Faculty of Applied Science

Bachelor of Science (Hons.) Chemistry (Forensic Analysis)

CHM457
FUNDAMENTAL ORGANIC CHEMISTRY

LABORATORY REPORT

EXPERIMENT NO. : 2
EXPERIMENT TITLE : Preparation of 4-Methylcyclohexene
NAME : Nur Fatini Ameera Binti
Mohammad Faizul
STUDENT ID : 2020985261
DATE OF EXPERIMENT : 16 March 2020
DATE OF SUBMISSION : 27 March 2020
GROUP : AS2532B2
LECTURER’S NAME : Dr. Najmah PS. Hassan
Introduction
Alcohol undergoes elimination reaction in the presence of a strong acid to form an alkene.
Strong acids such as sulphuric acid or phosphoric acid is used in the dehydration reaction of
alcohols as catalysts. The acid needs to protonate the alcohol, OH group to form water
molecule, H2O that is a better leaving group. Then, the OH group can leave and the nucleophile
will obstruct a beta hydrogen to form a carbon double bond or an alkene.

The equilibrium of the reaction is made by eliminating the product to decrease its concentration
and increase the concentration of the reactants to get enough product. A wash with saturated
sodium chloride solution will help remove the acid and most residual water from the distilled
product. In this experiment, 4-methylcyclohexene, the end product, also required removal from
the system as it being formed to prevent reverse reaction so the reaction is conducted in a
distillation apparatus. Some water is taken off with the product due to the closeness of their
boiling points while distilling the solution. However, 4-methylcyclohexene is insoluble in
water and thus it is easily separated from water. The last traces of water are removed from the
4-methylcyclohexene by drying the liquid over anhydrous sodium sulfate. Final purification is
achieved by simple distillation.

Objectives
1. To learn the distillation technique.
2. To understand the mechanism involved in the reaction.
3. To produce 4-methylcyclohexene through the acid-catalyzed dehydration from 4-
methylhexanol.

Procedure
1. An apparatus for simple distillation was set up. 50 ml round bottom flask and 25 ml round
bottom flask were used as the distilling flask and receiver. An ice bath was placed around the
receiver to lessen the loss of product by evaporation.
2. An empty 50 ml round bottom flask was weighed. 7.5 ml of 4-methylcyclohexanol was
placed in the round bottom flask using graduated cylinder. The flask was reweighed again to
get the mass of alcohol.
3. 2.0 ml of 85% phosphoric acid and 30 drops of concentrated sulfuric acid were added along
with 2 boiling chips in the distillation flask and mixed thoroughly.
4. The mixture was heated with a heating mantle and distilled slowly while maintaining the
distillation temperature below 100˚C. The distillation was continued until the mixture begins
to smoke.
5. The distillate was mixed with 3 ml of saturated sodium chloride solution and transferred to
a test tube. The test tube was corked tightly and mixed the layers by swirling and shaking
gently.
6. The tube was vented carefully and the steps was repeated. The layers was then allowed to
separate. The bottom aqueous layer was draw off using separatory funnel and discarded.
7. Crude 4-metylcyclohexene was transferred from the separatory funnel 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 15 minutes with occasional gentle swirling.
8. The simple distillation apparatus was cleaned, dried with acetone and reassembled during
the drying interval. 25 ml round bottom flask was weighed while capped and used as receiver.
9. The dried cyclohexene was transferred into the distillation apparatus. 2 boiling chips was
added and distilled, the portion was collected with a boiling range of 100 - 105˚C in the flask
and chilled in an ice bath.
10. The flask was reweighed. The percentage yield of 4-methylcyclohexene was calculated.

Unsaturation test using Bromine in CCl4 and potassium permanganate.

1. 3 drops of 4-methylcyclohexanol was placed in 2 separate test tubes. 6 drops of Bromine in
CCl4 and 4 drops of potassium permanganate was added separately in one of the test tube and
in the other test tube. Any colour changes was observed.
2. 3 drops of 4-methylcyclohexene that was obtained in the experiment was placed in 2 separate
test tubes. 6 drops of Bromine in CCl4 and 4 drops of potassium permanganate was added
separately in one of the test tube and in the other test tube. Any colour changes was observed.

