Experiment 9, Synthesis of Organic Compounds Cadag, Ma.

Evan Ezra Demotica, Claire Dianne Nero Francisco, Julie Anne Group 8, SAD2, Ms. Hazel Anne Pelagio 13 March 2013 I. Abstract

Organic synthesis is a branch of chemical synthesis dealing with the production of organic compounds by organic reactions. "Sudan-1" of 1-phenylazo-2-naphtol is synthesized in this experiment. These are azocompounds that have the general formula of that can be produced from the reaction of arenediazonium salts with phenols and other amines through azotization and then coupling reactions with highly activated aromatic compounds. Soap, on the other hand, is the salt of the fatty acid that can be produced by the saponification (hydrolysis) of a triglyceride (fat or oil) that is reacted with a strong base such as sodium or potassium hydroxide to produce glycerol and fatty acid salts. Aspirin or acetylsalicylic acid is one of the most widely used analgesic that can be produced via esterification by reacting salicylic acid with acetic anhydride and catalyzed using phosphoric acid. The products were subjected to physical and chemical tests and the results obtained were recorded. Several methods and information regarding organic reactions learned from the previous experiments were used. II. Keywords: azo-dyes, azotization-coupling reactions, arenediazonium salts, saponification, triglyceride, fatty acids, acetylsalicylic acid, salicylic acid, esterification III. Introduction Most of the things that we use in our everyday lives are organic compounds. These compounds can be synthesized in the laboratory. In this experiment, we synthesized dye, soap and aspirin. We used different compounds that are needed to produce these materials. We also tested for the physical and chemical properties of these materials. We can theoretically synthesize these materials by showing its reaction pathway and mechanism, which will be discussed in the rest of the report. IV. Experimental A. Synthesis of a Dye (1-phenylazo-2-naphthol 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 (0.75g in 3 mL H2O) was then dropped until the solution contains excess acid. A drop of the solution was placed on starch iodide paper 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. B. Synthesis of Soap A water bath was supported on an iron stand and it was heat to boiling. Then 2.5 grams of sodium hydroxide was dissolved in 5mL of distilled water and 10mL of 95% ethyl alcohol. It was then added to 5 grams of hydrogenated shortening in a 50mL beaker. The beaker was covered with a watch glass and heated on the water bath. The mixture was stirred constantly to prevent spattering and small amounts of 50% alcohol are added to keep the volume of the mixture constant. The reaction was said to be complete if the oil or melted fat dissolved and gives a clear homogenous mixture. The soap is diluted by adding 15mL of water and pouring it to brine made by dissolving 30g of sodium chloride in 100mL of distilled water. The mixture is stirred thoroughly and the precipitated soap is collected through fluted filter paper. The soap is then washed with 10mL portion of cold water twice.

2g of the crude soap is dissolved in 10mL portions of cold distilled water to be used as the test solution. The remaining soap is placed in an evaporating dish, heat on the water bath and stirred in it just enough soap to form a thick solution. The soap solution is allowed to cool, which will solidify into a cake that is almost similar to commercial soap. C. Synthesis of Aspirin Two grams of salicylic acid is combined with 5 mL of acetic anhydride and 5 drops of 85% phosphoric acid in an erlenmeyer flask that will be heat to boiling water bath for 5 minutes. Remove it from the bath and while still hot, add 2 mL of water. When decomposition is complete, add 40 mL of water, stir until crystals are formed. Cool the mixture in ice bath to complete crystallization. Collect products by suction filtration, and dry the product after washing it with 5 mL cold water. Recrystallize the product from 35 mL of hot water using decolorizing charcoal if product is colored. Dry the product and weigh. V. Results A. Synthesis of a Dye 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 B. Synthesis of Soap Physical Test Appearance: grainy Color: flesh/cream Texture: smooth Odor: banana like Melting Point: Chemical Test CaCl2 MgCl2 FeCl2 Soap dissolved, white, foamy, bubbly, runny More viscous More bubbly/foamy but least intense most intense moderately intense intense

H2O Mineral oil

Methylene chloride Litmus paper C. Synthesis of Aspirin Physical test

less viscous, orange-ish Bubbly, more watery Bubbly, more viscous, no visible separate layers, looks dissolved Residue/precipitate did not dissolved Blue/basic

