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Synthesis of 1-phenylazo-2-naphthol Anjelika Mae L.

Marquez Department of Mining, Metallurgical and Materials Engineering, University of the Philippines, Diliman, Quezon City February 14, 2014 March 5, 2014

Abstract 1-phenylazo-2-naphthol or known as Sudan-1 was synthesized by diazotization and coupling reactions. Diazonium salts are formed in the diazotization reaction while in the coupling reaction coupling products are formed because the positively charged aryl diazonium ion becomes electrophilic towards highly activated substrates. Aniline and -naphthol was made to react and recrystallization was done to obtain a product with 0.04g with a theoretical yield of 0.54 g. The percent yield is 7%. While the theoretical melting point is 131oC and the obtained melting point is 131.5oC I. Introduction

Azo compounds are compounds containing a diazene molecule where hydrogen is replaced by R. The general formula for an azo compound is R-N=N-R' where R and R can be an aryl or an alkyl group. Aryl azo compounds have vivid colors ranging from red to yellows. Because of this trait, azo compounds are usually used as dyes and are commonly known as azo dyes. Dyes are colored because of delocalization. The extended -N=N- bond causes light to be absorbed in the visible regions. The groups responsible for the delocalization and absorption of light are called chromophore. Most dyes also contain auxochromes like carboxylic acid, sulfonic acid, amino, and hydroxyl group which influence dye solubility and can shift the color of the dye. Dyes can be used as acid-base indicators, food coloring, biological staining agent, and textile dyes. The dyes are colored because light is absorbed in the visible region. Azo dyes are very easy to synthesize. The starting materials are readily available and cheap too. Azo dyeing is a technique where an insoluble dye is directly put into the fiber. The fiber is treated with both the diazo component and the coupling component. It reacts to produce desired product. Diazotization reaction is where an unstable diazonium salt intermediate is formed from a primary amine called a diazo component and nitrous acid in low temperature.

Figure 1: Overview of diazotization Coupling reactions involve the reaction of the diazonium salt with a coupling component like a phenol or an aromatic amine. This will produce the stable azo dye. (Azo dyes)

Figure 2: Overview of coupling reaction In this experiment aniline and -naphthol are made to react to form a red-orange product, 1-phenylazo-2naphthol or known as Sudan 1 by diazotization and coupling reactions. II. Methodology Phenyldiazonium chloride solution was prepared by combining 0.2 mL aniline, 0.35 mL water, and 0.5 mL concentrated HCl in a 50 mL Erlenmeyer flask. 1 mL icecold distilled water was then added to the mixture. To it, 0.3 g of NaNO2 crystals was added gradually. While preparing this mixture, the Erlenmeyer is placed in an ice bath to keep temperature under 5oC -naphthol solution was prepared by dissolving 0.35 g and -naphthol in 4.5 mL 5% aqueous NaOH in a 50mL beaker. This solution was kept under 4oC. A 2x3 fabric was dyed in the cold -naphthol solution while it was still in ice bath. Fiber was let to soak the solution for 2-3 minutes. The fabric was then removed and excess dye was removed by patting the

fabric between two filter papers. It was then immersed in phenyldiazonium chloride solution. After immersion, the fabric was washed with running water. After the ingrain dyeing, the remaining phenyldiazonium solution was slowly added to the cold -naphthol solution while stirring. The mixture was left to react in an ice bath for 1-5 minutes. The product was filtered and was washed thoroughly with small portions of cold water. The product obtained underwent recrystallization reaction. Minimal amount of ethanol was used in a steam bath. The recrystallized product was then dried and the melting point was determined. III. Results and Discussion The synthesis of 1-phenylazo-2-naphthol consists of two reactions: diazotization and coupling reactions. In the first part of the experiment, aniline is made to react with NaNO2 in acidic medium. Nitrous acid was produced in the reaction of NaNO2 with HCl. Then the acid is protonated releasing water and produces the nitrosonium ion. Nitrosonium ion is used because it is a better leaving group than NH2.

Aliphatic diazonium ions spontaneously decompose by releasing nitrogen gas N2 and the aromatic ring is protonated. The protonated aromatic ring can be attacked by OH- from water and Cl- from HCl.

Figure 5: Formation of side products When kept under 4oC, the positive charge is delocalized therefore making it resonance stabilized.

