ORGANIC CHEMISTRY I

PREPARATION OF CYCLOHEXENE FROM CYCLOHEXANOL: AN ELIMINATION

REACTION
Paula Ardila a ,b , Wendy Rosas a ,b , Lina Figueredoa , b , Kimberly Corala , b

a
Faculty of sciences and education Degree in Chemistry, Organic Chemistry I
b
District University Francisco Jos de Caldas

5th November, 2016 Bogot D.C.

Summary: The laboratory practice has the purpose of

Key words:
obtaining the cyclohexene, with the help the mechanism of
Elimination, cyclohexene, link sigma
elimination 1, the process is called the dehydration of
and pi, acid solution
alcohols, because are using strong acids, as the
phosphoric, and sulfuric. The elimination 1 has the
objective remove links (sigma), to form links (pi) in the
molecule. To ensures the purity of the product the boiling
point is measured, also the specter IR.

INTRODUCTION Elimination reactions are more complex than

Is an important reaction of alcohols. One
method that works particularly well for tertiary
alcohols is the acid-catalyzed reaction. For
example, treatment of 1-methylcyclohexanol
with warm aqueous sulfuric acid in a solvent
such as tetrahydrofuran results un loss of
water and formation of 1-methylcyclohexene.
substitution reactions from several reasons.
One is the problem of regiochemistry. What
products result by loss of HX from an
unsymmetrical halide? In fact, elimination
reactions almost always give mixtures of
alkene products, and the best we can usually
do is to predict which will be the major
product.
In the elimination of HX from an alkyl halide,
the more highly substituted alkene product
predominates.

Figure 1. Reaction of 1-methylcyclohexanol with

sulfuric acid.
Taken From: Organic Chemistry Mc Murry page
620
Acid-catalyzed dehydrations usually follow
Zaitsevs rule:
The nucleophile can either substitute for the
halide by reaction at carbon or can cause a
elimination of HX by reaction a neighboring
hydrogen:
Figure 2. reaction at a neighboring hydrogen
Taken from: Organic Chemistry Mc Murry page
398
Figure 3. Zaitsevs rule
Taken From: Organic Chemistry Mc Murry
page 398
The reaction is an E1 process, and occurs by
the three- step mechanism. Protonation of the
alcohol oxygen is water to generate a
carbocation intermediate and final loss of a
proton from the neighboring carbon atom to
complete the process. As usual for E1
reaction, tertiary carbocation intermediates.
Secondary alcohols can be made to react,
but the conditions are severe (75%
 ORGANIC CHEMISTRY I

H 2 S O 4 , 100 C ) and sensitive 50-mL flask with ground-glass

stopper
molecules dont survive. 10-mL graduated cylinder
To circumvent the need for strong acid and ice bath
allow the dehydration that are effective under 50-mL and 100-mL round-bottom
mild, basic conditions. One such reagent, flasks
phosphorus oxychloride ( POC l 3 ) in the 125-mL separator funnel
basic amine solvent pyridine is often able to
Reagents
effect the dehydration of secondary and
tertiary alcohols at 0C Anhydrous calcium chloride
Cyclohexanol
Sulfuric acid
Phosphoric acid
Saturated NaCl solution

Instruments
Figure 4. Reaction 1-methylcyclihexanol in Data sheet iraffinity1
presence of POC l 3 . special features
Interferometer: Michelson with an angle of
Taken from: Organic Chemistry Mc Murry page
incidence of 30 , Equipped with a Dynamic
642
Alignment System Patented (Patent JPN).
The mechanism of reaction as E1:
Optical system: Single beam. Self-drying
sealed optical system
Beam Divider: Germanium with KBr cover
Light Source: High Energy Ceramics
Detector: High-sensitivity temperature
controlled detector (DLATGS detector) S / N
Noise: Greater than 30,000: 1 (peak to
peak, resolution of 4, in a range of 2100 cm-
1)
Wavelength range: 7,800 to 350cm-1
Resolution: 0.5, 1, 2, 4, 8 or 16 cm-1
Mirror speed: 4 steps to select; 2.0, 2.8, 5, 9
mm / sec
Data sampling: He-Ne laser
Gain: Automatic or manual selection (x1 to
x128)
Sample compartment: Equipped with
automatic recognition of accessories 200mm
wide x 230mm long x 170mm high
Dimensions: 514mm wide x 606mm long x
273mm tall
Weight: 35 Kg
Figure 5. Mechanism of the acid-catalyzed Software: IR Solution
dehydration of a tertiary alcohol to yield Environmental conditions: 15-30 C, less
an alkene. The process is an E1 reaction than 70% relative humidity
and involves a carbocation intermediate. Power requirements: 100/120/220/230/240 /
Taken from: Organic Chemistry Mc Murry page V.A. 50/60 Hz.
643
(McMurry, 2012)
Methodology
MATERIALS AND METHODS
Take 10 g of cyclohexanol
Materials
(considering the density) in 100- mL round-
Distillation assembly
bottom flask, add 2.5 mL of 85% phosphoric
125-mL Erlenmeyer flask acid and 1mL of concentrated sulfuric acid
(both are strong acids). Mix the acidic
 ORGANIC CHEMISTRY I