Appearance - crystalline Texture - fine Color - white Odor - sour-smell, vinegar-like Melting point - 90-136 deg Celsius Chemical test Reaction with methanol - from clear, it formed a solution with two layers: purple at the bottom and clear at the top Reaction with salicylic acid - from clear to a fully purple-colored solution VI. Discussion A. Synthesis of Dye The synthesis of 1-phenylazo-2-naphthol was possible through diazotization, followed by a diazonium-coupling reaction. From the reaction of aniline to sodium nitrate in hydrochloric, a diazonium salt, phenyldiazonium chloride, was produced. 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. Low temperature is required, because the diazonium salt is very unstable and can decompose back into aniline when it warms up. The coupling reaction starts off when the diazonium salt was then reacted with -naphthol. Phenyldiazonium chloride attacks the ortho and para positions, forming a resonance-stabilized intermediate. The meta position was not attacked, because of the presence of an activator. Since activators are ortho and para directors, the product was in the ortho position. The product is now the dye, 1-phenylazo-2-naphthol. B. Synthesis of Soap Fats and oils are triesters of glycerol. Glycerol have three alcohol groups, meaning it can form three ester groups. Glycerol and carboxylate ions are formed when these ester groups are hydrolyzed

in a basic medium. Long chains of unbranched R groups are present in the carboxylic acid bonded to fats or oils. Since these long-chain unbranched R groups are obtained from fats, they are called fatty acids. Soaps are obtained from the fatty acids, which either can be sodium or potassium salts. The process of getting soap from fats or oils which are hydrolyzed under basic condition is called saponification. The carboxylate ions forms micelles which is a spherical cluster of these ions wherein the polar head of each carboxylate ion and its counterion are outside of the ball and its nonpolar tail is in the interior of the ball to minimize its contact with water. Soap has its cleansing ability because dirt which are carried by oil molecules which are nonpolar is dissolved in the interior of the micelle and is carried away with the soap when it is rinsed. C. Synthesis of Aspirin Aspirin or acetylsalicylic acid belongs to a group of organic compounds known as esters. Esters are the most common derivatives of carboxylic acids, having the general formula of RCOOR' wherein R may be hydrogen or an alkyl group and R' may be an alkyl group, but not hydrogen group. Aspirin or acetylsalicylic acid belongs to a group of organic compounds known as esters. Esters are the most common derivatives of carboxylic acids, having the general formula of RCOOR' wherein R may be hydrogen or an alkyl group and R' may be an alkyl group, but not hydrogen group. The reaction is an equilibrium reaction; thus it is reversible. The alcohol group from the salicylic acid reacts with the acetic anhydride causing a chemical reaction that turns the hydroxyl group of the salicylic acid into an acetyl group. (R-OH -> R-OCOCH3) Acetic anhydride is used because it is easily decomposed by the addition of water and can also be reused. The acid protonates the acetic anhydride by having the proton attack the carbonyl oxygen that pulls the two electrons in one of the pi bonds that delocalizes the electrons and spread them between the two oxygen atoms. In the presence of the hydroxyl groups, the delocalized electrons rearrange so as to create a temporary bond between the two reactants. The proton of the hydroxyl group attacks the carbon attached to the OH group of the anhydride, because it is positively charged. The oxygen of the -OH group in turn

becomes positively charged. The positive charge then shift to the oxygen between the two carbon atoms because the hydrogen atom from the -OH group is making a bond. The electrons in the -OH group group delocalizes because the positive charge must be neutralized, resulting in the bond breaking of the carbon and the oxygen the produces the protonated aspirin and the acetic acid. The nucleophile abstacts the hydrogen to removed the negative charge, resulting to the formation of acetylsalicylic acid and acetic acid. Then the phosphoric acid protonates the carbonyl oxygen of acetic anhydride to make it more susceptible to nucleophilic attack, facilitating the acetylation of the salicylic acid. The mixture was heated in a temperature not higher 80 deg Celsius to be able the crystal formation and the rate of reaction of the aspirin. If the temperature is higher, the aspirin might be hydrolyzed and go back to salicylic acid and acetic anhydride. Then, cold water was added to decompose the excess acetic acid and dissolve acetic acid and phosphoric acid, leaving the insoluble aspirin. The aspirin that are left are filtered. Then, recrystallization was done to separate aspirin from impurities. Ferric chloride test was done to check if the product is pure. Ferric chloride reacts with phenol to form iron-phenol complex that will induce a purple color in the solution. Having a purple product, the excess salicylic acid co-precipitates with the aspirin, making it impure. To avoid this, more acetic anhydride must be used that all salicylic acid will react. VII. Answers to Questions A. Synthesis of Dye 1. What are the reactions involved in the synthesis of 1-phenylazo-2-naphthol? As stated above, the synthesis of 1phenylazo-2-naphthol was possible through diazotization, followed by a diazoniumcoupling reaction. 2. Write the reaction pathway and mechanism for the synthesis of 1-phenylazo-2naphthol. Formation of the diazonium salt:

Mechanism of the formation of diazonium salt:

step)

3. Why should the temperature of the reaction mixture be kept below 5 C? 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? -naphthol was treated with NaOH in the experiment, because if not, it would lead to the formation of the diazotate ion, thus the coupling reaction will be slowed down.

