Organic Chemistry Laboratory CH 200L (2012 2013) 2B-Ph Group 9 Experiment 4

Synthesis of Acetanilide and its Purification through Recrystallization

Bianca Therese Rivera, Camille Aliana Rivera, Zarah Mae Roxas, Ma. Rosario Teresa Saylo, Jean Darlene Semilla and Adrian Yu Department of Pharmacy, Faculty of Pharmacy University of Santo Tomas, Espana Street, Manila 1008
Date Submitted: July 27, 2012 Abstract Acetylation of aniline was done in the experiment to synthesize acetanilide. The crude acetanilide was purified by recrystallization. A corn-grain amount of pure acetanilide was mixed with water, methanol and hexane separately to determine the appropriate recrystallizing solvent. The test showed that water was the most effective solvent. A mixture of aniline, distilled water and acetic anhydride was cool in an ice bath to hasten crystallization. The crude acetanilide obtained was dissolved in the water bath with the recrystallizing solvent and was filtered. The weight of the crystals collected is 0.21 grams and its melting o point reached 114-115 C.

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Introduction Recrystallization is the primary method for purifying solid organic compounds. Compounds obtained from natural sources or from reaction mixtures almost always contain impurities. The impurities may include some combination of insoluble, soluble, and colored impurities. Other techniques for purifying solids include sublimation, extraction and chromatography. Nevertheless, even when one of these alternative methods of purification has been used, the solid material thus isolated may still be recrystallized to achieve the highest possible state of purity. The process of recrystallization involves dissolution of the solid in an appropriate solvent at an elevated temperature and the subsequent reformation of the crystals upon cooling, so that any impurities remain in the solution. If the impurities present in the original solid mixture have dissolved and remain dissolved after the solution is cooled, isolation of the crystals that have formed should ideally provide pure material. Alternatively, the impurities may not dissolve at all in the hot solution and may be removed by filtration before the solution is cooled. The crystals that subsequently form should be purer than the original solid mixture. There are times even after a solid has been recrystallized, it may still not be pure. Thus, it is important to determine the purity of the sample, and one of the easiest methods to do this is by determining the melting point of the solid. The experiment aims to (1) synthesize acetanilide by the acetylation of aniline and (2) purify crude acetanilide product by recrystallization.

Methodology A. Choosing Solvent the Recrystallizing

Figure 1. Dissolving crude acetanilide and solvent mixture in water bath. While still hot, the solution was quickly filtered using a fluted filter paper. The filtrate was poured in a beaker containing tap water to be cooled. Formation of crystals occurred and these were collected and washed with distilled water. The crystals were dried by pressing these in-between filter papers. The pure acetanilide produced was weighed and the melting point was determined using an oil bath. The oil bath set-up is shown in Figure 2.

The best recrystallizing solvent for the experiment was determined by mixing in three separate test tubes a corn-grain amount of pure acetanilide and 1mL of the reagent to be tested, water, methanol and hexane. The test tubes were shook and placed in a warm water bath (37 - 40oC) for 1-5 minutes. The test tubes were cooled afterwards and observations were recorded. B. Synthesis of Acetanilide A certain amount (2 mL) of aniline was mixed with 20 mL of distilled water in an Erlenmeyer flask. The acetic anhydride (3 mL) was slowly added. The mixture was cooled in an ice bath to hasten crystallization. The mixture was filtered through a wet filter paper making the crude acetanilide as the residue. The crude acetanilide was made to dry and weighed. C. Purification of Crude Acetanilide The recrystallizing solvent (20 mL) was added to the crude acetanilide. This was heated in a water bath until the solid completely dissolved (Figure 1).

Figure 2. Oil bath set-up

Results and Discussion In the determination which is the appropriate recrystallizing solvent between water, methanol and hexane, the results obtained after heating the

mixtures in a water bath are shown in Table 1. At room temp. + During heating + Upon cooling -

water methanol hexane

It is important to determine the purity of the substance obtained and this is done by determining the melting point of the substance. The melting point of the pure acetanilide obtained was verified by heating it in an oil bath with a thermometer. The melting point of the pure acetanilide based on the experiment is 114-115oC. This means that the product does not have impurities anymore since the melting point observed has no difference with the theoretical melting point of acetanilide which is 114.3oC. References [1] Bayquen A. et.al.(2009).Laboratory Manual in Organic Chemistry .Quezon City: C&E Publishing Inc. [2] http://www.chem.umass.edu/~samal/26 9/cryst1.pdf [3] http://www.chem.utoronto.ca/coursenote s/CHM249/Recrystallization.pdf [4] http://chem.chem.rochester.edu/~chem2 07/Recrystallization.pdf

Table 1. Solubility of Recrystallizing Solvents Based on the results on Table 1, the pure acetanilide when mixed with water is insoluble at room temperature and upon cooling but soluble during heating. On the other hand, it is soluble in methanol only at room temperature and it is insoluble in hexane. The results showed that water is the best recrystallizing solvent since a suitable solvent should have high solubility at high temperatures and low solubility at low temperatures. In the acetylation of aniline, the amount of crude acetanilide produced was 4.3 grams. After the recrystallization process, the amount of crystals collected which is the pure acetanilide was 0.21 grams. The percentage yield was computed after the weighing of the product. The formula for solving the percentage yield is:

% yield =

0.21 grams x 100 2.97 grams

% yield = 7.07 %