solution by swirling, add 2-3 carborundum Taken from:

boiling chips, and equip the flask for simple http://www.sinorg.uji.es/Docencia/SO/tema7SO.pdf
distillation with receiver adapted on the The velocity is determinate for form the
condenser. Slowly distil the contents of the carbocation, and the formation of alkenes,
distillation flask into a 125- mL Erlenmeyer was determinate for stability to carbocation.
flask chilled in an ice bath (flammable). Adjust
the rate of the distillation flask (approximately
45 minutes), stop the distillation when about 8 Figure 7. velocity to dehydration
mL of residue remains in the distillation flask Taken from:
(approximately 4g of water and crude http://www.sinorg.uji.es/Docencia/SO/tema7SO.pdf
cyclohexene will be collected in the receiver). In the laboratory practice the following results
Transfer the distillate in the separator funnel were obtained
with 5mL of water followed by 5mL of Cyclohexano Cyclohexen
saturated NaCl solution. Drain the l e
cyclohexene from the separator funnel into a Dough 10g 4.045
50-mL round- bottom flask. Add 1g of (g)
anhydrous calcium chloride. Once the Density 0.962 0.809
cyclohexene has been obtained, determine (g/ml)
the boiling point as purity criterion and IR Volume 10.39 5
specter (mL)
Molecula 100.16 82.15
RESULTS AND DISCUSSION r
The reaction of laboratory is: Weight
(g/mol)
Moles 0.0998 0.049
(mol)

Percentage of income:
mol 1 mol Cyclohexene
Figure 6. Dehydration of cyclohexanol 10 g cyclohexanol
Taken from: 100.16 g 1 mol cyclohexanol 1mol
https://www.scribd.com/doc/14352986/7-
PREPARACION-DE-CICLOHEXENO
4.045 g
The balance has displaced to right is of income= 100=49.32
8.20 g
necessary remove the alkene and water as
the form. It was necessary the distillation The yield of the reaction is low, because lost
process of alkene because is more volatile in the distillation.
than alcohol and dehydrating agent. The Boiling point was obtained in the practice
The mechanism used is elimination 1. The is 79C, it is a low, because the theoretical
protonation of group hydroxyl makes it an boiling point is 83C. The difference can be
outgoing group, the elimination of water on attributed to conditions of pressure.
the protonated alcohol generates a IR SPECTRE
carbocation was lost a proton to form the The real specter obtain is:
alkene.

Figure 7 Mechanism E1 in acid medium to

dehydration of alcohols
 ORGANIC CHEMISTRY I

Figure 8. Specter IR of Cyclohexane (iraffinity1) Massachusetts Institute of Technology.

C6 H 10 "Inside tiny tubes, water turns solid when it
Molecular formula: IDH= 2
should be boiling: Astonishing behavior of
water confined in carbon nanotubes."
The molecule has an IDH of 2, indicating that
it has two unsaturation, therefore it is possible ScienceDaily. ScienceDaily, 28 November
to deduce at least one double bond, the other 2016.
unsaturation is of the cycle; Approximately at <www.sciencedaily.com/releases/2016/11/1
3085 c m1 is the tension ( C) , 61128152140.htm>.

approximately in 1646 c m1 appears a

range indicating the cycle and the alkene.
There are no bands characteristic of
C H 3 so there are only s p 2

carbons
CONCLUSIONS
The cyclohexanol is a secondary
alcohol, for this reason it reaction
velocity is medium.
The alcohol dehydrating occurs for
the E1 mechanism.
The distillation is imperative in the
process, because the alkene is
remove for it volatile.

REFERENCES
McMurry, J. (2012). Alcohols and phenols .
En J. McMurry, Organic Chemistry
(pgs. 638-645). Belmont:
CENGAGE.
ATTCHAMENTS

INSIDE TINY TUBES, WATER TURNS SOLID WHEN IT SHOULD BE BOILING

November 28, 2016
Massachusetts Institute of Technology

Summary
It's a well-known fact that water, at sea level, starts to boil at a temperature of 212 degrees
Fahrenheit, or 100 degrees Celsius. And scientists have long observed that when water is confined
in very small spaces, its boiling and freezing points can change a bit, usually dropping by around 10
C or so. But now, a team has found a completely unexpected set of changes: Inside the tiniest of
spaces -- in carbon nanotubes whose inner dimensions are not much bigger than a few water
molecules -- water can freeze solid even at high temperatures that would normally set it boiling.