Dehydration of Cyclohexanol to Produce Cyclohexene Oxidation of Cyclohexene to Produce Adipic Acid

Chemical Concepts
Dehydration of alcohols to produce alkenes; multistep syntheses; liquid-liquid extractions; drying agents; simple and fractional distillation; boiling point determination; infrared (IR) spectroscopy Oxidative cleavage of an alkene carbon-carbon double bond; phase transfer catalysis; recrystallization; melting point determination

Green Lessons
Less hazardous chemical syntheses; solventless reactions; "green" redox agents

Estimated Lab Time: 6 hours

Introduction and Reaction Mechanism

This is a two part experiment. In Part I we prepare an alkene by dehydrating an alcohol. In Part II we subject the alkene to vigorous oxidation conditions to form a dicarboxylic acid. The elimination reaction makes use of phosphoric acid to catalyze the reaction rather than the traditional strong acid, sulfuric acid. Sulfuric acid is highly corrosive, and it has a tendency to react with organic compounds producing dark colored residues (road tar in common lab conversation). Phosphoric acid is less corrosive than sulfuric acid, and it is less likely to react with your starting material. The chemistry of this elimination reaction is made green by the use of a less toxic acid and by the lack of a solvent. The reactants are all liquids that mix together.
H OH H H H
H+ + + :O ..

OH2 H H

OH2 H H
-H2O

H H

H H
-H+

+ H3O+

Dehydration of Cyclohexanol and Oxidation of Cyclohexene

Notice that the hydroxide group is converted into a better leaving group (H 2O) by the addition of an acid. The H+ is regenerated at the end as a catalyst should be. All the reactions are reversible. A carbon-carbon double bond is a site of relatively high electron density. As such, it is susceptible to oxidation. Vigorous conditions will result in cleavage of the double bond forming ketones and aldehydes (which are further oxidized to acids) depending on the substitution on the alkene.

O O HO OH cyclohexene 1,6-hexanedioic acid or adipic acid

In the laboratory, hot basic potassium permanganate solution is often used to accomplish this oxidation. The KMnO4 must be used in stoichiometric amounts. Large quantities of MnO2 waste are generated. In industry nitric acid is used to produce adipic acid. This method presents many chemical safety and environmental risks. Nitric acid can react violently with organic compounds, and serious accidents have been reported. Also the industrial process produces N2O emissions (a suspected greenhouse gas). We will use sodium tungstate, Na2WO4, as a catalyst for the oxidation of cyclohexene with hydrogen peroxide. Only a catalytic amount of sodium tungstate is required, and water is generated as a product. This avoids the decidedly ungreen strongly basic potassium permanganate reaction with the MnO 2 waste. The net reaction may be written as follows"

O 4 H2O2 + O HO OH cyclohexene 1,6-hexanedioic acid or adipic acid + 4 H2O

Sodium tungstate is water-soluble, but cyclohexene is not. To overcome the problem of a reaction mixture with two immiscible liquids we will use a phase transfer catalyst. Ammonium salts bearing hydrophobic groups are ionic, but they are much less polar than water. The diagram on the next page shows how this phase transfer catalyst works.

Dehydration of Cyclohexanol and Oxidation of Cyclohexene

adipic acid

2 R4N+X-

(R4N)2WO4

(R4N)2[reduced W]

2 R4N+Xorganic phase aqueous phase

Na2WO4

2 NaX

2 NaX

Na2[reduced W]

H2O2

Phase transfer catalysis K. Sato, M. Aoki, and R. Noyori, A Green Route to Adipic Acid: Direct Oxidation of Cyclohexenes with 30 Percent Hydroxide Peroxide, Science 1998, 281, 1646

Dehydration of Cyclohexanol and Oxidation of Cyclohexene

Dehydration of Cyclohexanol
Experimental Procedure
Pre-Lab Preparation
Carry out pre-lab preparations as called for by your instructor.

SAFETY PRECAUTIONS: Phosphoric acid is safer than sulfuric acid. However, phosphoric acid is still corrosive. Avoid contact and clean up any spills immediately. Cyclohexanol does not present any unusual hazards. Cyclohexene is flammable and has an objectionable odor.

Reaction
1. To a 25-mL round-bottom flask containing a magnetic stir bar (or boiling stone), add 0.074 moles of cyclohexanol and 1.75 mL of 85% H3PO4. Use gentle swirling to mix the two layers. 2. Fit the flask with a fractionating column, a distillation adapter, a thermometer, a condenser, and a vacuum adapter as for fractional distillation (see illustration). A rubber septum should be used to provide a seal between the thermocouple or thermometer and the glassware. Be sure that the seal is good if it is not, cyclohexene will escape from your glassware, causing your experiment to fail, and your classmates who find the odor of cyclohexene objectionable will complain loudly! A drying tube, as shown in the illustration on the next page, can help to control the disagreeable odor of cyclohexene. 3. Heat the reaction mixture first at a gentle reflux for about 5 minutes. Then heat the flask more strongly in order to distill the mixture into the collection flask. Keep distilling until the volume remaining in the distillation flask has been reduced to approximately 1 mL.

Dehydration of Cyclohexanol and Oxidation of Cyclohexene

Apparatus for dehydration of cvclohexanol

Workup
4. Transfer the distillate to a separatory funnel and wash with approximately 5 mL of water. Carefully separate the layers and transfer the organic layer into a small, dry Erlenmeyer flask. If any water droplets are visible, remove them before adding the drying agent (sodium sulfate). Add a small amount (~ 1 g/25 mL liquid) of anhydrous sodium sulfate to the flask. Let the mixture stand for 5 minutes, occasionally swirling it gently. If the drying agent completely clumps together, its capacity to remove water has been exceeded and a little more sodium sulfate should be added. If you have successfully removed the water, the liquid should be clear, and at least a little of the drying agent should remain free flowing. 5. Decant or pipette the organic liquid away from the drying agent and place it in a clean, dry round-bottom flask. This will be the distillation flask for the next step. The appropriate size depends upon your yield. The flask should be about half full at the beginning of the distillation.

