Part 1.

Dyes
The most common dyes are the azo dyes, formed by coupling diazotized amines to phenols. The dye can be made in bulk, or, as we shall see, the dye molecule can be developed on and in the fiber by combining the reactants in the presence of the fiber. One dye, Orange II, is made by coupling diazotized sulfanilic acid with 2-naphthol in alkaline solution; another, Methyl Orange, is prepared by coupling the same diazonium salt with N,N-dimethylaniline in a weakly acidic solution. Methyl Orange is used as an indicator as it changes color at pH 3.2-4.4. The change in color is due to transition from one chromophore (azo group) to another (quinonoid system). You are to prepare one of these two dyes and then exchange samples with a neighbor and do the tests with both dyes. Both substances dye wool, silk, and skin, and you must work carefully to avoid getting them on your hands or clothes. The dye will eventually wear off your hands or they can be cleaned by soaking them in warm, slightly acidic (H2SO4) permanganate solution until heavily stained with manganese dioxide and then removing the stain in a bath of warm, dilute bisulfite solution.

Experiments

531
1. Diazotization of Sulfanilic Acid
Avoid skin contact with diazonium salts. Some diazonium salts are explosive when dry. Always use in solution. In a 125-mL Erlenmeyer flask dissolve, by boiling, 4.8 g of sulfanilic acid monohydrate in 50 mL of 2.5% sodium carbonate solution (or use 1.33 g of anhydrous sodium carbonate and 50 mL of water). Cool the solution under the tap, add 1.9 g of sodium nitrite, and stir until it is dissolved. Pour the solution into a flask containing about 25 g of ice and 5 mL of concentrated hydrochloric acid. In a minute or two a powdery white precipitate of the diazonium salt should separate and the material is then ready for use. The product is not collected but is used in the preparation of the dye Orange II and/or Methyl Orange while in suspension. It is more stable than most diazonium salts and will keep for a few hours.

2. Orange II (1-p-Sulfobenzeneazo-2-Naphthol Sodium

In a 400-mL beaker dissolve 3.6 g of 2-naphthol in 20 mL of cold 10% sodium hydroxide solution and pour into this solution, with stirring, the suspension of diazotized sulfanilic acid from Section 2. Rinse the Erlen CAUTION: Handle 2-naphthol with care, in the hood. Do not breathe the dust or allow skin contact. Carcinogen. Extinguish flames! meyer flask with a small amount of water and add it to the beaker. Coupling occurs very rapidly and the dye, being a sodium salt, separates easily from the solution because a considerable excess of sodium ion from the carbonate, the nitrite, and the alkali is present. Stir the crystalline paste thoroughly to effect good mixing and, after 5-10 min, heat the mixture until the solid dissolves. Add 10 g of sodium chloride to further decrease the solubility of the product, bring this all into solution by heating and stirring, set the beaker in a pan of ice and water, and let the solution cool undisturbed. When near room temperature, cool further by stirring and collect the

product on a Buchner funnel. Use saturated sodium chloride solution rather than water for rinsing the material out of the beaker and for washing the filter cake free of the dark-colored mother liquor. The filtration is somewhat slow. 3 The product dries slowly and it contains about 20% of sodium chloride. The crude yield is thus not significant, and the material need not be dried before being purified. This particular azo dye is too soluble to be crystallized from water; it can be obtained in a fairly satisfactory form by adding saturated sodium chloride solution to a hot, filtered solution in water and cooling, but the best crystals are obtained from aqueous ethanol. Transfer the filter cake to a beaker, wash the material from the filter paper and funnel with water, and bring the cake into solution at the boiling point. Avoid a large excess of water, but use enough to prevent separation of solid during filtration (use about 50 mL). Filter by suction through a Buchner funnel that has been preheated on the steam bath. Pour the filtrate into an Erlenmeyer flask, rinse the filter flask with a small quantity of water, add it to the flask, estimate the volume, and if greater than 60 mL evaporate by boiling. Cool to 80C, add 100-125 mL of ethanol, and allow crystallization to proceed. Cool the solution well before collecting the product. Rinse the beaker with mother liquor and wash finally with a little ethanol. The yield of pure, crystalline material is 6.8 g. Orange II separates from aqueous alcohol with two molecules of water of crystallization and allowance for this should be made in calculating the yield. If the water of hydration is eliminated by drying at 120C the material becomes fiery red. Cleaning Up The filtrate from the reaction, although highly colored, contains little dye, but is very soluble in water. It can be diluted with a large quantity of water and flushed down the drain or, with the volume kept as small as possible, it can be placed in the aromatic amines hazardous waste container or it can be reduced with tin(II) chloride (see Experiment 4). The crystallization filtrate should go into the organic solvents container.
3. If the filtration must be interrupted, fill the funnel, close the rubber suction tubing (while the