Figure 5: Delocalization of the positive charge in aromatic diazonium ions Figure 3: Formation of nitrosonium ion The nitrosonium is then attacked by the nucleophilic NH2 from aniline producing the diazonium ion. -naphthol was mixed with 5% aqueous NaOH. The naphthol reacts readily with a weak base. If the base is too strong, the salt will be converted to a diazotate ion and will likely hinder the formation of Sudan-1 in its pure form.

Figure 6: Formation of diazotate ion Ingrain dyeing was performed using a 2x3 cm fabric. First it was immersed in the -naphthol solution and pat dried to remove excess coupling component. Next it was dipped in the diazonium salt solution. Dye was synthesized while dipping the fabric in the diazonium salt solution as evidenced by the change in color of the fabric. The fabric turned red-orange. It was washed with water but the color was permanent. The molecules of the azo dye were big enough to be trapped in the fibers of the fabric. The reaction took place on the fabric because if the reaction was done beforehand and the fabric was then dipped into the dye, the molecules will be too big to fit into the fibers of the fabric.

Figure 4: Formation of diazonium ion This reaction must be kept under 4oC to prevent decomposition which will form undesirable products. To help keep this temperature, rock salt may be added to the ice bath. The freezing point is lowered thus the ice melts slower and the freezing rate is increased.

The remaining solution was used to synthesize 1phenylazo-2-naphthol. The two reactants react via coupling. To produce the most stable carbocation, naphthol can be attacked on the carbon 1 position.

Figure 7: structure of -naphthol In the coupling reaction, the phenyldiazonium salt attacks the carbon in the carbon 1 position -naphthol couples with the diazonium ion forming a resonancestabilized intermediate. Electrons from the 1, 2 carbon bond shift to the nitrogen and the electrons from the oxygen shift in to form C=OH+ finally forming crude sudan-1. Figure 9: Resonance stabilized intermediate After obtaining the product, it was washed with cold water to remove excess reactants. The product was then prepared for recrystallization using hot ethanol. A product with a weight of 0.04g was obtained with a theoretical yield of 0.54 g. The percent yield is 7%. The percent yield may be small but the percent purity must be high since the theoretical melting point of 1phenylazo-2-naphthol 131oC and the melting point determined was 131.5 oC. IV. Conclusion The experiment is a successful one. Even if the percent yield is low, the percent purity must be high because the melting point of the product obtained is very close the theoretical melting point. The low percent yield must have been because of loss of sample while drying or while transferring from one vessel to another. V. References Azo dyes. 2002. 4 March 2014 < price/azo.htm>. Brown T., LeMay, H, E, & et al. Chemistry: The Central Science 11th Edition. Pearson education south asia PTE, LTD., 2009. Dietmar Kennepohl, David Law, Rob Carmichael, Lois Browne,. Organic chemistry II Lab Manual. Athabasca University, 2002. Figure 8: Coupling reaction Hein, Best, Pattison, Arena. Introduction to General, organic, and biochemistry 8th ed. John wiley & sons, Inc, 2005. J, McMurry. Organic Chemistry(1984). United states of america: wadsworth, n.d.

Organic Chemistry Laboratory Manual . University of the Philippines Quezon city, 2008. organic chemistry portal. n.d. 4 March 2014 < tm>. Prof. Dr. GregorFels, O.Kam,C.Biele. Reactions of Aromatic Compounds - Examples of Ar-SE Reaction. n.d. 4 March 2014 < /en/ch/12/oc/vlu_organik/aromaten/reaktione n/ar_se_beispiele.vlu/Page/vsc/en/ch/12/oc/ar omaten/reaktionen/ar_se/diazotierung/diazoti erung.vscml.html>.

2. Draw the resonance structures of the intermediate formed in the attack of the diazonium ion on carbon 1 of b-naphthol. Explain in terms of relative stabilities why the attack on carbon 1 is preferred.

Carbon 1 is more stable because of the tertiary cation. The more conjugated, the more stable the compund is. 3. Give two conditions that could lead to the formation of the side products. Write a chemical equation for these side reactions.

VI. Appendices 1. Give the amine and the coupling component that can be used as starting materials for the synthesis of the following dyes:


coupling component

4. Give two properties of a good dye. Define each of these properties A good dye should have good colour vibrance. It should be permanent and visible. A good dye should also be cheap to produce 5. Use the structure of cotton to explain why Sudan 1 cannot be used as a direct dye for a cotton Cotton is made up of cellulose. These cellulose contain many OH groups which form hydrogen bond. However, sudan 1 has only one OH group and the rest are nonpolar groups therefore it cannot adhere to cotton since the attraction is weak.