LBYKM32, NO2A, Group 7

Experiment 2: Synthesis of Cyclohexene from Cyclohexanol

Ching, D., Dela Peña, P., Espartero, F.
Mr. Glenn Kelly Tan
January 24, 2024
February 20, 2024

Abstract
The experiment revolves around the dehydration of cyclohexanol to cyclohexene through a unimolecular
elimination (E1) reaction using an acid-catalyst. Cyclohexanol is used as the starting material so that the
alcohol that will be used will not yield any unwanted product, is reactive enough, and will involve the
product in the liquid phase. As for the acid-catalyst, phosphoric acid was preferred over sulfuric acid
because of its weaker oxidizing properties as well as its weaker acidity. The main objective of the
experiment is the synthesis itself while other objectives include getting a satisfactory percent yield, and
characterizing the product produced by the reaction done. After the reaction is allowed to happen in the
boiling flask, the mixture is then distilled using a fractional distillation setup to separate the desired
product from the starting material, the remaining acid catalyst, and water. Then, liquid-liquid extraction is
then used to further separate the organic layer containing the cyclohexene from the aqueous layer. Then,
to further remove water, the extract was dried using calcium chloride. The dried product was then left for
the next class. The first step in the next session involves using a dropper to transfer the dried product to
the vial for the characterization using gas chromatography-mass spectroscopy but the dropper used was
contaminated so further extraction using saturated sodium chloride was used, Then the product was then
inserted into the vial for characterization. The product contained hexane and other impurities with a
retention factor of 1.50, the desired product cyclohexene with the highest peak and a retention factor of
1.63, and some starting material cyclohexanol with a retention factor of 2.38.

