azo

compound. (Clayden, J., et. al., 2001) Shown below is the molecular structure of the Sudan I dye.

Figure 1. Structure of Sudan dye I (screenshot from Open Access).

II. Methodology

In synthesizing the 1-phenylazo-2-naphthol dye, 0.9mL of aniline, 1.4mL of water and 2.1mL of

concentrated HCl were combined in a beaker. The contents were cooled and approximately 1g of ice was

added. The mixture was stirred constantly.

Sodium nitrite solution (0.75g in 3mL of water) was added dropwise until the mixture contained excess

nitrous acid. This was tested by spotting a drop of the mixture on starch-iodide paper, with a blue spot indicating

the presence of nitrous acid. All throughout these processes, the mixture should be kept at 0-5C.

In a separate beaker, 1.4g of -naphthol was dissolved in 3mL warm 3 M aqueous NaOH. This was then

slowly added to the initial mixture while stirring constantly. The mixture was left to stand for 15 minutes, again at

a temperature of 0-5C.

The product was collected via gravity filtration and washed with cold water. It was also recrystallized

with ethanol and was left to air dry. Some of its physical properties, such as its color, texture, and odor, were

noted.

III. Results and Discussion

The researchers obtained the following information during the experiment:

Theoretical Yield: 2.47g

Actual Yield: 38.83 g

Percent Yield: 1,572.06%

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 Property Theoretical Observation
Appearance solid Solid dissolved in liquid
Color orange-red Orange-red
Texture powdery Powder dissolved in liquid
Odor Slight odor Slight odor
Melting point 132C (Lide, 2004) Not tested
Table 1. Physical Properties of the Compound

Test Theoretical
NaOH Partially miscible
HCl Slightly miscible
NH4OH Slightly miscible
CH3COOH Slightly miscible
Table 2. Chemical Tests

Figure 2. Formation of nitrous acid and nitrosonium ions (screenshot from Klein).

Sudan I was prepared through a series of steps, starting with the mixing of aniline, concentrated

hydrochloric acid (HCl), and sodium nitrate (NaNO 3). In solution, NaNO2 was protonated by HCl to give nitrous

acid (HNO2). This preparation is done in situ since HNO2 is unstable; this was achieved by creating said acid in

the presence of the amine it will react with (aniline) and the addition of HCl (Klein, 2012). Nitrous acid was

further protonated with HCl to give an oxonium ion. The water in the ion then leaves, creating a nitrosonium ion.

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 Figure 2. Mechanism for the formation of a diazonium compound from aniline (screenshot from Bruice).

The solution was tested for excess nitrous acid in order to determine if all the HCl and NaNO 2 reacted to

create nitrosonium ions. The nitrosonium ion, a strong electrophile, underwent a nucleophilic attack by aniline, a

primary amine. It was then deprotonated by chloride (indicated by B), creating n-phenyl nitrosamine. The lone

pair on the benzyllic nitrogen delocalized to create a pi bond with the nitrogen attached to it, and the pi bond this

nitrogen had with oxygen delocalized to create a lone pair. This oxygen was then protonated by HCl, and the

remaining hydrogen on the benzyllic nitrogen was transferred to chloride, producing an N-hydroxyazo

compound. The hydroxyl group was further protonated to create water, which then left to create the diazonium

ion. Figure 2 shows the overall mechanism.

This diazonium ion forms ionic bonds with chloride to create phenyldiazonium chloride (Bruice, 2014).

Figure 4. Phenyldiazonium chloride (screenshot from Klein).

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 Figure 5. Azo coupling of B-naphthalene to phenyldiazonium anion to from 1-phenylazo-2-naphthol

(image from Wikipedia).

