CHM 457

FUNDAMENTAL TO ORGANIC CHEMISTRY

LABORATORY REPORT
EXPERIMENT 2: Preparation Of 4-Methylcyclohexene

NAME: MOHAMMAD AMIRUL ALIFF BIN MAHAZAM

STUDENT ID: 2018403148
GROUP: AS2452S1
LABORATORY DATE: 22 MARCH 2019
SUBMISSION DATE: 29 MARCH 2019
LECTURER NAME: DR FARIDAH HANIM
Objective
1. To learn distillation technique.
2. To understand mechanism involved.
3. To produce 4-methylcyclohexanol through acid-catalyzed dehydration of 4-
methylcyclohexanol.

Introduction
4-Methylcyclohexene is an alkene compounds which its uses has been increased recently. It has
been used in (1) the synthesis of an enantiomerically pure oxaliplatin derivative, {(1𝑅, 2𝑅, 4𝑅)-4-
Methyl-1,2-cyclohexanediamine}oxalatoplatinum(II), which exhibits good anticancer activity. (2)
preparation of 𝑁, 𝑁-diethyldithiocarbamatefunctionalized 1,4-polyisoprenes.

In the presence of strong acid, an alcohol can be dehydrated to form an alkene. The strong acid
serves to protonate the “OH” group of alcohols, which form a water molecule and that is much
better leaving group. As water leaves from 4-methylcyclohexene, a proton is also lost in this
elimination process. Which resulted into the alkene product. The presence of catalyst increase the
reaction. The dehydration reaction with the acid as catalyst is known as acid-catalyzed dehydration.

Apparatus
50-ml round bottom flask
25-ml round bottom flask
Erlenmeyer flask
Glass stirring rod
Pasteur pipets
Boiling stones
Distillation apparatus
Ice-water bath
Heating mantle
Reagents
7.5 ml of 4-methylcyclohexanol
2.0 ml 0f 85% phosphoric acid, 𝐻3 𝑃𝑂4
30 drops (0.40 ml) of concentrated sulphuric acid, 𝐻2 𝑆𝑂4
Saturated sodium chloride solution, NaCl
Granular anhydrous sodium sulphate, 𝑁𝑎2 𝑆𝑂4
Bromine test reagent
Potassium permanganate test reagent

Procedure
Part A (Preparation of 4-Methylcyclohexene)

1. The apparatus for simple distillation was set up as in Image 1.

Image 1

2. 50 mL and 25 mL round bottom flask has been used as distilling flask and receiver flask
respectively.

3. To lessen the loss of product by evaporation an ice bath has been placed around the
receiver.

4. The 50 mL round bottom flask (distillation flask) has been weighed.

5. 7.5 mL of 4-Methylcyclohexanol was placed into the round bottom flask by using
graduated pipets.
6. Mass of alcohol was obtained by reweigh the distilling flask again.

7. The mixture of 2.0 mL of phosphoric acid, 30 drops of concentrated sulfuric acid and 2
boiling chips was mixed thoroughly.

8. Then, the mixture was heated and distilled slowly while the temperature was being
maintained below 100℃ with a heating mantle.

9. The distillation was continued until the mixture has begun to smoke or bump.

10. 3 mL Saturated NaCl was mixed with the distillate and the mixture then transferred to a
separatory funnel.

11. The separatory funnel was close tightly with a cork then the layers was mixed by gentle
swirled and shake. Separatory funnel was carefully vented.

12. The process of swirled and shake and also vent the separatory funnel was repeated a few
times and the layers was allowed to separated.

13. Pasteur pipet was used to draw off and discarded the bottom aqueous layer.

14. Crude 4-methylcyclohexene was transferred to an Erlenmeyer flask by using a regular

Pasteur pipet.

15. Small amount (1 full of spatula) of anhydrous sodium sulphate was added into flask and
a stopper was placed.

16. With gentle swirling, the liquid was dried for 15 minutes at least.

17. The simple distillation apparatus was cleaned and dried with the acetone while the
drying take place.

18. 25 mL round bottom flask has been used as receiver flask and been weighed while
capped.

19. Distillation flask was filled with the dried cyclohexene that has been transferred using
Pasteur filter pipet and 1-2 boiling chips.

20. Then the mixture was distilled at temperature 100-105℃.

21. The portion was collected in the flask that was chilled in ice bath.

22. The flask was reweigh and percentage yield of 4-methylcyclohexene was calculated.
Part B (Unsaturation tests)
4-Methylcyclohexanol
1. 2 separate test tubes was placed with 3 drops of 4-methylcyclohexanol for each.

2. 6 drops of Bromine in 𝐶𝐶𝑙4 was added in one of the test tube.

3. Meanwhile the other test tube was added with 4 drops of potassium permanganate.

4. The colour changes were recorded.

4-Methylcyclohexene
1. 2 separate test tubes was placed with 3 drops of 4-methylcyclohexene for each.

2. 6 drops of Bromine in 𝐶𝐶𝑙4 was added in one of the test tube.