Result
Theoretical yield of 4-methylcyclohexene
4-methylcyclohexanol + H3PO4 → 4-methylcyclohexene + H2O
So, 1 mole of 4-methylcyclohexanol = 1 mole of 4-methylcyclohexene
6.5501 𝑔
Number of mol 4-methylcyclohexanol =
114.2 𝑔/𝑚𝑜𝑙
= 0.05736 moles
Thus, number of mol 4-methylcyclohexene = 0.05736 moles
Mass of 4-methylcyclohexene = 0.05736 moles x 96.2 g/mol
= 5.518 g
Percentage yield of 4-methylcyclohexene
Mass of 4-methylcyclohexene obtained = 3.2166 g
𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
Percentage yield of 4-methylcyclohexene = x 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
3.2166 𝑔
= x 100
5.518 𝑔

= 58.29 %
Boiling point of 4-methylcyclohexene

Observed boiling point 101˚C

Literature boiling point 101 – 102 ˚C

Discussion
Throughout the experiment, 4-methylcyclohexenol was converted completely to form
4-methylcyclohexene by dehydration process. In many cases, 4-methylcyclohexanol
dehydration falls under elimination reactions. Elimination reactions involve the loss of water
molecule from adjacent carbon atoms, resulting in pi bond formation. The loss of water is
consider as dehydration. Thus, elimination reactions are good synthetic methods for producing
alkene.
Furthermore, the hydroxyl group in 4-methylcyclohexanol is a bad leaving group so it
has to be protonated in order to convert it into a better leaving group. 85 % phosphoric acid
was added to provide the acidic condition as it is a poor nucleophile. The proton from the acid
catalyst was transferred to the oxygen atom of 4-methylcyclohexanol. This protonation forms
oxonium ion, the conjugate acid of the alcohol. Weak base are good leaving groups so changing
the leaving group from hydroxide to water helps the reaction. Then, the loss of water from
oxonium ion formed a positively charged secondary carbocation. The final step of dehydration
is a molecule of water deprotonated the carbocation at one of the adjacent carbons. The
remaining electrons flew towards the positive charge producing a sigma bond between the
carbons and double bond was formed.
The theoretical yield for 4-methylcyclohexene is 5.518 g while the experimental yield
is 3.2166 g, shows that the gap is too wide. With regard to the yield, the percentage yield
obtained is 58.29 % which is somewhat low. This could be due to the incomplete reaction or
distillation. Meanwhile, the observed boiling point is 101˚C which is in the range of literature
boiling point, 101-102˚C.
Last but not least, unsaturation tests, Bromine in CCl4 test and Baeyer’s test, were
carried out to determine whether the final distillate was actually 4-methylcyclohexene. 4-
methylcyclohexanol in the test tube showed no reaction for both tests. Meanwhile, the
colourless 4-methylcyclohexene turned to cloudy when reacted with Bromine in CCl4 and
produced two layer of colourless and dark brown with precipitate for Baeyer’s test. This
positive test shows that the product does contain double bond.
Conclusion
In a nutshell, the students have learned how to perform an acid-catalyzed dehydration
of 4-methylcyclohexanol to produce 4-methylcyclohexene with distillation technique. They
were also able to understand the mechanisms and elimination reactions deeper than before the
experiment. Although the dehydration process was succeed, the percentage yield shows that
there was some errors involved in the process. Thus, more precaution should be taken in order
to obtain the optimum amount of the end product. The observed boiling point is in the range of
literature boiling point and the purity of product was determined by unsaturation test. The tests
showed a positive sign for the presence of double bond in 4-methylcyclohexene.

Questions
1. Utilizing structural formulas, write a chemical equation for the preparation of 4-
methylcyclohexene from 4-methylcyclohexanol.

2. The preparation of cyclohexene from cyclohexanol is what basic type of reaction? What is
the name of this reaction?
The type of reaction for the preparation of cyclohexene from cyclohexanol is elimination
reaction. The secondary unsaturated alcohol, cyclohexanol, undergoes dehydration to form a
good leaving group, H2O because the OH group of an alcohol is a very strong base making it
a poor leaving group. The reaction is then followed by the obstruction of a hydrogen atom to
form a carbon double bond alcohol, cyclohexene.
3. Why is the receiving flask supposed to be kept on ice during the preparation of cyclohexene?
The receiving flask was kept on ice during the preparation of cyclohexene because the ice bath
removes heat so that it does not overheat the liquid reactants and lessen the loss of product by
evaporation.
4. If 2-methylcyclohexanol is dehydrated, two possible alkene products are obtained. Draw the
structure of these two products and predict which of the two products is the major product.

5. Show the complete acid-catalyzed mechanism for the dehydration of 2-methylcyclohexanol.

Jotter