Name: Eghan Kojo Experiment N 0 : O 2.2.

2 Graduate Assistant: Emmanuel Kwakye Boakye Date: 26 th February, 2013 TITLE: THE PREPARATION OF A COMMERCIALLY IMPORTANT ESTER AIMS 1. To synthesize and purify acetyl salicylic acid 2. To calculate the percentage yield of the product. INTRODUCTION Esters are an important class of organic chemical compounds. Two common esters, acetylsalicylic acid and methyl salicylate, are very important over-the-counter drugs. Since ancient times, it has been known that the barks of certain trees, when chewed or brewed as a tea, had analgesic (pain-killing) and antipyretic (Feverreducing) properties. The active ingredient in such barks was determined to be salicylic acid. When pure salicylic acid was isolated by chemists, however, it probed to be much too harsh to the linings of the mouth, esophagus, and stomach for direct use as a drug in the pure state. Salicylic acid contains the phenolic (-OH) functional group in addition to the carboxyl (acid) group, and it is the combination of these two groups that leads to the harshness of salicylic acid on the digestive tract. Esters were traditionally named by combining the name of the alcohol with the root name of the acid and adding ate as a suffix. Traditional names are still widely used by most chemists, particularly for the simple esters. The IUPAC naming system uses the systematic names for the alcohol and root name of the acid, followed by oate. Salicylic acid is the active ingredient in willow bark, which Hippocrates (5th century BCE) knew to reduce aches and pains and fever. This remedy was also mentioned in texts from ancient Sumer, Lebanon, and Assyria. The medicinal character of methyl salicylate arises from its ready hydrolysis to salicylic acid in the gut. The medicinal properties of aspirin, acetyl salicylic acid, are also due to its ready hydrolysis to salicylic acid. Methyl salicylate can be taken internally or absorbed through the skin. This ester also has a pleasant odor, and it is used to a small extent as a flavoring principle. Because salicylic acid contains both the organic acid group (-COOH) as well as the phenolic group (OH), salicylic acid is capable of undergoing two separate esterification reactions, depending on whether it is behaving as an acid (through the COOH) or as an alcohol analog (through the OH). Research was conducted in an attempt to modify the salicylic acid molecule in such a manner that its desirable analgesic and antipyretic properties would be preserved, but its harshness to the digestive system would be decreased. The Bayer Company of Germany, in the late 1800s, patented an ester of salicylic said that had been produced by reaction of salicylic acid with acetic acid. The ester, commonly called acetylsalicylic acid, or by its original trace name (aspirin), no longer has the phenolic functional group. The salicylic acid has acted as an alcohol when reacted with acetic acid. Acetylsalicylic acid is much less harsh to the digestive system. When acetylsalicylic acid reaches the intestinal tract, however, the basic environment of the small intestine causes hydrolysis of the ester (the reverse of the

esterification reaction) to occur. Acetylsalicylic acid is converted back into salicylic acid in the small intestine and is then absorbed into the bloodstream in that form. Aspirin tablets sold commercially generally contain binders (such as starch) that help keep the tablets dry and prevent the acetylsalicylic acid in the tablets from decomposing into salicylic acid. Since the other component in the production of acetylsalicylic acid is acetic acid, one indication that aspirin tablets have decomposed is and odor of vinegar from the acetic acid released by

the hydrolysis. C7H6O3 + C4H6O3 C9H8O4 + C2H4O2 The second common ester of salicylic acid that is used as a drug is methyl salicylate. When salicylic acid is heated with methyl alcohol, the carboxyl group of salicylic acid is esterified, producing a strong-smelling liquid ester (methyl salicylate).

The minty odor of many common liniments sold for sore muscles and joints is due to this ester. Methyl salicylate is absorbed through the skin when applied topically and may permit the pain-killing properties of salicylic acid to be localized on the irritated area. Methyl salicylate is a skin irritant, however, and causes a sensation of warmth to the area of the skin where it is applied. This is usually considered to be a desirable property of the ester. Methyl salicylate is also used as a flavoring/aroma agent in various products and is referred to commercially as oil of wintergreen. Esters typically have strong, often pleasant, scents and tastes, so many esters are used as flavorings and perfume agents, either individually or in combination. For example, the scent and taste of strawberries is due to the presence of methyl cinnamate, ethyl butyrate, ethyl caproate, isobutyl acetate, and benzyl acetate CHEMICALS 1. 2. 3. 4. 5. Acetic acid anhydride Concentrated sulphric acid Salicylic acid Distilled water Iced water

