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Enguero, Danilo Jr.

; Soriano, Serville James Department of Chemical Engineering, University of the Philippines, Diliman, Quezon City Date Performed: Date Submitted: October 5, 2011ll
SYNTHESIS OF 1-PHENYLAZO-2-NAPHTOL

Abstract Synthesis of 1-phenylazo-2-naphtol or Sudan 1 consists of two reactions, namely diazotization and coupling reactions. In the diazotization reaction, primary aromatic amines are reacted with nitrous acid to form diazonium salts. For the coupling reaction, the positively charged aryl diazonium ion becomes electrophilic towards activated aromatic substrates resulting to the desired coupling product. In this experiment, synthesis of Sudan 1was obtained from the reaction between aniline and -naphtol, following the two processes: diazotization and coupling. Recrystallization was done on the product to obtain 0.66g of Sudan 1, which was 121% of the theoretical yield, 0.5456g. this discrepancy can be accounted in the presence of contaminants.

I. Introduction Dyes are diazo compounds used as acid-base indicators, food coloring biological staining agents, and coloring of textiles. They are colored because they absorb light in the visible region. This absorption is caused by chromophores. Dyes also have auxochromes or color deepener which are of the type NHR, NR2, -OH, and OR. A good dye should have a permanent color when trapped on fabric. Thus, the dye must either be able to have strong interactions with the fabric or must be able to be trapped in the spaces between the fibers of the fabric. But not all dyes are compatible with every fabric, depending on the method used. Either direct dyeing, or ingrain dyeing. The first method is achieved via chemical interactions called salt linkages. As for the

ingrain method, the dye is synthesized inside the fabric. Dyes are coupling products formed by using two reactions. The first raction is called diazotization reaction, where diazonium salt is formed from the reaction of primary aromatic amines and nitrous acid. These diazonium salts are one of the most versatile intermediates in synthesis of organic compounds.

For the coupling reaction, the positively charged aryl diazonium ion becomes electrophilic towards highly activated aromatic substrates to form the desired coupling product.

water. The crude product collected was recrystallized. Lastly, the meting point was determined. III. Results and Discussion The synthesis of 1-phenylazo-2naphthol (Sudan 1) consists of two reactions diazotization and coupling reaction. The phenyldiazonium is prepared through the process of diazotization. In this reaction, aniline is made to react with nitrous acid to produce the diazonium ion. The nitrous acid was produced in reaction by letting NaNO2 react with an acid. The nitrous acid is then protonated, releases water, and produces the nitrosonium ion.

This experiment was conducted to synthesize Sudan 1 from the reaction of aniline and -naphtol and to examine its property of being an ingrain dye. II. Methodology To prepare the phenyldiazonium chloride solution, 0.2 mL of aniline, 0.35 mL water, and 0.5 mL conc. Hcl were combined in a 50-mL Erlenmeyer Flask. The mixture was the cooled to 4C. approximately 1 mL of ice-cold distilled water. Add gradually 0.3g of NaNO2 crystals. The temperature was maintained at below 5C. To preapare the -naphtol, 0.35g of -naphtol was dissolved in a 4.5 mL 5% aq. NaOH in a 50-mL beaker and was cooled to 4C. A 2x3 fabric was then dyed in the naphtol solution, which was still in the cold water bath. The fabric was allowed to soak for 2-3 minutes. The fabric was then removed from the bath. The fabric was then immersed in the phenyldiazonium chloride solution. The fabric was removed from the solution and was washed with running water. The remaining phenyldiazonium chloride solution was added to the cold naphtol solution. The mixture was allowed to stand for another 1-5 minutes. The products were collected through filtration and was washed with little amount of cold

This is then attacked by the nucleophilic amine of aniline, ultimately producing the diazonium ion. Although aliphatic diazonium ions readily decompose, aromatic diazonium ions can be isolated due to delocalization of the positive charge on the nitrogen.

This solution is kept at cool temperatures to prevent the decomposition of the diazonium ion, which will release N2. Throughout the experiment, the temperature of the phenyldiazonium solution was kept below 4C to prevent decomposition. At higher temperatures, the salt tends to become unstable, thus a side reaction occurs, as shown below:

Next, the -naphthol solution was prepared. 5% aq. NaOH was added because -naphthol is a phenol, and as coupling agents, they react more readily in weakly basic solutions. However, only 5% aq. NaOH was used because if the solution becomes too basic, the salt is converted to a diazotate ion, with the reaction as shown below:

diazotate ion

This side reaction makes the salt unable to undergo a coupling reaction. -naphthol, or 2-naphthol, has a hydroxyl group attached to the -carbon, or the carbon that is 2 carbons away from the shared carbons in naphthalene. The carbons directly attached to the shared carbons are in the position:

