FACULTY OF APPLIED SCIENCE

CHM457 – FUNDAMENTAL OF ORGANIC CHEMISTRY

LABORATORY REPORT

NO. OF EXPERIMENT: 2

TITLE OF Preparation of 4-methylcyclohexene

EXPERIMENT:
STUDENT’S NAME: UMIE SOFEA NADIA BINTI ABU BAKAR

MATRIC NO: 2022621854

CLASS GROUP: AS2532A2

DATE OF 6/4/2023
EXPERIMENT:
DATE OF 13/4/2023
SUBMISSION:
LECTURER’S NAME: PROF. MADYA DR. MOHD TAJUDIN
MOHD ALI
Experiment 2: Preparation of 4-methycyclohexene
Objectives:
i. To learn the distillation technique and understand the mechanism
involved in the reaction.
ii. To synthesize 4-methylcyclohexene from 4-methylcyclohexanol
by acid-catalyzed dehydration.
Introduction
The dehydration of alcohols using strong mineral acids, such as
sulphuric acid or phosphoric acid, as a catalyst is a general laboratory
method for preparing alkenes. The reaction is conducted in a
distillation apparatus. As the reaction mixture is heated, the lower
boiling products (cyclohexene, boiling point = 83℃, and water,
boiling point = 100℃) distill out and are collected in the receiving
flask. Any unreacted cyclohexanol (the starting material) and
phosphoric acid (the catalyst) are left in the distilling flask because of
their high boiling points (161℃ and 213℃, respectively). However,
since a small amount of phosphoric acid still appears in the receiving
flask, the product is washed with aqueous sodium carbonate to
neutralize the acid. Cyclohexene is insoluble in water and thus is not
lost during the washing with aqueous sodium carbonate solution. The
last traces of water are removed from the crude cyclohexene by
drying the liquid over anhydrous sodium sulfate ( a salt which forms a
hydrate). Final purification is achieved by simple distillation.
Procedures
1) An apparatus for simple distillation was set up. A 50mL round-
bottom flask was used as the distilling flask and a 25mL round-
bottom flask as a receiver. An ice bath was placed around the
receiver to lessen the loss of product by evaporation.
2) An empty 50mL round-bottom flask was weighed. 7.5mL of 4-
methylcyclohexanol was placed in the round-bottom flask using
 graduated pipettes. The flask was reweighed again to get the mass
of the alcohol.
3) 2.0mL of 85% phosphoric acid and 30 drops of concentrated
sulfuric acid was added along with 1 or 2 boiling chips in the
distillation flask and was mixed thoroughly.
4) The mixture was heated with a heating mantle and was distilled
slowly while maintaining the distillation temperature below 100℃.
The heating was continued until only 0.5-0.6mL of residue
remains in the distillation flask or the mixture begins to smoke or
bump.
5) The distillate was mixed with 3mL of saturated NaCl solution and
transfer the mixture to a test tube. The test tube was corked tightly
and the layers was mixed by swirling and shaking gently. The tube
was vented carefully and repeated. The layers was allowed to
separate. The bottom aqueous layer was drawn off with a Pasteur
pipette and was discarded.
6) The crude 4-methylcyclohexene was transferred using a regular
Pasteur pipette to an Erlenmeyer flask. A small amount of
anhydrous sodium sulfate was added and a stopper was placed on
the flask. The liquid was dried for at least 15 minutes with
occasional gentle swirling.
7) The simple distillation apparatus was cleaned,dried with acetone
during the drying interval.
8) A 25mL round-bottom flask that has been weighed while capped
was used as a receiver. The dried cyclohexene was transferred
with a Pasteur pipette into the distillation apparatus. 1 or 2 boiling
chips was added and was distilled, collecting the portion with
boiling range of 100-105℃ in the flask, chilled in an ice bath. The
flask was reweighed. The percentage yield of 4-
methylcyclohexene was calculated.
9) For unsaturation tests using Bromine in CCl4 and potassium
permanganate, 3 drops of 4-methylcyclohexanol was placed in 2
 separate test tubes. 6 drops of Bromine in CCl4 was added in one
of the test tube and 4 drops of potassium permanganate was added
in other test tube. For any colour change was observed.
10) Next, 3 drops of 4-methylcyclohexene that is obtained in the
experiment was placed in 2 separate test tubes. 6 drops of Bromine
in CCl4 was added in one of the test tube and 4 drops of potassium
permanganate was added in other test tube. For any colour change
was observed.

