University of Research and Technological Investigation

“YACHAY TECH”
d
School of Chemical Sciences and Engineering
d

ORGANIC CHEMISTRY I
D

PRACTICE 7:

Studying Elimination Reactions:

Acid-catalyzed dehydration of a
secondary alcohol.

Authors:
Luzuriaga Espinoza Kenia Michelle
Palma Loor María Daniela
f

Professor:
Hortensia Rodriguez, Ph.D.
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Date:
08 - Jul - 2021
f

SEMESTER I - 2021
❖OBJECTIVES
● To prepare cyclohexene from cyclohexanol and determine the efficiency of this
conversion using chemical test and Spectroscopy.
● Learn to develop different experimental activities such as setting up a distillation
apparatus to perform a distillation, washing and drying of an organic liquid.
● Analyze and identify the organic phase in an immiscible aqueous mixture.
● Synthesise an alkene by dehydration of an alcohol.
● Identify the presence of unsaturation in an organic molecule using both chemical
reactions and spectroscopy.

❖INTRODUCTION
Alcohol can be dehydrated to form an alkene in the presence of a strong acid. The
mechanism is defined by the substrate and the strength of the base.
In this experiment, an alkene (cyclohexene) will be prepared by dehydration of an
alcohol (cyclohexanol), where phosphoric acid will be used as an acid catalyst.

The crude product is contaminated with water, unreacted alcohol, phosphoric acid
and some side products. Washing with saline solution removes most of the
impurities. Treatment with sodium carbonate solution removes traces of acid.
The mechanism of the dehydration of cyclohexanol probably involves the formation
of a carbocation.

A competitive Nucleophilic Substitution reaction with cyclohexanol to yield

dicyclohexyl ether would be possible.
 Dicyclohexyl ether then is a probable side product of the dehydration of
cyclohexanol. It is immiscible with water is likely to co-distill and may therefore be
present in the first distillate. To remove dicylcohexy ether completely a second
distillation of the product is usually carried out.

❖SAFETY DATA SHEET

❖MATERIALS
● 100 mL round bottom flask
● boiling chips
● funnel

❖REAGENTS
● Phosphoric acid ● sodium chloride
● Bromine ● calcium chloride
● Cyclohexanol ● calcium carbonate
● Cyclohexene ● Distilled water
● sodium carbonate solution
❖PROCEDURE
● Cyclohexene preparation

● Solvent Extraction

● Final purification-Simple distillation

 ● Chemical Tests to Distinguish Alkenes

● Bromine in Water

SPECTROSCOPIC CHARACTERIZATION
Into techniques of characterization, in this section practice we must analyze the
following sprectos.
- Infrared Spectroscopy
- NMR spectroscopy
- The 1H-NMR spectrum of cyclohexanol.
- The 1H-NMR spectrum of cyclohexene.
- The 13C-NMR spectrum of cyclohexanol.
- The 13C-NMR spectrum of cyclohexene

❖OBSERVATIONS
If the liquid is cloudy indicating the presence of moisture, add a few lumps of
calcium chloride to the test tube and allow the mixture to stand until clear.
Decant the liquid to a clean, dry pre-weighed vial that has been labelled in the
usual way.

If the liquid is clear, place the sample in a suitably labelled vial. Calculate the
determine the yield and percentage yield of cyclohexene. Carry out the
bromine/dichloromethane and permanganate tests (see Appendix I on Tests for
functional groups) on your product. Have the remainder of your sample
available for grading.

❖DISCUSSION AND RESULTS

In this experiment an alkene (cyclohexene) will be prepared by dehydration of an
alcohol (cyclohexanol) using an acid catalyst such as phosphoric acid. This is one of
the most common methods of preparing alkenes.
 The crude product is contaminated with water, unreacted alcohol, phosphoric acid
and some side products. Washing with water removes most of the impurities.
Treatment with sodium carbonate solution removes traces of acid and a final wash
with water removes any remaining carbonate.