3. Methyl Orange (p-Sulfobenzeneazo-4-Dimethylaniline

In a test tube, thoroughly mix 3.2 mL of dimethylaniline and 2.5 mL of glacial acetic acid. To the suspension of diazotized sulfanilic acid from Experiment 1 contained in a 400-mL beaker add, with stirring, the solution of dimethylaniline acetate. Rinse the test tube with a small quantity of water and add it to the beaker. Stir and mix thoroughly and within a few minutes the red, acid-stable form of the dye should separate. A stiff paste should result in 5-10 min and 35 mL of 10% sodium hydroxide solution is then added to produce the orange sodium salt. Stir well and heat the mixture to the boiling point, when a large part of the dye should dissolve. Place the beaker in a pan of ice and water and allow the solution to cool undisturbed. When cooled thoroughly, collect the product on a Biichner funnel, using saturated sodium chloride solution rather than water to rinse the flask and to wash the dark mother liquor from the filter cake. The crude product need not be dried but can be crystallized from water after making preliminary solubility tests to determine the proper conditions.

The yield is 5-6 g. Methyl Orange is an acidbase Indicator.

Part 2. Dyeing
Experiments. 1. Direct Dyes
The sulfonate groups on the Methyl Orange and Orange II molecules are polar and thus enable these dyes to combine with polar sites in the fibers. Wool and silk have many polar sites on their polypeptide chains and hence bind strongly to a dye of this type. Martius Yellow, picric acid, and eosin are also highly polar dyes and thus dye directly to wool and silk. NO2
Picric Acid NO2 Martius Yellow Eosin A (Amax 516,483 nm)

Orange II or Methyl Orange

The dye bath is prepared from 50 mg of Orange II or Methyl Orange, 0.5 mL of 10% sodium sulfate solution, 15 mL of water, and 5 drops of 10% sulfuric acid in a 30-mL beaker. Place a piece of test fabric, a strip 3/4-in. wide, in the bath for 5 min at a temperature near the boiling point. Remove the fabric from the dye bath, allow it to cool, and then wash it thoroughly with soap under running water before drying it. Dye untreated test fabric and one or more of the pieces of test fabric that have been treated with a mordant following this same procedure. See Experiment 3 for application of mordants. Source: Fieser

25.15 Coupling Reactions of Aryl Diazonium Salts

The second general reaction of diazonium salts is coupling. When a diazonium salt is treated with an aromatic compound that contains a strong electron-donor group, the two rings join together to form an azo compound, a compound with a nitrogennitrogen double bond.

Azo coupling

Azo compounds are highly conjugated, rendering them colored (Section 16.15). Many of these compounds, such as the azo compound butter yellow, are synthetic dyes. Butter yellow was once used to color margarine.
butter yellow Example

This reaction is another example of electrophilic aromatic substitution, with the diazonium salt acting as the electrophile. Like all electrophilic substitutions (Section 18.2), the mechanism has two steps: addition of the electrophile (the diazonium ion) to form a resonance- stabilized carbocation, followed by deprotonation, as shown in Mechanism 25.4.
Synthetic dyes are described in more detail in Section 25.16.

Because a diazonium salt is only weakly electrophilic, the reaction occurs only when the benzene ring has a strong electron-donor group Y, where Y = NH2, NHR, NR2, or OH. Although these groups activate both the ortho and para positions, para substitution occurs unless the para position already has another substituent present. To determine what starting materials are needed to synthesize a particular azo compound, always divide the molecule into two components: one has a benzene ring with a diazonium ion, and one has a benzene ring with a very strong electron-donor group.

25.16B How Dyes Bind to Fabric

To be classifi ed as a dye, a compound must be colored and it must bind to fabric. There are many ways for this binding to occur. Compounds that bind to fabric by some type of attractive forces are called direct dyes. These attractive forces may involve electrostatic interactions, van der Waals forces, hydrogen bonding, or sometimes, even covalent bonding. The type of interaction depends on the structure of the dye and the fi ber. Thus, a compound that is good for dyeing wool or silk, both polyamides, may be poor for dyeing cotton, a carbohydrate (Figure 22.4). Wool and silk contain charged functional groups, such as NH3 + and COO. Because of this, they bind to ionic dyes by electrostatic interactions. For example, positively charged NH3 + groups bonded to the protein backbone are electrostatically attracted to anionic groups in a dye like methyl orange.

Cotton, on the other hand, binds dyes by hydrogen bonding interactions with its many OH groups. Thus, Congo red is bound to the cellulose backbone by hydrogen bonds.