Result and Data

Mass of 50mL round-bottom flask, g =48.5024

Mass of 50mL round-bottom flask + 4-methylcyclohexanol, g =64.2067

Mass of 4-methylcyclohexanol, g =15.7043

Mass of 25mL round-bottom flask, g = 38.8634

Mass of 25mL round-bottom flask + 4-methylcyclohexene, g =50.2467

Mass of 4-methylcyclohexene, g =11.3833

Boiling point of 4-methylcyclohexene, ℃ = 102

Theoretical yield of 4-methylcyclohexene:

15.7043g
Mole 4-methylcyclohexanol = 114.2 �/��� = 0.1375 mol

Since, 1 mole 4-methylcyclohexanol = 1 mole of 4-methylcyclohexene

Thus, 0.1375 mol of 4-methylcyclohexanol = 0.1375 mol 0f 4-methylcyclohexene
Mass of 4-methylcyclohexene, g = 0.1375 mol x 96 g/mol
= 13.2015g
������������ ����� 11.3833�
Percentage yield = �ℎ��������� �����
� 100% = 13.2015� � 100% = 86.23%
Observation unsaturation tests using Bromine in CCl4 and potassium
permanganate:
4-methylcyclohexanol + Bromine in CCl4 Yellow to colourless
4-methylcyclohexanol + potassium permanganate No changes
4-methylcyclohexene + Bromine in CCl4 Reddish brown colour of
bromine decolourised
4-methylcyclohexene + potassium permanganate Purple colour of KMnO4
decolourised and brown
precipitate MnO2 formed.

Discussion
In this experiment, the preparation of 4-methylcyclohexene
through alcohol dehydration have been done. The alkene is being
generate from the dehydration reaction of alcohols by heating the
alcohols in the presence of a strong acid such as sulfuric acid and
phosphoric acid at temperature below 100℃.The acid protonates the
alcoholic hydroxyl group, permitting it to dissociate as water. Loss of
a proton from the intermediate (an elimination reaction) brings about
an alkene. Phosphoric acid in this experiment is used as a catalyst to
make the reaction proceed faster and also a minimal amount of
sulfuric acid.
When distill the product from the reaction mixture as it is
formed, the equilibrium of this reaction will also being achieved. The
4-methylcyclohexene (boiling point = 101-102℃) will codistill with
the water that is also formed. A high yield of 4-methylcyclohexene
can be obtained by continuously removing the products. Since 4-
methylcyclohexanol have a low boiling point, the distillation must be
done carefully so that the alcohol does not also distill.
A small amount of phosphoric acid that appears in the receiving
flask is being removed by washing the distillate mixture with a
saturated sodium chloride solution. This step also partially removes
the water from the 4-methylcyclohexene layer. In drying process,
anhydrous sodium sulfate is used.
In unsaturation tests using Bromine in CCl4 and potassium
permanganate, when 4-methylcyclohexanol react with Bromine in
CCl4 the yellow colour of the solution turns to colourless after several
minutes and when react with the potassium permanganate, the
reaction have no observable changes. Next, 4-methylcyclohexene
obtained from the experiment is react with Bromine in CCl4, the
reddish brown colour of bromine decolourised and when react with
the potassium permanganate, purple colour of KMnO4 decolourised
and brown precipitate MnO2 formed.

Conclusion
The percentage yield of 4-methylcyclohexene is 86.23% with
11.3833g produced experimentally. 4-methycyclohexene have been
managed to form from the starting material, 4-methylcyclohexanol
through the acid-catalyzed elimination of water.

References
Pozhydaiev, V., Power, M., Gandon, V., Moran, J., & Lebœuf, D.
(2020). Exploiting hexafluoroisopropanol (HFIP) in Lewis and
Brønsted acid-catalyzed reactions. Chemical Communications, 56(78),
11548-11564.
Parliment, T. H. (2020). Solvent extraction and distillation
techniques. Techniques for Analyzing, 1-26.
Questions