B-naphthol was first dissolved in sodium hydroxide, where the hydroxyl group is deprotonated by a

hydroxide ion. The lone pair on oxygen delocalizes into the benzene ring, and one of the pi bonds will delocalize

to create a negative charge on one of the carbons. 1-phenylazo-2-naphthol is then synthesized through azo

coupling, wherein an aryldiazonium salt (phenyldiazonium chloride) acts as an electrophile which will substitute

onto an nucleophilic activated aromatic ring (naphthol) to create a dye. Diazonium coupling reactions usually

occur at the para position; however, it can also occur at the ortho position if the para position is blocked

(McMurry, 2008). Since B-naphthol is considered a strong activator and ortho-para director due to its hydroxyl

group (Klein, 2012), and the para position in B-naphthol was blocked, the diazonium ion attached at the ortho

position. Figure 4 shows the overall mechanism.

The azo coupling of arenediazonium ions and phenols (naphthalene) is done in slightly alkaline

conditions. A large amount of the phenol is present as phenoxide ions in these conditions, which are more

receptive to electrophilic aromatic substitution. If the pH is greater than 10, the arenediazonium salt reacts with

hydroxide ion to form a relatively unreactive diazohydroxide or diazotate ion (Solomon, 2011).

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 Figure 6. Structure of phenol and phenoxide ion and formation of diazohydroxide and diazotate ion

(screenshot from Solomon).

The entire process is performed below 5C because arenediazonium salts are unstable and will

decompose at a temperature above 5C (Solomon, 2011).

IV. Guide Questions

1. What reactions are involved in the synthesis of 1-phenylazo-2-naphthol?

Diazotization and azo coupling were involved in the synthesis of the dye.

2. Write the reaction pathway and mechanism for the synthesis of 1-phenylazo-2-naphthol.

A. Diazotization

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 B. Coupling

3. Why should the temperature of the reaction mixture be kept below 5C?

Arenediazonium salts will decompose above the given temperature (Solomon, 2011).

4. Explain the principle behind the use of starch iodide paste in detecting excess nitrous acid.

Starch forms a blue complex with the triiodide ion in the presence of excess oxidizing agent. Nitrous

acid is a strong oxidizing agent, so the blue complex will form (Skoog, West, Holler, & Crouch, 2014).

5. Why is the rate of coupling of phenyldiazonium ion with -naphthol dependent upon the pH of the

reaction medium?

According to Solomon:

Couplings between arenediazonium cations and phenols take place most rapidly in slightly alkaline

solution. Under these conditions an appreciable amount of the phenol is present as a phenoxide

ion, and phenoxide ions are even more reactive toward electrophilic substitution than are phenols

themselves. If the solution is too alkaline (pH>10), however, the arenediazonium salt itself reacts

with hydroxide ion to form a relatively unreactive diazohydroxide or diazotate ion. (2011)

V. References

Atkins, P., & de Paula, J. (2006). Physical Chemistry, 8th edition. New York, NY: W.H. Freeman and Company.

Chang, R. (2010). Chemistry, 10th edition. New York, NY: McGraw-Hill.

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Clayden, J., Warren, S., Wothers, P. (2001). Organic Chemistry, 1st edition. United

Kingdom: Oxford University

Press.

Laidler, K., & Meiser, J. (1999). Physical Chemistry, 3rd edition. Boston, MA: Houghton Mifflin Company.

Lide, D. (Ed.). (2004). CRC Handbook of Chemistry and Physics (84th ed.). CRC Press LLC.

Klein, D. (2012). Organic chemistry. Hoboken, New Jersey: John Wiley & Sons, Inc.

Bruice, P. (2014). Organic chemistry (7th ed.). (A. Jaworski, Ed.) Upper Saddle River, New Jersey: Pearson

Education, Inc.

McMurry, J. (2008). Organic chemistry. Belson, California: Thomson Learning, Inc.

Solomon, T. (2011). Organic chemistry (10th ed.). (C. Fryhle, Ed.) Hoboken, New Jersey: John Wiley & Sons,

Inc.

Skoog, D., West, D., Holler, F., & Crouch, S. (2014). Fundamentals of analytical chemistry (9th ed.). Belmont,

California: Brooks/Cole.

Image sources:

https://upload.wikimedia.org/wikipedia/commons/0/06/Synthesis_azo_3.png

https://www.omicsonline.org/scientific-reports/srep586.php