Dehydration of Cyclohexanol and Oxidation of Cyclohexene Distillation

6. Fit the flask with a distillation adapter and condenser in preparation for a simple distillation. The apparatus will look the same as that used for fractional distillation, except that there will be no Vigreux or other fractionating column. 7. Be sure that your thermometer is properly positioned in order to measure the temperature of the distilling liquid accurately (see the illustration above). Carefully distill the organic material, collecting the material that distills in the range of 80 90C. Typically there will he very little material remaining in the distillation flask. Be sure to record the boiling range that you observe.

Characterization
8. Transfer the distilled cyclohexene to a clean, dry, pre-weighed sample vial and determine the mass of the product. If time permits, record an infrared spectrum of the distilled product.

Storage
9. You will need the cyclohexene for the synthesis of adipic acid. Keep it in a well-sealed and suitably labeled sample vial until then.

Post-Lab Questions and Exercises

1. Describe the color and state of your purified product. Report the mass and percent of theoretical yield of the purified product. 2. What boiling point range did you observe during your (a) initial distillation and (b) your final distillation? How do you explain the difference between these, if there was one? 3. What does the phosphoric acid do in the reaction? 4. Interpret your IR spectrum. Assign vibrations for the major peaks in the spectrum. 5. One of the objectives of green chemistry is to prevent waste. Hence, synthetic methods should attempt to incorporate all the starting reagents into the final product. If all starting reagents are incorporated into the final product, the atom economy is said to be 100%. Atom economy can be calculated using the following equation:

% atom economy

FormulaM ass of Product 100 (FormulaM asses of All ReactantsUsed)

Calculate the atom economy for the reaction.

Dehydration of Cyclohexanol and Oxidation of Cyclohexene

Synthesis of Adipic Acid

Experimental Procedure
Pre-Lab Preparation
Carry out pre-lab preparations as called for by your instructor.

SAFETY PRECAUTIONS: Avoid contact with the phase transfer catalyst as irritating and can transport contaminants through the skin. Avoid getting hydrogen peroxide on you or your clothing. Cyclohexene is flammable and its odor is often considered to be disagreeable.

Note: You need at least 2 g of cyclohexene to perform this experiment. If you did not obtain this quantity of cyclohexene from the prior experiment, obtain the necessary amount of cyclohexene from your instructor.

Reaction
I. Place 0.50 g of sodium tungstate dihydrate (Na2WO42H2O) in a 50-mL round-bottom flask containing a stir bar and fitted with a water-cooled condenser. Notes: The efficient stirring important for the success of this reaction is more easily achieved in a round-bottom flask than in a pear-shaped flask. An efficient water-cooled condenser is required to avoid loss of cvclohexene during the reaction. 2. Add 0.5 g of Aliquat 336 this is a very viscous liquid that is hard to transfer, so weigh it directly into your reaction flask. It is not necessary to obtain exactly 0.50 g. Next, add 11.98 g of 30% hydrogen peroxide and 0.37 g of KHSO4 to the reaction mixture. Stir, then add 2.00 g of cyclohexene. Note: The order of addition of the reagents is important. 3. Heat the mixture to reflux on a sand bath, then continue to heat at reflux for I hour while stirring vigorously. About halfway through the reflux period, rinse down any cyclohexene trapped in the condenser with a few mL of water, added via pipette. Phase transfer catalysis depends upon very efficient mixing of the organic and aqueous layers, so it is important to stir as fast as possible throughout the reaction. (Generally, when using a magnetic stirrer, the closer your flask is to the surface of the stirrer, the easier it is to maintain rapid stirring.) The reaction will not proceed if it is heated at below reflux, but it is also very important that you do not heat the mixture too strongly. If you do, cyclohexene may be lost through the top of the condenser. Watch the condenser closely If you see liquid condensing near the top, you need to reduce the heat. You may need to remove the flask from the heat source temporarily in order to bring the reflux back under control. Stop the stirring occasionally to see if there are still two layers present. The reaction is complete when it no longer separates into two layers.

Dehydration of Cyclohexanol and Oxidation of Cyclohexene Workup

4. Use a Pasteur pipette to transfer the hot reaction mixture into a small beaker. Leave behind any of the phase transfer catalyst that may have separated. (If the catalyst separates and it does not always do so it will stick to the walls of the flask or form a separate oily layer at the bottom of the flask. Careful execution of this step is the key to a successful purification. It is better to leave a little of the aqueous solution behind than to risk contamination of your solution with the phase transfer catalyst.) 5. Cool the beaker containing the reaction mixture rapidly in an ice bath. A precipitate should form within 20 minutes. Collect the crude product by vacuum filtration using a Buchner funnel. 6. After the crude material has air-dried, weigh it and determine its melting point.

Purification and Characterization

7. Recrystallize the crude product from the minimum required amount of hot water. Determine the mass and melting point of the recrystallized product and (if time permits) obtain its infrared spectrum.

Post-Lab Questions and Exercises

1. Describe the color and melting point range of your crude product. 2. Describe the color and melting point range of your recrystallized product. Report the mass and percent of theoretical yield of the recrystallized product. 3. Attach the IR spectrum and identify the major peaks of the spectrum. 4. Calculate the atom economy for the reaction. Modified July 10, 2008 by Sharmaine S. Cady, East Stroudsburg University