I. Introduction of the acid-catalyst for it to have 3 bonds and a

The preparation of alkenes is done
through elimination reactions, may it be
bimolecular (E2) or unimolecular (E1). The
common starting materials used are alkyl
halides and alcohols. The type of reaction that
these starting materials undergo depends on
the number of R groups (i.e. carbon atoms or
hydrocarbon chains) attached to the alpha
carbon, which is the carbon in which the halo
group for alkyl halides, or the hydroxy (-OH)
group for alcohols, is attached. In alkyl halides,
elimination is done using a base but, the
problem is a non-bulky base can also function
as a nucleophile to do substitution so there
would be two competing reactions. (1) That’s
why the synthesis of alkenes will be more
favorable when alcohols are used because the
reagents used for substitution are different from
those used in elimination.
The experiment involves the
dehydration of alcohols using an acid-catalyst to
do an elimination reaction. Both E2 and E1
reactions require an acid-base reaction first,
which includes a lone pair of the oxygen from
the hydroxy group attacking an acidic hydrogen
lone pair and therefore having a positive
charge. This converts the bad leaving group
-OH to a good leaving group -+OH2 as it will
prefer to leave as a water molecule. E2
reactions are a concerted process, which
means that all of the steps will be happening at
the same time after the acid-base reaction. The
-+OH2 group leaves as a water molecule while
the conjugate base coming from the acid-base
reaction attacks a beta hydrogen, whose broken
bond will be used to form a pi bond between the
beta carbon and alpha carbon which then
results in the desired alkene product. E1
reactions are similar to E2 reactions but the
generation of the water molecule will come first
forming a carbocation intermediate. This does
not happen for E2 reactions because they
cannot form a stable carbocation. The attack of
the conjugate base then follows through to form
the desired alkene product.
The importance of learning the process
of synthesizing alkenes lies in the reactivity of
the pi-bond which means they can act as
intermediates in the synthesis of other complex
compounds used in industrial applications. (3)
LBYKM32, NO2A, Group 7
For instance, ethylene, the simplest alkene (1),
is the organic compound produced at the
greatest quantity worldwide, which reaches up
to more than 130 billion kilograms per year. A
bulk of the produced ethylene is polymerized to
polyethylene which is the most commonly found
plastic. (3)
II. Experimental
Figure 1 : Distillation Set-Up
In a 50-mL boiling flask, 5.2 mL of
cyclohexanol and 1 mL of 85% phosphoric acid
(H2PO4) were mixed and swirled together.
Combining these formed a clear solution. A
boiling chip was added into the distilling flask
before it was attached into a fractional
distillation set-up.
Heat was applied into the solution,
allowing it to gently boil for about 5 minutes first
before distilling. Clear distillate was collected
between 95.0-105.0 deg C until the residue in
the flask is reduced to 1-1.5 mL. The receiver
was submerged in an ice bath to prevent loss of
product by evaporation.
The distillate was then extracted in a
separatory funnel by mixing it together with 5
mL of distilled water. Two-way separation was
performed, extracting the product with two 2.5
mL-portions of water. The solution then
separated into two clear layers. In every
extraction, the lower aqueous layer was drawn
off. After this process, the upper organic layer
was decanted into a dry Erlenmeyer flask and
was dried using small amounts of anhydrous
calcium chloride (CaCl2) pellets. The drying
agent clumped together while swirling the flask.
After adding more pellets, the clumping stopped
and the colorless final product was decanted
into a clean, dry test tube and stored with an
aluminum foil and stopper.
The sample obtained in this experiment
was soon contaminated with impurities,
indicated by its murky appearance. To fix this,
the product was mixed with saturated sodium
chloride (NaCl) solution and was extracted
again. After removing the aqueous layer, the
organic layer was extracted with hexane to
draw off organic impurities. Anhydrous CaCl2
was added to dry off any water content left in
the extracted sample.
The assumed cyclohexene and hexane
sample was transferred into a small vial by
passing it through a microfilter to remove any
solvents. This vial was run into a gas
chromatography-mass spectrometry (GC-MS)
machine to determine the identity of the
product. (2)
III. Results and Discussion
The utmost rationale of the experiment is
to perform an elimination reaction mechanism
to dehydrate cyclohexanol to form cyclohexene
with the maximum purity and yield. Ensuring
that the reaction proceeds both effectively and
efficiently almost diminishing the appearance of
impurities. It also optimizes the reaction
condition such as temperature, time, and
concentration of the acid catalyst, minimizing
decomposition. Understanding the underlying
role of acid catalysts, formation of carbocation
intermediates, and the implications of the
principles of acid-catalyzed dehydration
reactions. Ultimately, to characterize and
acquire products using analytical techniques
available such an Infrared (IR) Spectroscopy
and Gas Chromatography--Mass spectroscopy
(GC-MS) in determining the identity and purity
of the product.
The preparation of cyclohexene from
cyclohexanol is via elimination reaction,
specifically dehydration reaction, where a
molecule of water is removed from the alcohol
to form the corresponding alkene. It involves
protonation of the alcohol in the presence of a
strong acid catalyst, the 85% phosphoric acid.
Cyclohexanol reacts with the hydronium ion
from the acid, paving the way for protonation of
LBYKM32, NO2A, Group 7
the hydroxy group (-OH) of the starting
chemical. It forms an alcohol intermediate as
the hydroxyl group was transformed into a
better leaving group. Therefore, it undergoes an
elimination reaction where a water molecule is
extracted. The formation of a carbocation
intermediate resulted from a hydrogen atom on
the carbon atom bonded to the hydroxyl group.
This intermediate therefore undergoes
deprotonation to generate the desired
cyclohexene product— Resulting in the
formation of a double bond between the carbon
atoms previously bonded to the hydroxyl group.
During the dehydration, a 50-mL
round-bottom flask with 5.0g cyclohexanol,
1-mL of 85% phosphoric acid, and a boiling chip
was equipped with a fractionating column for a
reflux to prevent the loss of volatile components
and ensures continuous reaction until the
volume has been reduce to 1 to 1.5-mL. Thus, a
heedful temperature control is critical to prevent
overheating and decomposition of the product.
Fractional distillation is utilized to obtain
relative pure cyclohexene ensuring separation
from other substances. Whereas, cyclohexene
