Experiment 21

Dehydration of Methylcyclohexanols and the Evelyn Effect

2 3 0 The methylcyclohexanols and alkenes are flammable; inhalation, ingestion, or skin absorption may be harmful. Avoid contact, do not breathe their vapors, and keep them away from flames and hot surfaces. Phosphoric Acid can cause serious burns, particularly to the eyes; avoid eye or skin contact.

Purpose: The purpose of this lab is to carry out the dehydration of 2-methylcyclohexanol and 4methylcyclohexanol by heating the alcohols in the presence of phosphoric acid. Using this, we hope to observe the Evelyn effect in one or both of the alcohols. Equations and Properties:
Name Molecular Weight Boiling point (C) Density (g/mL)

2-methylcyclohexanol 4-methylcyclohexanol 1-methylcyclohexene 3-methylcyclohexene 4-methylcyclohexene Phosphoric acid (85%)

114.2 114.2 96.2 96.2 96.2 98.0

166 173 110 104 102

0.930 0.914 0.813 0.801 0.799 1.70

Equation for dehydration of 2-methylcyclohexanol

Equation for dehydration of 4-methylcyclohexanol

Calculations: Volume of 2-methylcyclohexanol 150 mmol * (1mol/1000mmol)(114.2g/1mol)(1mL/0.930g) = 18.42 mL Volume of 4-methylcyclohexanol 150 mmol * (1mol/1000mmol)(114.2g/1mol)(1mL/0.914g) = 18.74 mL Theoretical Volume of 1-methylcyclohexene 18.74 mL * (0.914g/1mL)(1mol/114.2g)(96.2g/1mol)(1mL/0.813g) = 17.75 mL Theoretical Volume of 3-methylcyclohexene 18.74 mL * (0.914g/1mL)(1mol/114.2g)(96.2g/1mol)(1mL/0.801g) = 18.01 mL Theoretical Volume of 4-methylcyclohexene 18.74 mL * (0.914g/1mL)(1mol/114.2g)(96.2g/1mol)(1mL/0.799g) = 18.06 mL Materials and Supplies:

Reagents: 2-methylcyclohexanol, 4-methylcyclohexanol, Phosphoric acid (85%), saturated sodium bicarbonate. Materials: stir bar/boiling chips, round-bottom vial, simple distillation glassware, 10 mL graduated cylinder, two numbered 15 mL crew-cap centrifuge tubes, Pasteur pipette, anhydrous calcium chloride or another suitable drying agent, centrifuge.

Experimental Procedure: 1. Work in pairs. Accurately weight 150 mmol of 2-methylcyclohexanol or 4methylcyclohexanol into a 50-mL round-bottom flask. 2. Mix in 5.0 mL of 85% phosphoric acid and drop in a stir bar or a few acid-resistant boiling chips. Clamp the flask to a ring stand over a suitable heat source and assemble an apparatus for a simple distillation. 3. Use a 10.0 mL graduated cylinder or another graduated container as the receiver. Have ready two clean, numbered 15-mL screw-cap centrifuge tubes. 4. Start the stirrer, if you are using one, and then heat the reactants so that the product mixture distills at a rate of 1 drop per second or less. 5. Record the vapor temperature after distillation begins, and observe it at intervals during the reaction. 6. Monitor the volume of the alkene (top) layer in the distillate. When the alkene volume is at about 8 mL, quickly pour the distillate into the first centrifuge tube, cap the tube, replace the graduated cylinder and continue distilling. 7. After the alkene volume reaches about 6 mL, monitor the still-head temperature continually. Lower the heat source and turn it off when you observe a marked temperature drop at the still head, which may be accompanied by foaming and dense white fumes in the reaction flask. 8. Pour the distillate into the second centrifuge tube and cap the tube. 9. For each separate fraction, wash the distillate by shaking it cautiously with two 5 mL portions of saturated sodium bicarbonate, and remove the aqueous (lower) layer with a Pasteur pipet. 10. Dry each alkene mixture separately in the centrifuge tube with anhydrous calcium chloride or another suitable drying agent. 11. Centrifuge it, if necessary, and decant the liquid into a labeled, tarred screw-cap vial. Measure the mass of each alkene fraction and calculate the total mass of alkenes. 12. Analyze both fractions by gas chromatography as directed by your instructor. Measure the area and retention time of each peak on your gas chromatograms. 13. Identify the peaks by comparison with a chromatogram provided by your instructor or by spiking your product mixture with an authentic sample of 1-methylcyclohexene and obtaining a chromatogram of the resulting mixture. 14. Assuming that the detector response factors for the alkenes are equal, calculate the percentage composition of each fraction and obtain the same data from a coworker who started with the other alcohol. 15. Decide whether either or both alcohols exhibit an Evelyn Effect. Data and Results:

