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Experimental In a 50-mL beaker, 0.9 mL of aniline, 1.4 mL of water and 2.1 mL of concentrated hydrochloric acid were combined.

It was then cooled to 0-5 C, with 1 g of ice and stirred constantly. Sodium nitrate (0.75 in 3 mL H2O) was then dropped until the solution contains excess acid. A drop of the solution was placed to test reaction for excess nitrous acid, indicated by a blue color. Note that the temperature must be below 5 C. 1.4 g of -naphthol was dissolved in 3 mL warm sodium hydroxide. This was then cooled to 5C. Afterwards, the phenyldiazonium chloride was added dropwise, while stirring. For 15 minutes, the solution was kept standing in 0-5 C. The product was collected through filtration on fluted filter paper. Cold water was used to wash several portions of it. It was recrystallized from ethanol. It was then dried and weighed. A pinch of the product was dissolved in 5 mL distilled water. Three drops of the solution was then added to 2 mL 0.1 M sodium hydroxide. This test was repeated using 0.1 M hydrochloric acid, ammonium hydroxide and acetic acid. Results Physical test Appearance: powder Color: red-orange

Texture: fine Odor: paint-like smell Melting Point: 131-133 C Chemical test 0.1 M NaOH 1 M HCl NH4OH CH3COOH Discussion The synthesis of 1-phenylazo-2naphthol was possible through diazotization, followed by a diazoniumcoupling reaction. From the reaction of aniline to sodium nitrate in hydrochloric acid, a diazonium salt, phenyldiazonium chloride, was produced. The solution was cooled, to ensure that the intermediate does not decompose, as it is very unstable. It goes back to aniline when it warms up to a temperature slightly higher than the boiling point. From here, the salt can either undergo coupling reaction or nucleophilic aromatic substitution (NAS). NAS does not occur in this experiment, because it was made sure that the solution was cold. The coupling reaction starts off when the diazonium salt was then reacted with -naphthol. Phenyldiazonium chloride attacks the ortho and para positions with respect to the activator, -OH, forming a resonance-stabilized intermediate. The least intense most intense moderately intense intense

meta position was not attacked, because activating groups are not meta-directors. The ortho position was favored here, because more resonance represantion products are present in this state. The product is now the dye, 1-phenylazo-2naphthol. When it was tested with 0.1 M sodium hydroxide, 1 M hydrochloric acid, ammonium hydroxide and acetic acid, it was found the the intensity of the color varied. The color intensity decreases from the hydrochloric acid solution, followed by acetic acid, ammonium hydroxide, to sodium hydroxide. The phenyldiazonium intermediate was to be kept acidic, to prevent nucleophilic attack of OH. When that happens, the solution turns into pink. This was evident in the addition of the bases, ammonium hydroxide and sodium hydroxide. On the other hand, the naphthol was to be kept basic, to prevent protonation. It has the auxochrome of the dye, -OH, which is the color deepener. In the industrial setting, dyeing baths are acidified to protonate the auxochrome. In this experiment, the addition of acids did protonate the auxochrome, which resulted in the intensification of the color of the dye. Questions: 1. What are the reactions involved in the synthesis of 1-phenylazo-2naphthol? As stated above, the synthesis of 1phenylazo-2-naphthol was possible

through diazotization, followed by a diazonium-coupling reaction. 2. Write the reaction pathway and mechanism for the synthesis of 1phenylazo-2-naphthol. Formation of the diazonium salt:

Mechanism of the formation of diazonium salt:

Attack of diazonium salt to naphthol:

As stated above, the unstability of the diazonium salt requires low temperature for it not to go decompose into aniline. 4. Explain the principle behind the use of starch iodide paste in detecting excess nitrous acid. Iodine is formed by the oxidation of the iodide ion by nitrous acid. When the ion reacts with the acid, it forms a blue product. In this experiment, the presence of the blue color indicates the presence of excess nitrous acid. 5. Why is the rate of coupling of phenyldiazonium ion with naphthol dependent upon the pH of the reaction medium? When the reaction mediums pH is high, the coupling reaction is slowed down by the conversion of amines into ions. Applications (Congo red) Structure of congo red:

Resonance stabilized intermediate:

Synthesis of Congo red (diazotization and coupling steps) 3. Why should the temperature of the reaction mixture be kept below 5 C?

Conclusion and recommendation The formation of the diazonium salt is very useful in synthesizing different compounds, because it allows the benzene ring to link with other aromatic compounds. In this experiment, phenyldiazonium chloride was formed from the nitration of aniline. The only limitation that this experiment has is the availability of the reagents. This experiment was not done in the laboratory, because of that. References: Two resonance structures for the second protonated substance that shows the nature of the chromophore responsible for the blue color: Structures in (b) is when it is acidic (blue in color) nthesis_of_1_phenylazo_2_naphthol.pdf Org%20Chem%20Lab_2012/Exp.11[1].pdf otes/B.Sc.I%20Chemistry%20Diazonium%20 salts.pdf cle/pii/S0304389406013860 -Fr-Chem-31 Sir Quimings lecture

Site of protonation largely responsible for the blue color of Congo red: N=N