The mechanism of the dehydration of cyclohexanol probably involves the formation

of a carbocation.

This carbocation can react in any of the ways shown below:

1. With water to yield cyclohexanol - the starting material. (Note that all the steps in
this reaction are reversible);

2. by losing a proton to yield cyclohexene;

3. with cyclohexanol to yield dicyclohexyl ether.

Dicyclohexyl ether then is a probable side product of the dehydration of

cyclohexanol. It is immiscible with water and is likely to co-distill and may therefore
be present in the first distillate. To remove dicyclohexyl ether completely a second
distillation of the product is usually carried out.

RESULTS
A secondary alcohol, such as cyclohexanol, undergoes dehydration by an E1
mechanism. The key intermediate in the mechanism is a cyclohexyl cation, which can
undergo substitution as well as elimination. To prepare an alkene in good yield, it is
necessary to suppress the substitution reaction. In this experiment, the substitution
reaction is suppressed by: (1) the use of strong acids with anions that are relatively
poor nucleophiles ; (2) a high reaction temperature, which favors elimination; and (3)
distillation of cyclohexene from the reaction mixture as it is formed. Any strong acid
can be used as a dehydrating agent. Phosphoric acid has all been employed
successfully. The anion of this acid(phosphate ion) is a poor nucleophile, and thus
substitution reaction is not favored. Other strong acids, such as HBr, have nucleophilic
anions, and thus yield more substitution than elimination products.
Fewer side reactions occur when concentrated phosphoric acid is used as the
dehydrating agent, but the rate of the alkene formation is slow.
Removal of the alkene by distillation as it is being formed in the reaction mixture is an
excellent technique for preventing side reactions. Unfortunately, this technique is
applicable only for dehydration reactions that produce low-boiling alkenes, such as
cyclohexene. Removal of the alkene reduces tar (polymer) formation by minimizing the
contact time between the acid and the alkene. Water is also removed from the acidic
reaction mixture in this distillation, which prevents the reverse reaction (reconversion
of the cyclohexene to cyclohexanol) from occurring.
In this section an important observation even with careful distillation, the
cyclohexene-water distillate will be contaminated with some cyclohexanol, which must
be removed in the subsequent work-up.The crude distillate is transferred to a
separatory funnel and the aqueous layer is drawn off. Since cyclohexanol is slightly
water-soluble, it is removed from the crude cyclohexene by a water extraction. Next,
the cyclohexene is extracted with saturated NaCl solution as a preliminary drying step.
Because cyclohexene forms an azeotrope with water, it must be scrupulously dried at
this point or the final product will be wet. After drying, the cyclohexene is purified by
distillation.

Chemical Tests. The presence of the alkene functional group can be indicated by
carrying out simple reactions in which a color change can be observed. One such
reaction is with bromine in dichloromethane. The bromine reagent is a reddish-orange
color. When it is dripped slowly into a sample of alkene, the bromine reacts with the
alkene to form a nearly colorless dibromide. Because the bromine is consumed, the
mixture loses the reddish-orange color. If a sample decolorizes bromine under these
conditions it can be inferred that an alkene functional group is likely present.

Calculating the Percent Yield.

Theoretical yield
The phosphoric acid is a catalyst and is not involved in the yield calculation.

One molecule of cyclohexanol should produce one molecule of cyclohexene. One mole
(mol) of cyclohexanol should produce one mole of cyclohexene.
2.05 g cyclohexanol / 100.2 g/mol = 0.0205 mol (or 20.5 mmol)
Therefore, 0.0205 mol of cyclohexanol should produce 0.0205 mol of cyclohexene.
Convert this number of moles of cyclohexene to grams of cyclohexene by multiplying
by the MW of cyclohexene (82.1 g/mol).
0.0205 mol x 82.1 g/mol = 1.68 g cyclohexene
Finally, 2.05 g of cyclohexanol should produce 1.68 g of cyclohexene. This is the
best-case yield also known as the theoretical yield.