3. Meanwhile the other test tube was added with 4 drops of potassium permanganate.

4. The colour changes were recorded.

Results and Data

 Preparation of 4-methylcyclohexene
Weight of 4-methylcyclohexanol 6.8009
used (g)
Weight of pure 4- 2.8035
methylcyclohexene obtained (g)
Melting point range for 174
experimental (℃)
Melting point range for literature 102
(℃)

 Unsaturation test
Compound
4-methylcyclohexanol
4-methylcyclohexene
In Bromine in 𝐶𝐶𝑙4 In potassium permanganate
No change No change
From yellow to colourless From purple to dark brown
precipitate
Calculation
 Theoretical yield calculation (Using Conversion Factor)
4-methylcyclohexanol
Volume of 4-methylcyclohexanol 7.5 mL
used
Density of 4-methylcyclohexanol 0.92 g/mL
Molar mass of 4-methylcyclohexanol 114.2 g/mol

0.92 𝑔 1 𝑚𝑜𝑙𝑒
7.5 𝑚𝐿 × × = 0.0604 𝑚𝑜𝑙𝑒𝑠
1𝑚𝑙 114.2 𝑔

 Percentage yield of 4-methylcyclohexene

4-methylcyclohexene
Mass of 4-methylcyclohexene 2.8035g
obtained
Moles of 4-methylcyclohexene 2.8035𝑔
obtained 96.173 𝑔/𝑚𝑜𝑙
= 0.0292 𝑚𝑜𝑙𝑒𝑠

Theoretical yield 0.0604 moles

𝐹𝑜𝑟𝑚𝑢𝑙𝑎

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑙𝑘𝑒𝑛𝑒 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑

× 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑

0.0292 𝑚𝑜𝑙𝑒𝑠
× 100 = 48.34%
0.0604 𝑚𝑜𝑙𝑒𝑠
Discussion
In elimination reaction, a small molecule loss from the carbon atoms resulting in the
formation of unsaturated double bond. Elimination reactions are widely used as synthetic
method for producing alkene. The reactions happen in a process called heterolytic bond
cleavage. Heterolytic bond cleavage occurs when one atom leaves a compound with both
electrons of the original bond, produce ions. The leaving group depart with both electrons
from original C-X bond. The electrons in the adjacent C-H bond form the new pi bond (𝜋) of
the alkene, with the loss of proton.
The elimination of water (H-OH) from the alcohol is called dehydration reaction and the
alcohol dehydration in this cases mostly is an acid-catalyzed dehydration. The acid-catalyzed
dehydration of alcohol is when the elimination reaction occur with strong acid act as catalyst
and turn alcohol into alkene.
The experiment that been carried is expected to produce 4-methylcyclohexene. In the
experiment, 4-methylcyclohexanol undergoes acid-catalyzed dehydration by heated with the
presence of 85% phosphoric acid (𝐻3 𝑃𝑂4 ) as catalyst at high temperature to produce 4-
methylcyclohexene. The process in produce alkene is significant to learn the distillation
technique, understand the mechanism involved and to produce alkene from acid-catalyzed
dehydration method.
From the experiments, various compilation of data have been obtained. Firstly, from
unsaturation test for 2 compounds the data is as below;
Compound In Bromine in 𝐶𝐶𝑙4 In potassium permanganate
4-methylcyclohexanol No change No change
4-methylcyclohexene From yellow to colourless From dark purple to brown
precipitate

4-methylcyclohexanol does not have any changes in bromine in 𝐶𝐶𝑙4 and in potassium
permanganate while for 4-methylcyclohexene the solution in bromine change colour from
yellow to colourless and in potassium from dark purple to brown precipitate. The
unsaturation test is a test to determine the present of double, triple bond. The 4-
methylcyclohexanol have no double or triple bond thus, doesn’t change the colour of bromine
and potassium permanganate. 4-methylcyclohexene have changes both bromine and
potassium permanganate colour because it’s have the presence of double bond.
Second is about the theoretical yield and actual percent yield. Theoretical yield obtained is
0.0604 in moles and the actual percent yield is 48.34%. The value is very low and this may
be due to incomplete reaction or distillation. While in extraction and washing phenomenon
some product also lost, which resulted in low recovery. Long reaction time with proper
handling may increase the recovery percentage.
To better the result some adjustment need to be taken. In the reaction yield of alkene is very
low, and it can be increased by increasing the time of reaction and by decreasing losses
during washing and extraction.
Conclusion
In conclusion, the unsaturation test that has been conducted to the product of distillation show
changes from yellow to colourless (in Bromine in CCl4) and dark purple to brown precipitate
( in Potassium permanganate) indicate that the 4-methylcyclohexene has been produced with
percentage yield of the reaction done is 48%. Overall, the experiment succeeded to shows
that the dehydration of alcohol compound with the presence of strong organic acid will
produce alkene.

References
1) Martin S. Silberberg, Patricia G. Amateis, “CHEMISTRY: THE MOLECULAR NATURE
OF MATTER AND CHANGE”, 7TH edition, McGraw-Hill Education, Inc. N.Y 2015, page
617-658

2) Giese, B., Formation of CC bonds by addition of free radicals to

alkenes. Angewandte Chemie International Edition in English, 1983. 22(10): p. 753-
764.

Questions and Answers

1. Utilizing structural formula, 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?
Type of reaction is elimination reaction. The name of the reaction is dehydration.

3. Why is receiving flask supposed to be kept on ice during preparation of cyclohexene?

To prevent 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.

1-methylcyclohexene 3-methylcyclohexene
(Major product)

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

methylcyclohexanol.