Source: Smith

Diazonium Coupling Reaction: Methyl Red

Common names: methyl red CA number: [493-52-7] CA name as indexed: benzoic acid, 2-[[4-(dimethylamino)phenyl]azo]Purpose. In this experiment you will learn the process of generating arenediazonium salts in solution. The arenediazonium salt generated will be used in an electrophilic aromatic substitution reaction (diazo coupling) to prepare an azobenzene derivative. Many azobenzene derivatives, including the one prepared here, have extensively conjugated _-electron systems. Because these are highly colored compounds, they are generally referred to as azo dyes.

DISCUSSION
The coupling of a diazonium salt to a suitable aromatic substrate is an example of an aromatic electrophilic substitution reaction. When primary aromatic (and also aliphatic) amines (ArNH2) are treated with nitrous acid , they are converted into diazonium cations, . In solution, nitrous acid (HONO) is in equilibrium with its anhydride, dinitrogen trioxide (N2O3), which is the actual diazotizing agent. The primary amine reacts with the dinitrogen trioxide to form a nitrosamine:

The nitrosamine is in equilibrium with its tautomer, a diazoic acid. The diazoic acid then undergoes dehydration to form the diazonium salt. Diazonium salts are explosive when dry, and therefore are generally not isolated.

Reaction of the diazonium salt with various aromatic compounds leads to the formation of azo derivatives by what is generally called a coupling reaction,but is mechanistically simply an ordinary electrophilic aromatic substitution reaction. The mechanism of the reaction is given here:

Azo dyes find use as acidbase indicators. For example, Methyl Red prepared in this experiment, Methyl Orange, and Congo Red are well-known acidbase indicators. Azo dyes are commonly used in the textile, food, and cosmetic industries; FD&C Yellow No. 6, a yellow azo dye is used to color candy, ice cream, beverages, and so on. Several azo dyes (including Butter Yellow and FD&C Red No. 2) have been banned by the FDA from use in foods, drugs, and cosmetics in the United States because of suspected carcinogenic properties

EXPERIMENTAL PROCEDURE
Reaction Conditions. When both solutions in the ice bath are cooled to a temperature below 5 _C slowly add (dropwise) the nitrite solution to the stirred anthranilic acid solution, while maintaining the temperature below 5 _C. This transfer is accomplished using a Pasteur pipet. The solution must be kept cool so that the diazonium salt will not hydrolyze to the corresponding phenol. After a period of 45 min, check the clear solution of anthranyldiazonium chloride for the presence of excess nitrous acid by placing a drop of the solution on a piece of potassium iodidestarch test paper. If an excess is present, the test paper gives an immediate blue color. If no color is obtained, prepare additional nitrite solution and add as before until a positive test is observed. Remove the air condenser from the reaction vial containing the solution of

anthranyldiazonium chloride. Fairly rapidly, add 89 _L (85 mg, 0.71 mmol) of N,N-dimethylaniline (automatic delivery pipet). Reattach the air condenser. Prepare a solution of 68 mg (0.83 mmol) of sodium acetate dissolved in 200 _L of water in a 10 _ 75-mm test tube. Transfer this solution (Pasteur pipet) to the reaction mixture. Make this addition without removing the air condenser. Maintain the resulting solution at 5 _C with stirring, for an additional 20 min. Remove the reaction vial from the ice bath and allow it to stand for 15 min in order to warm to ambient temperature. Now add 100 _L of 10% aqueous NaOH solution (automatic delivery pipet) to the solution. Allow the reaction mixture to stand at room temperature for about 30 min. The formation of the azo compound is a very slow reaction, but the rate of formation is increased by raising the pH of the solution. Isolation of Product. Collect the precipitate of crude Methyl Red dye by vacuum filtration using a Hirsch funnel ( ). Rinse the reaction flask with 0.5 mL of water and use this rinse to wash the crystals. Then wash the crystals with 0.5 mL of 3 M acetic acid, to remove unreacted N,N-dimethylaniline from the product, followed by another wash with 0.5 mL of water. This last wash is usually pale pink in color. NOTE. Dispense the small amounts of water and acetic acid using a calibrated Pasteur pipet. Purification and Characterization. Dissolve the crude product in 500 _L of methanol. If necessary, warm the mixture in a beaker of hot water to aid in the dissolution. Cool the solution in an ice bath and collect the resulting crystals of Methyl Red by vacuum filtration using a Hirsch funnel. Dry the material on filter paper or under vacuum at room temperature. Weigh the product and calculate the percent yield. Determine the melting point and compare it to the value given in the literature. If further purification is desired, recrystallize the material from toluene using a Craig tube.

Background Dyes play an indispensable role in human history since ancient time. Dyeing processes are often considered as an important characteristic of a particular civilisation or culture. Dyes are used in almost every commercial product such as food, clothing, pigments and paints, etc. There are many different classes of dyes in which azo dyes are certainly one of the most important classes. About half of the dyes used in industry are azo dyes. Azo dyes have the basic structure, ArN=NAr, where Ar and Ar are two aromatic grop