APPARATUS 1. 2. 3. 4. Water bath 50ml measuring cylinder 25ml measuring cylinder Stirring rod

5. Spatula 6. Electronic balance

PROCEDURE

STEP A dry filter paper was weighed on an electronic balance A distillation flask was weighed and the electronic balance tared. An amount of salicylic acid was put in it and the weight recorded. 8ml of acetic acid anhydride and 7 drops of conc. Sulphric acid was added to the salicylic acid in the flask. The solution was heated for about 20 minutes 25ml of cold water was added to the solution slowly and a further 50ml was added. The precipitate was filtered using a vacuum pump and dried and the weight taken. CALCULATIONS Mass of filter paper = 1.08g

OBSERVATION The electronic balance recorded a weight of 1.08g. The electronic balance recorded a weight of 4.0g.

The sample dissolved.

A clear solution was obtained with evolution of a gas with a sharp smell. White chalky precipitate was formed which thickened gradually. The weight of dry filter paper was 1.0g and that of the filter paper and the sample 6.065g.

Mass of crystals obtained = 6.065g Mass of only crystals Actual yield is 4.0g Salicylic acid + acetic anhydride aspirin + acetic acid The mole ratios are 1:1:1 so one mole salicylic acid reacts with one mole acetic anhydride to produce one mole of aspirin. Molar mass of salicylic acid = 138.1 gm/mole Molar mass of acetic anhydride = 102 gm/mole; 1.082gm/ml density Molar mass of aspirin = 180.2 gm/mole 4.00gm/138.1 = 0.029 moles salicylic acid 8.0 ml acetic anhydride x 1.082 gm/ml = 8.656 gm/102 = 0.085 moles Therefore the limiting reactant is salicylic acid and acetic anhydride is in excess. = 6.065g - 1.08g is 4.985g

The most aspirin that can be made under these conditions is 0.085 moles. 180.2gm/mole x 0.085 moles = 15.292 gms Theoretical yield = 15.292 %Yield = %Yield = %Yield = 26.16% DISCUSSION It is possible to prepare esters using either the acid or the anhydride of the acid together with the Alcohol. Acid anhydrides are much more reactive than the free acid. The synthesis process used in the commercial preparation of Acetylsalicylic acid was carried out. An esterification reaction occurs where the hydroxyl group functional group reacts with part of the acetic anhydride to form an ester in the acetylsalicylic acid product. The other part of the acetic anhydride reacts to produce the byproduct acetic acid. Sulfuric acid was added to the beaker after the addition of salicylic acid and acetic anhydride to allow the reaction to proceed to completion with ease. It didnt take part in the reaction; it was only used as a catalyst. Energy had to be applied to the mixture of salicylic acid and acetic anhydride so that the reacting molecules will collide with enough force to disintegrate their bonds to form newer bonds for the formation of the product. The heating of the sample was done in the water bath to prevent too much heat from attacking the sample since if too much heat is applied the formation of the product will be impossible. Cold water was added to the sample to break up any lumps present, this helps in obtaining a powered form of the product. The sample was changed from the aqueous form to a solid from with the use of the vacuum pump to extract all moisture content making it readily available for weighing.

PRECAUTIONS 1. All acid additions were done in the fume hood, since they were exothermic reactions 2. Sufficient heat was applied for the reaction to proceed more effectively. 3. After the additions of cold water, the sample was dried using a vacuum pump before the experiment continued. ERROR ANALYSIS 1. There were no capillary tubes and thermometers provided to measure the melting point of the sample. Hence the test for purity was not done. 2. Impurities might have gotten into contact with the sample and had reacted and may have reduced its weight. CONCLUSION

Acetylsalicylic acid know commercially as aspirin, often used as an analgesic to relieve minor aches and pains, as an antipyretic to reduce fever, and as an anti-inflammatory medication was produced. The Actual yield is 4.0g and the theoretical yield was calculated to be 15.292g, giving rise to a percentage yield of 26.16%. REFERENCES 1. Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience 2. Palleros, Daniel R. (2000). Experimental Organic Chemistry. New York: John Wiley & Sons, Page 494 3. Lide, D. R., ed. (2005). CRC Handbook of Chemistry and Physics (86th Ed.). Boca Raton (FL): CRC Press. 4. Wang, TH; Bhatt, DL; Topol, EJ (March 2006). "Aspirin and clopidogrel resistance: an emerging clinical entity. European heart journal 27 Pages 647654 5. Singer, H. (1901). "Ueber Aspirin". Pflgers Archiv: European Journal of Physiology Pages 527546