PHAR 1123 PHARMACEUTICAL CHEMISTRY II

EXPERIMENT 4 Classification and Identification of Aldehydes and Ketones OBJECTIVES 1. To learn the chemical characteristics of aldehydes and ketones. 2. To use these chemical characteristics in simple tests to distinguish between examples of aldehydes and ketones. APPARATUS Test tubes Cork Dropper 400 mL beaker CHEMICALS Formaldehyde Benzaldehyde Cyclohexanone Acetone Acetone (reagent grade) Chromic acid BACKGROUND
Aldehydes and ketones are representative of compounds which possess the carbonyl group:

Hotplate Thermometer Tongs

Diethyl ether Tollens reagent 1 M HNO3 I2-KI reagent 10% NaOH 2,4-dinitrophenylhydrazine

Aldehydes have at least one hydrogen attached to the carbonyl carbon; in ketones, no hydrogens are directly attached to the carbonyl carbon, only carbon containing R-groups:

Aldehydes and ketones of low molecular weight have commercial importance. Many others occur naturally. In this experiment you will investigate the chemical properties of representative aldehydes and ketones. Classification Tests Chromic acid test. Aldehydes are oxidized to carboxylic acids by chromic acid; ketones are not oxidized. A positive test results in the formation of a blue-green solution from the brown-red color of chromic acid. Tollens test. Most aldehydes reduce Tollens reagent (ammonia and silver nitrate) to give a precipitate of silver metal. The free silver forms a silver mirror on the

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PHAR 1123 PHARMACEUTICAL CHEMISTRY II

sides of the test tube. (This test is sometimes referred to as the silver mirror test.) The aldehyde is oxidized to a carboxylic acid. Iodoform test. Methyl ketones give the yellow precipitate iodoform when reacted with iodine in aqueous sodium hydroxide. 2,4-Dinitrophenylhydrazine test. All aldehydes and ketones give an immediate precipitate with 2,4-dinitrophenylhydrazine reagent. This reaction is general for both these functional groups. The color of the precipitate varies from yellow to red. (Note that alcohols do not give this test.)

PROCEDURE Classification Tests 1. 2. Classification tests are to be carried out on four known compounds and one unknown. Any one test should be carried out on all five samples at the same time for comparison. Label test tubes are as shown in the table below. Test Tube No. 1 2 3 4 5 Experiment I Chromic Acid Test Caution: Chromic acid is toxic and corrosive. Handle with care and promptly wash any spill. Use gloves with this reagent. 1. 2. 3. 4. 5. 6. Place 5 drops of each substance into separate test tubes. Dissolve each compound in 20 drops of reagent-grade acetone (to serve as solvent). Add to each test tube 4 drops of chromic acid reagent, 1 drop at a time; after each drop, mix by sharply tapping the test tube with your finger. Let stand for 10 minutes. Aliphatic aldehydes should show a change within a minute; aromatic aldehydes take longer. Note the approximate time for any change in color or formation of a precipitate on the Report Sheet. Compound Formaldehyde Benzaldehyde Cyclohexanone Acetone Unknown

Experiment II Tollens Test Caution: This reagent must be freshly prepared before it is to be used and any excess disposed of immediately after use. Organic residues should be discarded in appropriate waste containers. Unused Tollens reagent should eb collected from every student by the instructor. Do not store Tollens reagent; it is explosive when dry. The instructor should dispose of the excess reagent by adding 1 M HNO3 until acidic, warming on a hot plate. The solution can then be stored in a waste container for heavy metals. 1. Place 5 drops of each sample into separate test tubes and labeled them.
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PHAR 1123 PHARMACEUTICAL CHEMISTRY II

2. 3. 4. 5. 6. 7.

Dissolve the compound in diethyl ether by adding this solvent dropwise until a homogenous solution is obtained. Then add 2 mL (approximately 40 drops) of the Tollens reagent and mix by sharply tapping the test tube with your finger. Place the test tube in a 60 oC water bath for 5 minutes. Remove the test tubes from the water and look for a silver mirror. If the tube is clean, a silver mirror will be formed; if not, a black precipitate of finely divided silver will appear. Record your results on the Report Sheet. (Clean your test tubes with 1 M HNO3 and discard the solution in a waste container designated by your instructor.)

Experiment III Iodoform Test 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. Prepare a water bath of 60 oC in a 400-mL beaker. Place 5 drops of sample into 5 separate clean and dry test tubes. Add 2 mL of water to each test tube. If the compound is not soluble, add diethyl ether (dropwise) until the solution is homogeneous. Add to each test tube (dropwise) 2 mL of 10% NaOH; tap the test tube with your finger to mix. Warm the mixtures in the 60 oC water bath. Add the solution of I2-KI test reagent (dropwise) to each test tube, with shaking, until each solution becomes brown. Cork each test tube and shake vigorously; remove the cork and return to the warm water bath. If the color fades, add more I2-KI test reagent until the dark color persists for 2 minutes at 60 oC. Add 10% NaOH (dropwise) until each solution becomes colorless; cork and shake again. Return the test tubes to the warm water bath for 5 minutes. While heating, remember to remove the corks. Remove the test tubes from the water and dilute each solution with cold water; leave enough room so you can cork and shake one last time. Let cool and look for a light yellow precipitate. The formation of the yellow precipitate tends to be slow. Put these test tubes to one side and makes your observations when the other tests are completed. Record your observations.

Experiment IV 2,4-Dinitrophenylhydrazine Test 1. 2. 3. 4. Place 5 drops of each sample into separate test tubes and labeled them. Add 20 drops of the 2,4-dinitrophenylhydrazine reagent to each. If no precipitate forms immediately, heat for 5 minutes in a warm water bath (60 o C); let cool. Record your observations.

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PHAR 1123 PHARMACEUTICAL CHEMISTRY II

NAME: ___________________________________ MATRIC NUM: ____________________________ REPORT SHEET: EXPERIMENT 4 Classification and Identification of Aldehydes and Ketones Test Formaldehyde Benzaldehyde Cyclohexanone Acetone Unknown

Chromic acid

Tollens

Iodoform

2,4Dinitrophenylhydrazine

The unknown compound is _________________

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