Temperature at start of distillation: 94C Total volume of collected products: 14.9 mL Description of Product: Clear with a slight odor. Percent Yield: (14.9 mL actual / 18.01 mL theoretical) * 100 = 82.73% Percent Recovery: (14.9 mL component recovered / 18.5 mL mixture) * 100 = 80.54% Additional data attached on last page. Discussion and Conclusion: Discussion: A few changes were made to this lab, the first being that the dehydration for only 2-methylcyclohexanol was conducted, as well as the amount of phosphoric acid to be used becoming 5 mL. Lastly, instead of collecting two fraction of liquid during the distillation, only one was collected and analyzed using gas chromatography. Step-wise, the lab was a very simple distillation once the reagents were combined in the initial flask. After the distillation, the solution was washed and dried, preserving the organic layer which was kept for analysis. The gas chromatography results allowed us to see how many products the reaction yielded and in what quantities so that we would be able compare this to our initial assumption on which reactions would occur. Each solution in this lab had its own purpose even if it did not partake in the reaction we were examining, for example, that of the phosphoric acid being a catalyst to increase the rate of the reaction by lowering the activation energy needed for the reaction to commence. Anhydrous calcium chloride pellets were added to dry the solution as it binds strongly to any stray water molecules in the solution, allowing the remaining product to be cleanly poured into another container. Sodium bicarbonate was used to wash the solution as it is amphoteric, allowing it to react with any unwanted acids or bases in the solution while leaving the desired solution alone. In regards to the mechanism, the first step was the protonation of the alcohol group by the acid. The second step was the loss of water to form the carbocation, which should be noted to be highly exothermic. Finally, the removal of a beta hydrogen by base, in this case water, was used to form the alkene. This can all be seen in Postlab Q1. Conclusion: The percent recovery was fair though to the highest, most likely due to lost product during transference of solution from one container to another. When analyzed with gas chromatography, luckily, it would seem that there was no notable contamination. The results from the gas chromatography showed that there were still trace amounts of the 2-methylcyclohexanol present. This aside, we encountered two products for this reaction, 1-methylcyclohexene, and 3methylcyclohexene. 66.08% 1-methylcyclohexene, and 17.61% 3-methylcyclohexene was observed in the gas chromatography report attached at the end of this lab report. I would say that we succeeded in reaching the objective of this experiment, obtaining amounts close to what were expected in theory.

Post Lab Questions:

1.
a. Which kind of mechanism can better account for the product mixture obtained from the dehydration of cis- and trans 4-methylcyclohexanol: E1, E2, or a combination of the two? (Keep in mind the actual mechanism may be none of these.) E1 would best account for the obtained products as the protonated hydroxyl would leave, giving the carbocation intermediate. Based on your answer, write detailed mechanisms explaining the formation of all of the observed products.

b.

3.

4.

Describe and explain the possible effect on your results of the following experimental errors or variations. a. You forgot to add the phosphoric acid The dehydration reaction would not take place. b. You collected all the distillate in one container rather than two Products collected at the two boiling point regions would be collected, leading in a sample that contained high amounts of two or more products. c. The 2-methylcyclohexanol you used was the pure trans rather than a mixture of isomers. We would be seeing more 3-methylcyclohexene in the solution, than if we were using the cis variation. In Understanding the Experiment, 1-methylcyclohexene and 3-methylcyclohexene were mentioned as possible products of the dehydration of 2-methylcyclohexanol. Why wasnt 2-methylcyclohexene mentioned as a possible product? Because 1-methylcyclohexene and 2-methylcyclohexe have the same structure. a. Predict the major alkene product that would result from dehydrating each of the following alcohols, with no carbocation rearrangements.

7.

b.

In each case, predict the most stable dehydration product that could result after a single carbocation rearrangement.