was collected. While, water and unreacted
cyclohexanol are left behind in the flask. Careful
employment of techniques is required for
minimizing contamination.
Further distillation of the reaction mixture
to isolate cyclohexane from the solvent with a
boiling point: 83°C. It was collected in a
separate flask while leaving behind the solvent
and other impurities.
Purification through separation to meet
purity necessities and removal of excess
aqueous mixture. Additionally, dehydration
through the use of anhydrous calcium chloride
to remove excess water will pave the way for a
more purified product.
The starting material, cyclohexanol was
carried out using a strong acid catalyst, 85%
phosphoric acid and subjected to heat under
reflux which promoted the removal or water in
the dehydration process. The mixture
containing cyclohexene, water, and probable
unreacted cyclohexanol and acid catalyst
underwent distillation to separate cyclohexene
from water and other impurities. Specifically,
fractional distillation was employed for
purification purposes. This technique separates
different components of a mixture based on
their boiling points, allowing for the isolation of
pure cyclohexene. Cyclohexene has a lower
boiling point than water, thus it was distilled off
first, leaving behind the water and other heavier
components.
The mixture was separated through the
use of separator funnel and technique. Further
purification was then performed through the
drying agent, anhydrous calcium chloride
(CaCl2) to remove any remaining water traces.
Upon transferring the yield of the
experiment in a vial to be used on a gas
chromatography–mass spectrometer, the
dropper used was contaminated with an
unknown organic material. Thus, making the
mixture become cloudy. The initial resolution
was to dilute the contaminated mixture with
water— Observing a homogenous cloudy
solution.
Saturated sodium chloride (NaCl2) was
added to allow two layers to separate. Unveiling
to three layers: lower aqueous layer, middle
presumed organic contaminant, upper organic
layer. The mixture was then concentrated with
hexene for the unknown organic material to
cohere with. The extracted cyclohexene with
hexane is then dehydrated with anhydrous
CaCl2 and decanted. A micro filter was used in
drawing out the murky mixture in a vial, making
it translucent.
Gas chromatography-mass spectrometry
(GC-MS) was utilized to determine the identity
of the by-product. With this combination of
analytical techniques, the sample mixture was
separated into its components and these were
detected to determine their presence. The
mass-to-charge ratio was also measured with
this instrument to confirm its molecular weight
and to clarify the chemical structure of the
sample. (3)
LBYKM32, NO2A, Group 7
Figure 2 : Gas Chromatography analysis of the
product
Figure above shows the gas
chromatography results of the assumed
cyclohexene and hexane sample. At retention
time = 1.50, a peak was generated from the
presence of hexane and other impurities. The
highest peak at retention time = 1.63, confirmed
the appearance of cyclohexene, the desired
product in this experiment. Lastly, a peak
generated at retention time = 2.38 was an
indication that the starting reagent,
cyclohexanol, is still in the sample. With this,
this can confirm that the mixture comprises
cyclohexene, cyclohexanol, hexane, and other
organic impurities.
Figure 3 : Mass Spectrometry analysis of the
product
Next figure is the mass spectrometry
results of the sample. The mass-to-charge (m/z)
= 72 was the molecular ion [C6H10]+, the
heaviest ion that passed through the machine.
Its difference to the base peak (m/z = 67) was
15 m/z, which confirmed the loss of CH3 group.
To the next molecular ion peak (m/z = 54), there
is a difference of 13 m/z, indicating
disappearance of CH group in the sample. To
the last peak (m/z) = 39, the difference of the
ratio was 15, confirming the loss of CH3 group.
With this fragmentation pattern, the mass
spectrometry results confirmed the structure of
cyclohexene, the desired product.
IV. Conclusion and Recommendations
In conclusion, the synthesis of
cyclohexane from cyclohexanol involves several
crucial yet straightforward steps, including
dehydration, distillation, and purification, which
necessitate careful precision and attention. By
employing laboratory techniques, a successful
conversion of cyclohexanol into cyclohexene
was observed.
Throughout the experiment, special
considerations were implemented to optimize
reaction outcomes and minimize side reactions.
Temperature control, fractional distillation to
separate cyclohexene from other components,
and selection of appropriate catalyst.
The final product, cyclohexane, was
obtained through distillation. Although it
demonstrated inadequate purity as it is a mixture
of cyclohexane and hexane. Further purification
techniques could be employed if higher purity is
required for specific applications.
Overall, the experiment amplified the
importance of meticulous experimental design,
proper technique execution, and attention to
safety protocols in organic synthesis. It could still
be inferred as a successful synthesis of
cyclohexane as it underscores the effectiveness
of the methods and serves as a foundation for
further exploration in organic chemistry
processes.
Moreover, based on the experiment
conducted for the synthesis of cyclohexane from
cyclohexanol, several recommendations can be
made to improve its efficiency and effectivity:
1. Increase parameters such as reaction
time and concentration of reactants to
maximize the yield of cyclohexane.
2. Conduct on varying conditions.
3. Using higher measures of excess
reagents to ensure a reaction that aims
towards completion.
4. Enhance separation and purification
techniques as these are the processes
where loss of products is prominent.
5. Explore different catalysts available for
LBYKM32, NO2A, Group 7

higher activity. “I hereby certify that I have given a

substantial contribution to this report and I
Through implementing these did not copy and/or quote from any resource
recommendations, it is possible to achieve material unless being cited as reference. I
higher yields of cyclohexane from cyclohexanol, am make known that failure to accomplish
thereby increasing the overall efficiency of the the second clause would be grounds for
reaction. plagiarism and a failing grade for my final
laboratory report.”
References

(1) Ault A. Techniques and Experiments for

Organic Chemistry, 6th ed. University Science
Books, 1998.

(2) Smith, J. Organic Chemistry; Third Edition; CHING, DAVID O.

McGraw-Hill: New York, 2011.

(3) Turner, D. 2022. Available at:

https://www.technologynetworks.com/analysis/a
rticles/gc-ms-principle-instrument-and-analyses-
and-gc-msms-362513. Accessed February 21, DELA PEÑA, PARIS RACHEL V.
2024.

(4) Wade, L; Simek,; J. W. Organic Chemistry;

Tenth Global Edition; Pearson Education: ESPARTERO, FRANCES CHERLEE
United Kingdom, 2023.