Genika Ferrer

07/18/12

Experiment 43; pg. 348-358

Lab #4 Enamine Reactions: 2-acetylcyclohexanone

Abstract

The purpose of this lab is to prepare 2-acetylcyclohexanone by first preparing enamines through an acid catalyzed addition-elimination reaction from cyclohexanone and pyrrolidine. The water, the by-product, will be removed by azeotropic distillation with toluene, which also drives the reaction to the right.

Important Equations

Procedure Running the Reaction 1. Place 0.64ml of cyclohexanone into a preweighed 10ml roundbottom flask. Determine mass of cyclohexanone. 2. Add 4ml of toluene Add 20mg p-toluenesulfonic acid monohydrate Add 0.54ml of (cooled) pyrrolidine 3. Add a magnetic stirring bar, and attach a Hickman head, water-cooled condenser, and a drying tube that contains moistened cotton. (picture on figure 15.15, pg 730, and figure 14.5 on page 708)

Distillation

4. While stirring, distill mixture with aluminum block adjusted to at least 140oC. Adjust rate so that it takes 30 minutes. 5. Collect distillate in Hickman head. Detach condenser, remove 2ml of distillate, and transfer to conical vial for storage. 6. Discard the azeotrope, the cloudy part that seperates from the water, from the conical vial. 7. Allow reaction mixture to cool to room temperature.

Running the reaction 8. Dissolve 0.64ml of acetic anhydride in 1ml of toluene in a conical vial. Add this solution with a Pasteur pipet to the enamine prepared. 9. Cap the roundbottom flask, swirl at room temperature, and allow mixture to stand for 48 hours. 10. Add 1ml of water. Attach a water-cooled condenser without the Hickman head, and boil the mixture with stirring for 30 minutes in an aluminum block at 120 oC. Cool to room temperature. 11. 12. 13. Transfer with a Pasteur pipet into 15ml centrifuge tube with a screw cap. Add 1ml of water, cap the centrifuge tube, and allow layers to separate. The 2-acetylcyclohexanone is contained in the upper toluene layer. Remove the lower aqueous

layer.

Extraction 14. Add 2ml of 6M HCl to the toluene layer remaining in the tube and shake. Then, allow layers to

separate. Remove the lower aqueous layer. 15. 16. Add 1ml of water and shake. Remove the lower aqueous layer. Transfer the organic layer with dry Pasteur piper into a dry conical vial. Add four

microspatulafuls measured in the v-grooved end, of granular anhydrous sodium sulfate. 17. Transfer the dried organic phase from the drying agent and place into a dry 5ml conical vial. Evaporate the toluene in a water bath at 70 oC using a stream of dry air or nitrogen. Watch liquid

Rinse drying agent with minimum amount of fresh toluene and add this to the vial. 18.

carefully so it does not evaporate. 19. Save yellow liquid residue for purification by column chromatography.

Column Chromatography 20. Prepare a column for column chromatography using 5-3/4 inch Pasteur piper as a column. Use

alumina as the absorbent and methylene chloride as the eluent. 21. Place small piece of cotton in the Piper and gently push it into constriction.

22. 23.

Pour 1g of alumina into column. Obtain 5ml of methylene chloride in a graduated cylinder. Dissolve the crude product in 0.5ml of methylene chloride. Clamp the column above a 10ml

Erlenmeyer flask. 24. 25. 26. 27. 28. Add 1ml of methylene chloride to the column and let it percolate through the alumina. Allow the solvent to drain until the solvent surface just begins to enter the alumina. Add the crude product to top of column and let mixture pass onto the column. Use about 0.5ml of methylene chloride to rinse the vial that contained the crude product. When first batch of crude product has drained so that the surface of the liquid just begins to enter

the alumina, add the methylene chloride rinse to the column. 29. When solvent level has again reached the top of the alumina, add more methylene chloride with a

Pasteur piper to elute the product into the flask. 30. Continue adding methylene chloride to the column until the colored material has eluted off the

column. Collect liquid that passes through as one fraction.

Evaporation of Solvent 31. Preweigh 5ml conical vial and transfer about half of the liquid in the Erlenmeyer flask into the Place conical vial into a warm water bath (50 oC) and evaporate the methylene chloride with a

conical vial. 32.

light stream of nitrogen until the volume is about 0.5ml. 33. Transfer the remaining liquid in the Erlenmeyer flask to the conical vial and continue evaporating

the methylene chloride to give the 2-acetylcyclohexanone as a yellow liquid. 34. 35. When the solvent has been removed, determine weight of product. Calculate the percent yield.

Conclusion In this lab, we formed 2-acetylcyclohexanone. First, we prepared the enamine from the carbonyl compound cyclohexanone, and a secondary amine, pyrrolidine through an acid-catalyzed additionelimination reaction. Then, we used distillation to purify it from the pyrrolidine, toluene, and the water. We prepared the 2-acetylcyclohexanone by adding acetic anhydride and toluene to the enamine we prepared. We purified and extracted the mixture through distillation and column chromatography. Our percent yield was about 76%.