EXPERIMENT 4 ALDEHYDES AND KETONES: PREPARATION AND QUALITATIVE ANALYSIS

Materials Needed 20 mL 70% 2-propanol (isopropyl alcohol) 100 mL acidic dichromate (K2Cr2O7/H2SO4) solution Distillation apparatus including thermometer 2 mL propanal (propionaldehyde) 2 mL cyclohexanone 4 mL 5% AgNO3(aq) 12 mL 5% NaOH(aq) 5% NH3(aq) or conc. NH4OH(aq) 6 mL copper(II) citrate solution (Benedict's reagent) 4-hydroxy-3-methoxybenzaldehyde Additional Reading Assignment McMurry, chap 14.5 (pp 375-377), chap 16 Introduction I. Structure and Preparation of Aldehydes and Ketones

Aldehydes and ketones both contain the C=O or carbonyl group. Aldehydes have at least one hydrogen bonded directly to the C=O whereas ketones always have two alkyl groups attached to the C=O.
O C R H an aldehyde R O C R' a ketone

Aldehydes may be prepared by oxidation of 1 alcohols; potassium dichromate (K2Cr2O7) in acidic solution (H2SO4(aq)) can sometimes be used as the oxidizing agent (eq 1). H H+ | --- R-C=O + (aldehyde)

R-CH2-OH + K2Cr2O7 (1 alcohol)

Cr3+

(1)

However it is difficult to prevent further oxidation of the aldehyde product to a carboxylic acid (see McMurry p 375-376 and Part III of this Introduction). Ketones may be prepared by oxidation of 2 alcohols. Again, acidic K2Cr2O7 may be used (eq 2). R' | H+ R-CH-OH + K2Cr2O7 --- R' | R-C=O

Cr3+

(2)

1 Adapted from E. Boschmann & Norman Wells, Chemistry in Action: A Laboratory Manual for General,
Organic, and Biological Chemistry, 4th Edition, page 309. 1

(2alcohol)

(ketone)

Unlike with aldehydes (see above) further oxidation of the ketone product is not a problem (see McMurry p 376 and part III of this Introduction). The common and important compound acetone (IUPAC name, 2-propanone) is the simplest ketone) Acetone is a commercial solvent and is used in paint thinners and nail polish removers. Acetone is easily prepared by the oxidation of 2-propanol with acidic dichromate, a reaction that you will carry out in this lab. The acetone product will be purified using a distillation. II. Physical Properties (see McMurry chapter 16.3)
O C CH3 acetone CH3

Because they contain the polar carbonyl group, aldehydes and ketones are polar compounds. However, they cannot form hydrogen bonds one to another, as do alcohols. Therefore, the boiling points of aldehydes and ketones are less than those of alcohols of similar molecular weight, but greater than those of hydrocarbons of similar molecular weight (see McMurry Table 16.2, p 421). The solubility of aldehydes and ketones in H2O is significant if they contain less than five carbons. This is because hydrogen bonds to the water molecules are formed (see p 422). Acetaldehyde (ethanal, CH3CHO) and acetone are miscible with water in all proportions. III. Chemical Properties (see McMurry chapter 16.5)

Aldehydes are easily oxidized a fact due to the presence of the hydrogen attached to the carbonyl group (this is not present in ketones, which are less easily oxidized). Oxidation of aldehydes yields carboxylic acids. Even air will oxidize an aldehyde (eq 3). H OH | | R-C=O + O2 --- R-C=O (3) (aldehyde) (from air) (carboxylic acid) Other weak oxidizing agents can bring about this reaction. One of these is Tollens' reagent, a basic (OH-) solution of the silver complex ion, Ag(NH3)+. The reaction produces metallic silver (Ag0), which often forms a shiny "mirror" on the sides of the container (eq 4). H OH | | R-C=O + Ag(NH3)2+ --- R-C=O + Ag0 (4) (Tollens' reagent) (silver mirror) Tollens' reagent is used to detect the presence of aldehydes. A solution of Benedict's reagent can also oxidize aldehydes. This solution consists of a basic (OH-) solution of copper(II) citrate (whose complex composition cannot be represented by a simple formula): H OH | | R-C=O + copper(II) citrate --- R-C=O + Cu2O (5) (Benedict's reagent) (copper(I) oxide) The conversion of the clear, blue copper(II) citrate to insoluble, reddish copper(I) oxide indicates a positive test. The reaction occurs not only with simple aldehydes but also with "reducing sugars" such as glucose.