Site of protonation largely responsible for the blue color of Congo red: N=N Two resonance structures for the second protonated substance that shows the nature of the chromophore responsible for the blue color: Structures in (b) are when it is acidic (blue in color)

Applications (Congo red) Structure of congo red:

Synthesis of Congo red (diazotization and coupling

B. Synthesis of Soap 1. What is the reaction involved in the synthesis of soap? Alkaline hydrolysis (reaction with water or dilute alkali) of triglyceride (fat/oil) is involved, called saponification. A lye (NaOH solution) or other

strong bases are reacted to triglyceride to produce fatty acid salts (which is the soap) and glycerol. 2. Write the reaction pathway and mechanism for the synthesis of soap. Reaction pathway producing glycerol and fatty acid salt C. Synthesis of Aspirin 1. What is the reaction involved in the synthesis of Aspirin? Esterification is the chemical reaction in which the two reactants (typically an alcohol and an acid) form an ester as the reaction product. 3. Why was the dilute soap solution poured in a solution of sodium chloride in water? Adding NaCl in the soap solution will precipitate the soap, which is the process of salting out. 4. Explain the result obtained when the dilute soap solution is treated with calcium chloride, magnesium chloride and ferric chloride solutions. Sodium salts are generally soluble in water. When it is replaced by calcium, magnesium or iron ions, the new salt will now be insoluble in water forming a soap scum which is a white solution usually found in bathrooms. This means that when you successfully synthesized soap you will form soap scum. 5. How does soap function as an emulsifying agent for oil in water? Draw a picture of an oil droplet and several soap molecules to illustrate your answer. Soaps have ionic head which is polar enough to dissolve in water. Its long hydrocarbon chains are very much like oil so they mix well with oil. 3. Explain why the recrystallization of Aspirin in the water should not be heated above 80 deg Celsius. To prevent the hydrolysis of the ester, yielding back to carboxylic acid. 4. Explain the results obtained when Aspirin and salicylic acid were treated with FeCl3. Ferric chloride or iron (III) chloride will react with salicylic acid and not with aspirin. The phenolic -OH of the salicylic acid will give a purple color. Application: Salol (phenyl salicylate), the phenyl ester of the salicylic acid, is derived by heating salicylic acid, 2. Write the reaction pathway and mechanism for the synthesis of Aspirin

Application Suppose that you wanted to emulsify a water insoluble compound in water. Would soap be a reasonable choice for the emulsifying agent if the water were slightly acidic? Why? If it would not be a good choice, draw the structure of an organic molecule that might be more suitable. No, hydronium ions will attach the polar end of the soap. This causes the water to not interact with soap, thus no emulsification happens. You can use detergent which can tolerate acidic environment.

phenol, and phosphorus oxychloride to 120-125 deg Celsius or by heating salicyl metaphosphoric acid and phenol to 140-150 deg Celsius, which crystallizes in rhombic plates that has the melting point of 42 deg Celsius and boiling point of 172 deg Celsius. Which is a stronger acid, aspirin or salol? Aspirin is stronger because it has a carboxylic group that has a reciprocal hydrogen bonding and hiughly positive hydrogen, its conjugate base is also more stable that is easily hydrolyzed in alkaline medium because of high ionization constant derived from its acidic properties, and its hydrogen is easily ionized due to the presence of oxygen that is highly electronegative in the carbonyl group. VIII. Conclusion 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, then the dye was produced by reacting the intermediate with -naphthol. The only limitation that this experiment has is the availability of the reagents. This experiment was not done in the laboratory, because of that. Soap is an important material that we use in our everyday lives. It is nice to know that the synthesis of creating soap is by reacting triglyceride with lye which is a strong base to form fatty acid salts. The fatty acid salt is now the soap. It is also good to know that soap has nonpolar ends which is the responsible for removing dirt trapped in oil from clothes and polar ends which is responsible for attaching to water which is also polar. Aspirin or acetylsalicylic acid can be synthesized by the process of esterification of salicylic acid and acetic anhydride. IX. References http://www.freewebs.com/mpniistal/fr3_synthesis_of _1_phenylazo_2_naphthol.pdf http://www.chemistry.sc.chula.ac.th/bsac/Org%20C hem%20Lab_2012/Exp.11[1].pdf http://devchandcollege.org/chemistry%20notes/B.S c.I%20Chemistry%20Diazonium%20salts.pdf http://www.sciencedirect.com/science/article/pii/S03 04389406013860 Sir Quimings lecture

http://swc2.hccs.edu/pahlavan/2425L9.pdf http://www.orgsyn.org/ http://www.laney.edu/wp/chelifossum/files/2012/01/13-Saponification.pdf Organic Chemistry 4 . Ed. Paula Yurkanis Bruice pp. 700-702
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I hereby certify that I have given substantial contribution to this report.

Cadag, Ma. Evan Ezra

Demotica, Claire Dianne Nero

Francisco, Julie Anne N.