Sythesization and Purification of Acetanilide by Acetylation and Recrystallization

K.A. Dimaano, G.P. Directo, C. Ducut, T.* Encinares, M.H. Encinas

Abstract Recrystallization is the most common and simplest method for purifying organic solids that differ in solubility and temperature. In this experiment, acetanilide was produced by the reaction of aniline and acetic anhydride. The crude acetanilide undergoes a crystallization process using a recrystallizing solvent.

Introduction Acetanilide can be formed by using recrystallization and synthesization. Crystallization is a technique which chemists use to purify solid compounds. It is based on the principles of solubility: compounds (solutes) tend to be more soluble in hot liquids (solvents) than they are in cold liquids. If a saturated hot solution is allowed to cool, the solute is no longer soluble in the solvent and forms crystals of pure compound. Impurities are excluded from the growing crystals and the pure solid crystals can be separated from the dissolved impurities by filtration (1). Recrystallization of acetanilide can be done by using a recrystallization solvent that can be determined using the solubility test. Recrystallization solvent is based on these following criteria: a. the crude crystals should have low solubility in the chosen solvent at room temperature, b. the crude crystals should have high solubility in the chosen

solvent when heated to boiling, c. The crude crystals should not react with the solvent, d. The solvent should boil at temperature below the solid melting point, e. The solvent should moderately be volatile so crystals dried readily, f. The solvent should be non-toxic, nonflammable, and inexpensive (2). Synthesization of acetanilide can be done by acetylation of aniline. Acetic anhydride is the reagent added to aniline to undergo acteylation. Acetylation is the process of introducing an acetyl functional group into a compound. Acetic anhydride or ethanoic anhydride, whose chemical formula is C4H6O3, is widely used as reagent in chemical synthesis. It has a vinegar-like odor and reacts with water to form acetic acid. It is also used in manufacturing aspirin, formed due to acetylation of salicylic acid (3). The experiment aims to synthesize acetanilide by the acetylation of aniline and purify crude acetanilide product by recrystallization.

Methodology A corn-grain amount of pure acetanilide is placed into three (3) different test tubes, adding distilled water to one test tube, hexane to another, and methanol to the last, then shaken well. Note the solubility of acetanilide. After shaking, put them in a water bath for 1-5 minutes; again, note the solubility of A\acetanilide in its respective solvents under heat. Let the test tube cool and record the solubility of the Acetanilide. This process determined the appropriate and the best recrystallizing solvent. Two (2) mL of analine and 20 mL of distilled water is mixed in an Erlenmeyer flask. Three (3) mL of acetic anhydride is added to the solution and was cooled in the ice bath to hasten crystallization. It was filtered and left to dry before weighing. Twenty (20) mL of the recrystallizing solvent was poured into the crude acetanilide and is heated in the water bath until the entire solid dissolved. It is filtered while still hot. The filtrate is then cooled by placing the receiver in a beaker containing tap water. After cooling, the crystals were collected and washed with distilled water; it was placed in the fume hood to dry. After drying, pure acetanilide is obtained and was weighed. Percentage yield was calculated by using the formula: also

Percentage yield =

x 100%

To calculate for the theoretical yield, the rate limiting step is identified using the formula:
GramsA x Molecular MassA x Molecular MassB

The grams of aniline and acetic anhydride use in the experiment are calculated by using the formula:
Grams = mL x density

In order to test the purity of the acetanilide, the melting point of recrystallized acetanilide was determined together with the melting point of the pure acetanilide that was available in the lab.

Results Table 1 shows the solubility of pure acetanilide in water, methanol, and hexane at room temperature, during heating and upon cooling.
Table 1: Solubility of Pure Acetanilide in Various Solvents Water at room temp. during heating upon cooling insoluble soluble Insoluble Methanol at room temp. during heating upon cooling soluble soluble soluble

Hexane at room temp. during heating upon cooling insoluble insoluble with crystal residue

Discussion In table 1, it shows the result of the experiment done to test the best recrystallizing solvent. Since a good recrystallizing solvent should show that a solute should be insoluble at room temperature and soluble at high temperature (4), water is shown as the best recrystallization solvent. Results shown in table tell us that the weight of the crude acetanilide contains a lot of impurities as the weight of the pure acetanilide that was obtained is only 0.627 g. Based on the data gathered, the recrystallized acetanilide melting point range is within 112o 114o C. Since the pure acetanilide melting point falls under these numbers, we could assume that the recrystallized acetanilide is pure. In calculating the percentage yield, the theoretical yield is needed. The theoretical yield can be computed by calculating the amount in grams contained in aniline and acetic anhydride using their densities and amount used in milliliters. After obtaining the amount in grams of the substances, the limiting reagent is determined. Limiting reagent is defined as the reactant that is completely consumed in a reaction, thereby limiting the amounts of products formed. To determine the limiting reagent, calculate the amount of product (moles or grams) that can be formed from each reactant. The reactant producing the smallest amount of product is the limiting reagent (5). Thus, from the definition, Aniline is the limiting reagent and the theoretical yield.

Table 2 shows the weight of the crude acetanilide and pure acetanilide together with the melting point of the recrystallized acetanilide.
Table 2: Weight and Melting Point of Acetanilide Crude Acetanilide Pure Acetanilide Recrystallized Acetanilide Pure Acetanilide

Weight Melting Point

2.7555 g 0.627 g 112 -114 C 114 -115 C

o o o o

The theoretical yield and percentage yield was also computed:

Aniline = 2mL x = 2.0434 g = 3.426 g

Acetic Anhydride = 3mL x

Limiting determined:
Aniline = 2.0434 g x

Reagent

was

also

= 2.24 g x = 2.96 g

Acetic Anhydride = 3.426 g x

Limiting Reagent: Aniline The computed: percentage yield is

Percentage yield =

x 100% = 30.68%

After the determination of the limiting reagent and the theoretical yield, the percentage yield was computed. The result was 30.68%. Conclusion Synthesizing acetanilide by acetylation can be done by reacting aniline and acetic anhydride. In recrystallizing the crude acetanilide, water was use as it is the best recrystallizing agent. Purifying by means of recrystallization results in a purified acetanilide. References 1. http://orgchem.colorado.edu/hndbksupport/cryst/cryst.html Date Accessed: August 19, 2011 2. Pahlavan, G. (2010). Chemistry 1411/1412 Lab Manual Third Edition. Minesota, USA. Blue Door Publishing 3. Lehman, J.W. (2009). Operational Organic Chemistry A Problem-Solving Approach to the Laboratory Course Fourth Edition. Upper Saddle River, New Jersey, USA. Pearson Education, Inc. 4. http://courses.chem.psu.edu/chem35/LecSp06/Lec2Sp06.pdf Date Accessed: August 20, 2011 5. http://www.chem.latech.edu/~deddy/chem104/L1Limit.html Date Accessed: August 20, 2011