SAFETY PRECAUTIONS
- WEAR YOUR SAFETY GLASSES AT ALL TIMES. - IF YOU SPILL A SOLUTION ON YOUR SKIN, BE SURE TO FLUSH THE AREA PROMPTLY WITH LOTS OF WATER. - TAKE SPECIAL CARE WITH ACIDIC DICHROMATE SOLUTION, WHICH IS AN EXTREMELY CORROSIVE AND DANGEROUS SUBSTANCE. IF YOU GET ANY ON YOUR SKIN OR CLOTHING, RINSE IT WITH WATER IMMEDIATELY. DOING SO WILL AVOID SERIOUS INJURY. 2 - It is important that the directions be followed exactly. Carelessness can be DANGEROUS!

Procedure I. Preparation of Acetone from 2-Propanol Prepare an ice/water bath; this may be conveniently done in a large (i.e., > 500 mL) beaker. Place 20 mL of 70% 2-propanol in a 250-mL beaker, and add 20 mL of distilled H2O. Stir to mix, and cool the beaker in an ice bath to about 10C. With the solution still in the ice bath, add, all at once, 100 mL of "acidic dichromate" solution (CAUTION: Corrosive!). In a few seconds, the mixture will turn dark, followed by a rather sudden rise in temperature to 5060C. Stir the mixture (still in the ice bath!) until its temperature has fallen to below 50C. NOTE: Do not use the thermometer as a stirring rod. Pour the mixture into a 250-mL (or larger) distilling flask using a funnel to prevent spilling any. Assemble a distillation apparatus as demonstrated by your lab instructor. Use a graduated cylinder as the receiver. Heat gently. After 10-15 minutes, the liquid should begin to boil and drops of acetone begin to collect in the receiver. Record the temperature when the first drop appears. Continue the distillation until at least 5 mL of acetone has collected. Record the temperature again, and then stop the distillation. Measure the volume of acetone obtained. Use the acetone you prepared for the qualitative analysis tests. Leave the distillation apparatus as is. It will be disassembled and cleaned by stockroom personnel. II. Qualitative Analysis 1. Solubility Tests Place 2 mL of distilled H2O in each of three test tubes. - To the first, add 10 drops of acetone. - To the second, add 10 drops of propanal. - To the third, add 10 drops of cyclohexanone. Gently shake each test tube, and note the degree of solubility on the data table. How do you account for differences between the three compounds tested? 1. Chemical Tests: Oxidation A. Tollens' Test: To prepare the reagent, clean a medium-size test tube thoroughly with soap and water and rinse with distilled H2O. Place 4 mL of 5% AgNO3 in the test tube, and add 2 drops of 5% NaOH, mixing thoroughly. A dark brown precipitate of silver oxide (Ag2O) will form. Now dissolve the precipitate by adding 5% aqueous NH3 (conc. NH4OH) until the solid disappears and a clear colorless solution is obtained. Divide the Ag(NH3)2+ reagent you have just prepared approximately equally between three clean test tubes. - To the first, add 3 drops of acetone. - To the second, add 3 drops of propanal. - To the third, add 3 drops of cyclohexanone. If no precipitate forms and no mirror appear, heat the tubes in the water bath provided. Record your observations on each tube on the data table. CAUTION: Do not let the Tollens' reagent stand around, since it may form explosive substances. Dispose of it in the appropriately labeled waste beaker in the hood. B. Benedict's Test: Place 2 mL of Benedict's solution in each of three test tubes. - To the first, add 20 drops of acetone. - To the second, add 20 drops of propanal. 3

- To the third, add 20 drops of cyclohexanone. Heat the test tubes in the water bath provided for 10 minutes (in the hood). Watch for the appearance of reddish Cu2O. Record your observations on each tube on the data table. III. A Natural Product

A bottle of the material whose structure is shown below will be available. Fan your hand over the open bottle and toward your nose. What does its odor remind you of? Using a handbook (e.g., the CRC Handbook of Chemistry & Physics or Aldrich Chemical Co. Catalog), find the common name for this naturally occurring compound.

