Sim.Yura.OCL.

DEHYDRATION OF CYCLOHEXANOL
INTRODUCTION
Acid catalyzed dehydration refers to the removal of a hydroxyl group and a proton as water from an alcohol, forming an alkene. Acid catalyzed dehydration is considered a unimolecular elimination reaction, where the rate is determined by the rate of the elimination of the leaving group from the substrate. Figures 1-{A-B} describe a general unimolecular elimination reaction.1

FIGURE 0-A: GENERAL UNIMOLECULAR ELIMINATION: FORMATION OF THE CARBOCATION

After the carbocation is formed there is a basic attack by the solvent on a -hydrogen to form an alkene and a protonated solvent.

FIGURE 0-B: GENERAL UNIMOLECULAR ELIMINATION: ALKENE FORMATION

For an alcohol, the leaving group is the hydroxyl group. By itself, a hydroxyl group is a poor leaving group, but, its conjugate acid, the oxonium ion, is a better leaving group. The rate-determining step for a dehydration reaction is dependent on the rate at which this oxonium ion leaves the substrate, thereby forming a carbocation. Figures 1-{C-E} describe a general hydration of an alcohol.

FIGURE 0-C: GENERAL DEHYDRATION REACTION: PROTONATION

(Hoffman, 2004)

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FIGURE 0-D: GENERAL DEHYDRATION REACTION: CARBOCATION FORMATION

An adjacent water molecule could then attack the - hydrogen relative to the carbocation, which promotes the formation of the double bond and completes the dehydration reaction.

FIGURE 0-E: GENERAL DEHYDRATION REACTION: ALKENE FORMATION

Because the acid regenerates itself, a small amount of acid could be used for the reaction. Figures 1-{F-H} show the experimental hydration mechanism.2

FIGURE 0-F: EXPERIMENTAL DEHYDRATION MECHANISM: PROTONATION

FIGURE 0-G: EXPERIMENTAL DEHYDRATION MECHANISM: CARBOCATION FORMATION

FIGURE 0-H: EXPERIMENTAL DEHYDRATION MECHANISM: ALKENE FORMATION

(Atkinson & Wolcott, 2011)

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EXPERIMENTAL
Cyclohexanol (20 grams) and H2PO4 (6 mL of 85%) was distilled (45 min), decanted and washed with NaHCO3 (15 mL of 5%). It was dried with CaCl2 (10 min) and distilled again (45 min). A bromine absorption test and Baeyers test was performed on the product.3

DATA & ANALYSIS

The percent yield was calculated to be roughly 66% (10.79 grams). A discussion of the yield is offered in the appendix. The product tested positive on a bromine absorption test and a Baeyers test when used with cyclohexane and cyclohexene as negative and positive controls, respectively, indicating the presence of a double bond. The IR spectrum showed no presence of ether or alcohol contamination There may have been alcohol or ethers in the first distillation flask, but it was not analyzed.

CONCLUSION
Overall, the experiment resulted in high yields (66% w/ 10.79 grams). Baeyers test and a bromine absorption test on the product indicated the presence of unsaturated bonds. An IR spectrum of the product indicated no foreign contaminants.

APPENDIX
LE CHATELIERS PRINCIPLE
By removing the cyclohexene as it forms, the reaction will push towards the production of cyclohexene to counteract the change in concentration. Although the experiment does not measure the molarity of products in experiment, a theoretical approach is offered with pseudo reactions. Consider the reactions below in the same reaction vessel.
EQUATION 0-1 EQUATION 0-2 EQUATION 0-3

Each will have their own reaction quotient. That is, [ [ [ [ [ [

3

] ] ] ] ] ]

EQUATION 0-4 EQUATION 0-5 EQUATION 0-6

(Atkinson & Wolcott, 2011)

Sim.Yura.OCL.4 Suppose that Thus, is preferred over the other products. [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] and can be written in terms of B and
EQUATION 0-7

EQUATION 0-8

Now suppose B is eliminated as it forms, taking the limit of equations 5-{7-8} as [ ] {

yields,

EQUATION 0-9 [ ] [ ] } } { } { [ ] [ ] [ ] The significance is that the formation constants for the additional reactions tend to be small. Unfortunately, it is difficult to remove as soon as it is formed, so in reality, { } { }. It is more accurate to say that { } { }. Side reactions of this experiment are discussed in section 5.2.

In simpler terms, Any change in status quo prompts an opposing reaction in the responding system.4 Thus, by decreasing the concentration of cyclohexene in solution, there is an increase in the amount produced. This method helps to decrease the amount of side reactions that are shown in section 5.2.

SIDE REACTIONS ALCOHOL

FIGURE 0-A: ALCOHOL: OXONIUM FORMATION

From Figure 5-A, the oxonium ion can either pull in the electrons from the C-O bond and regenerate the carbocation, or it can be deprotonated by a nearby water molecule, creating the starting reagent.

FIGURE 0-B: ALCOHOL: DEPROTONATION OF OXONIUM

(Solomons & Fryhle, 2011)

Sim.Yura.OCL.5 This reaction is harmless, as it recreates the reagent or transition states of our preferred reaction.

ETHER
An ether can be formed from a cyclohexanol reacting with a carbocation. This may be a destructive reaction, as once formed it may be difficult to break the ether bond. This ether will probably be in the initial distillation heating vessel, due to its high boiling point of .5

FIGURE 0-C: ETHER: OXONIUM FORMATION

FIGURE 0-D: ETHER: DEPROTONATION OF OXONIUM

BICYCLOHEXYL

FIGURE 0-E: FORMATION OF A BICYCLOHEXYL CARBOCATION

The formation of this carbocation could lead to a slew of products due to its reactivity. However, due to the distillation removing the desired product, there are limits to the formation of the cyclohexylcyclohexane carbocation simply due to the low concentration of cyclohexene in solution by distillation. This bicyclohexyl and its derivatives will probably be in the initial distillation heating vessel, due to its high boiling point of .6

YIELD

5 6

(Merck Index, 2007) (Merck Index, 2007)

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EQUATION 0-10: TOTAL POSSIBLE YIELD EQUATION 0-11: ACTUAL YIELD EQUATION 0-12: PERCENT YIELD

TABLE 0-1: ACRONYMNS FOR YIELD

Cyclohexanol Cyclohexene

CITATIONS
Merck Index (14th ed.). (2007). Whitehouse Station, New Jersey, United States of America: Merck Publishing. Atkinson, E., & Wolcott, R. (2011, October 26). CYCLOHEXENE FROM CYCLOHEXANOL. Retrieved from Linfield College: http://www.linfield.edu/assets/files/chem/Courses/CHEM%20321/cyclohexene_%28E1 %29%202011.pdf Hoffman, R. V. (2004). Organic Chemistry, an intermediate text (2 ed.). Hoboken, New Jersey, United States of America: John Wiley & Sons. Solomons, T. G., & Fryhle, C. B. (2011). Organic Chemistry (10th ed.). Danvers, Massachusetts, United States of America: Wiley.