Carbons 1, 4, 5, and 8 are in the positions while carbons 2, 3, 6, and 7 are in the positions. The hydroxyl group of naphthol is located on the position; hence, the name. The hydroxyl group is an electron donor, making the naphthol more susceptible to electrophilic attack. The dyeing process that was done in this experiment was ingrain dyeing. The cotton fabric was first immersed in the slightly alkaline -naphthol solution. Afterwards,the fabric was pat dried and it was immersed in the diazonium salt (phenyldiazonium chloride) solution. Pat drying was done to remove the excess coupling agent solution from the fabric so just enough dye would be synthesized upon immersing the fabric in the diazonium salt solution. In the experiment, upon immersing the fabric in the diazonium salt solution, it was observed that the color of the fabric immediately

changed to orange. The fabric also had some bits of gold or bright yellow color. This indicates that the desired azo dye was synthesized in the cotton fabric. Also, the color was permanent and could not be removed even after washing, indicating that the azo dye molecules have been trapped in the fibers of the fabric. Ingrain dyeing was done in this experiment because cotton cannot be dyed effectively with azo dyes via either direct dyeing or disperse dyeing. In fact, cotton cannot be dyed by simple cationic or anionic dyes. Cotton is composed of cellulose, long polysaccharide molecules composed of glucose units bonded by betaglycosydic linkages. The structure of cellulose indicates that it cannot produce strong interactions with anions or cations since it does not contain any strongly polarized groups. Thus, azo dyes are used to dye cotton. However, cotton cannot be dyed using direct or disperse dyeing. Effective dyeing of cotton requires di-azo compounds (like the azo dye synthesized in this experiment) with molecules big enough to be trapped in the fibers of the cotton fabric. Dyes with single azo groups have molecules that are too small and would be able to diffuse out of the fibers of the cotton fabric and thus would not produce a permanent color. Thus, di-azo compounds have to be used. However, if these di-azo compounds would be synthesized outside the cotton fabric, the molecules would also be too big and would not be able to diffuse into the fibers of the cotton fabric. The structure of cotton is shown on the next page. It can be noticed that its molecules are incapable of strong interactions with 1-phenylazo-2naphthol. It is only capable of hydrogenbonding with other cellulose molecules but not with the azo dye molecules. Thus, the only way to produce a permanent color in cotton is the use of azo dyes like 1phenylazo-2-naphthol which molecules are big enough to be trapped among the fabric fibers. The molecules can be trapped by employing ingrain dyeing instead of direct dyeing.

After doing the ingrain dyeing process, the remaining solutions were used to synthesize 1-phenylazo-2-naphthol. The remaining diazonium salt (phenyldiazonium chloride) solution was added to the remaining naphthol solution. Again, the reaction was conducted at a temperature lower than 5 oC to avoid the decomposition of the diazonium salt. The two reactants, the diazonium ion, and -naphthol, are made to react by coupling. The second resonance structure of the diazonium ion above has a positive charge on the terminal nitrogen. This positive charge makes the ion slightly electrophilic. However, their electrophilicity is only weak because of the delocalization of the positive charge. Hence, they would only react with highly activated compounds, like naphthol, since the hydroxyl group is a strong activator. Being an electron donor, the hydroxyl group is also an ortho/paradirector. However, the para position cannot be attacked since there are no hydrogen atoms to be substituted. Hence, carbon 1 is attacked by the diazonium ion.

Sudan 1 is a major constituent of the solid. The % yield is 121%. One major source of this is that the product, Sudan 1, was not completely dried and the measured weight includes the weight of the liquid. Other contaminants in air could have mixed with the Sudan 1 that could have affected its deviation from the theoretical melting point and could have increased its weight. IV. Conclusions The experiment was successful in synthesizing 1-phenylazo-2-naphtol or Sudan 1 from the diazotization of aniline using conc. HCl to form phenyldiazonium chloride. It was then coupled with naphtol. 0.66 grams of the Sudan 1 was obtained, which was 121% of the theoretical yield, 0.5456 grams. Discrepancies could be attributed to the imperfect experimentation environment and set-up, loss of sample due to execution errors, and impurities in the final product due to contamination. V. References [1] McMurry, J. 2003. Organic Chemistry, 6th Edition. Brooks/Cole Publishing Company, California. [2] Bettelheim, F.A. and March, J. 1998. Introduction to Organic Chemistry and Biochemistry, 3rd Edition. Saunders College Publishing, Florida. [3] Robertson, G.R and Jacobs T. 1962. Laboratory Practice of Organic Chemistry, 4th Edition. The MacMillan Company, New York.

The naphthol loses the hydrogen in the hydroxyl group. To offset the lost hydrogen, oxygen doubly bonds with carbon, as one double C-C bond is broken. Hence, there will be a carbon susceptible to electrophilic attack. The terminal nitrogen of the diazonium ion attaches to this carbon (at the position). Once the diazonium is attached, hydrogen is expelled, reforming the double bond. The oxygen returns to being singly bonded to carbon, and regains hydrogen, forming Sudan 1. The melting point of the synthesized Sudan 1 was determined. The experimental value was 138oC. The value is close to the theoretical value (131-133C). Thus, the