PRE-LABORATORY QUESTIONS EXPERIMENT 4: ALDEHYDES AND KETONES: PREPARATION AND QUALITATIVE ANALYSIS
Name _________________________________________________ Section ____________ Date ____________ 1. Give the structure of a. Acetone

b. Propanal

c. Cyclohexanone

2.

(a) What is the result observed experimentally which indicates a positive test with the Tollens' reagent? (b) What kind of compounds give a positive test?

IN-LAB OBSERVATIONS/DATA EXPERIMENT 4: ALDEHYDES AND KETONES: PREPARATION AND QUALITATIVE ANALYSIS
Name ________________________________________________ Section ____________ Date ____________ Partner _______________________________________________ I. Preparation of Acetone Observations on reaction of 2-propanol with K2Cr2O7/H2SO4. Appearance of reactants___________________________________________________________ ______________________________________________________________________________ ______________________________________________________________________________ Appearance of solution after reaction_________________________________________________ Highest temperature reached by the reacting solution _________ C Distillation results 1. 2. 3. 4. 5. Temperature when first drop of distillate is obtained Temperature at which distillation is stopped Handbook value for boiling point of acetone Volume of distillate obtained (yield of acetone) _________ C _________ C _________ C _________ C

Observations on the distillate (appearance, odor, etc.)____________________________________ ______________________________________________________________________________ ______________________________________________________________________________

II.

Qualitative Analysis

As in experiments #2 and #3 you should carefully observe all stages of each part of the experiment and note your observations regarding each test directly in the table. Acetone: solubility in water ______________________________________________________________________ reactivity with Tollens reagent_____________________________________________________________ reactivity with Benedict's reagent___________________________________________________________ Propanal general observations ____________________________________________________________________ solubility in water ______________________________________________________________________ reactivity with Tollens reagent_____________________________________________________________ reactivity with Benedict's reagent___________________________________________________________ Cyclohexanone general observations ____________________________________________________________________ solubility in water ______________________________________________________________________ reactivity with Tollens reagent_____________________________________________________________ reactivity with Benedict's reagent___________________________________________________________ III. A Natural Product Describe the odor and appearance of 4-hydroxy-3-methoxybenzaldehyde.

REPORT SHEET EXPERIMENT 4: ALDEHYDES AND KETONES: PREPARATION AND QUALITATIVE ANALYSIS
I. Preparation of Acetone Results Yield _____________ bp range ________________ literature bp ________________

II. Qualitative Analysis Results Table Compound Acetone Structure Appearance H2O solubility Tollens' test Benedict's test

Propanal

Cyclohexanone

III.

A Natural Product Common name of 4-hydroxy-3-methoxybenzaldehyde ________________________________________

Questions I. Preparation of Acetone 1. How does the handbook value for the boiling point of acetone compare to the temperature range over which your distillation proceeded? What distilling temperature would be expected for a distillation of pure acetone?

II. Qualitative Analysis 1. How do you account for the differences in water solubility between the three compounds tested? Explain clearly and completely.

2.

Tollens' Test. Which compound(s) gave a positive test? Why?

3.

Benedict's Test. Which compound(s) gave a positive test? Why?

4.

Write chemical equations (not necessarily balanced) for the reaction of propanal with a. Tollens' reagent

b. Benedict's reagent

5.

What results would be expected if the following tests were carried out on the natural product used in part III of this lab? (Explain your answers.) a. H2O solubility

b. Tollens' test

c. Benedict's test