Percent Yield
Let’s say that after the final fractional distillation of the cyclohexene, 1.22 g was
collected. The percent yield then would be
Percent yield = (actual / theoretical) x 100 = (1.22 g / 1.68 g) x 100 = 73 %
This assumes that the 1.22 g that was obtained was 100% pure.

❖CONCLUSION
● Through this practice, we learned how to prepare cyclohexene from
cyclohexanol, as well as the theoretical process of distillation, decantation,
washing, and drying of an organic liquid, identification of the organic phase in an
organic mixture, and mainly how to synthesize an alkene by dehydration of an
alcohol.
It was also analyzed that to carry out the synthesis of cyclohexene, it is essential
to start from an elimination reaction catalyzed by phosphoric acid to
cyclohexane. Another important fact that was analyzed is that adding phosphoric
acid to cyclohexanol helps to protonate the alcohol, so that this is a good leaving
group of the mechanism.

● The reaction is carried out in a fractional distillation apparatus. As the alcohol

and acid are heated, alkene and water are produced and co-distill into a
collection vial. As in any distillation, unless precautions are taken, some of the
product will be lost as hold-up in the apparatus. Hold-up would result in a
reduced yield of product. To overcome this problem and to ensure that a
maximum amount of product is distilled, a higher boiling "chaser" solvent is
added to the distillation flask and the distillation is continued until the
temperature rises well over the BP of cyclohexene. At this point it can be
assumed that all product has been distilled into the collection vial, along with
some chaser.

❖REFERENCES
● Organic Chemistry, 2nd Edition by J. Clayden, N. Greeves, S. Warren. Oxford
University Press. 2012
● Comprehensive Organic Chemistry Experiments for the Laboratory Classroom
(RSC Publishing), (n.d.).
https://pubs.rsc.org/en/content/ebook/978-1-84973-963-4 (accessed June 26,
2021).

❖ QUESTION FINAL

1.) Draw the structure of the major product that would be obtained from the
dehydration of cyclohexanol and the possible byproducts.
Alkene (cyclohexene) is the main product, which is the product prepared from the
dehydration of an alcohol (cyclohexanol) using an acid catalyst such as phosphoric acid.

The dehydration mechanism of cyclohexanol probably involves the formation of a

carbocation.

This carbocation can react in any of the ways shown below:

1. With water to yield cyclohexanol - the starting material. (Note that all the steps in
this reaction are reversible);

2. by losing a proton to yield cyclohexene:

3. with cyclohexanol to yield dicyclohexyl ether.

Dicyclohexyl ether then is a probable side product of the dehydration of cyclohexanol.

It is immiscible with water is likely to co-distill and may therefore be present in the first
distillate. To remove dicylcohexy ether completely a second distillation of the product is
usually carried out.

2.) If we consider that this reaction is carried out using water as solvent. Does this
solvent favor the proposed mechanism? Explain

Water does not favor water as a mechanism. It does not favor the mechanism because
it does not help the protonation of the hydroxyl group, and water is not a strong acid.

Water, being a polar protic solvent, effectively solvates cations and anions. This solvent
favors the elimination mechanisms, E1 and E2. However, in the dehydration reaction,
water appears not only as a solvent but also as an acidic medium, as a catalyst, and as a
byproduct in the dehydration mechanism.
❖ EVALUATION FINAL
1) Mixing cyclohexanol with phosphoric acid is an exothermic process,
whereas the overall reaction from cyclohexanol to cyclohexene is
endothermic. Referring to the mechanism above, construct an energy diagram
showing the course of the reaction. Label the diagram with the starting
alcohol, the protonated alcohol, the carbocation, and the product.

2) Draw the structure of the product from the reaction of cyclohexene plus
bromine. Show stereochemistry clearly.