EXPERIMENT 2: PREPARATION OF 4-METHYLCYCLOHEXENE FROM

DEHYDRATION OF 4-METHYLHEXANOL

Objectives

i. To prepare 4-methylcyclohexene from dehydration of 4-methylcyclohexanol

ii. To test the unsaturation through bromine and permanganate tests

Introduction

OH
H₃PO₄/H₂SO₄ + H₂O

CH₃ CH₃
4-Methylcyclohexanol 4-Methylcyclohexene

Alcohol dehydration is an acid-catalyzed reaction performed by strong, concentrated mineral

acids such as sulfuric and phosphoric acids. The acid protonated the alcoholic hydroxyl group,
permitting it to dissociate as water. Loss of a proton from an intermediate (elimination) brings
out an alkene. Sulfuric acid often causes extensive charring in this reaction. However,
phosphoric acid is comparatively free of this problem. In order to accelerate this reaction,
minimal amount of H₂SO₄ is added.
This reaction is carried out under reflux. As the mixture is heated, cyclohexene with lower
boiling point (b.p 83˚C) and water (b.p 100˚C) distilled out and collected in receiving flask. The
4-methylcyclohexene (bp 101-102˚C) will codistill with the water that formed. By continuously
removing the products, high yield of 4-methylcyclohexene can be obtained. Unreacted
cyclohexanol (starting material) and phosphoric acid (catalyst) are left in the distilling flask
because of their high boiling point. Therefore, distillation must be done carefully so that the
alcohol does not distill. However, small amount of H₃PO₄ still presence in the flask, it is then
washed with saturated NaCl to neutralize the acid.This step also partially removes water from 4-
methylcyclohexene layer;the drying process is completed by adding anhydrous Na₂SO₄.
 Compounds that contain double bonds will react with Br solution (red) to decolorize it.
Similarly, they’ll react with KMnO₄ (purple) to discharge the colour and form brown precipitate
(MnO₂). These qualitative tests are used to determine the presence of double bond in an organic
molecule. Both tests will be performed on 4-methylcyclohexene formed in this experiment.
OH
Br CH₃ CH₃ CH₃
Br₂ KMnO₄
+ MnO₄
(red) (purple)
Br
OH (brown)

(colourless) (colourless)

Procedure
50 mL of round-bottom flask was weighed and 7.5 mL of 4-methylcyclohexanol was poured into
the pre-weighed flask. The flask containing the solution was weighed again. Next, 2.0 mL of
85% H₃PO₄ and 30 drops (0.40 mL) of H₂SO₄ was added into the volumetric flask. The mixture
was then mixed thoroughly using a glass rod and boiling stone was added. Distillation was
conducted as shown:

Dehydration
The circulating of the cooling water in the condenser was started and the mixture was heated
with a heating mantle until the product starting to distill and collected in the receiver flas. The
heating was continued for 30 minutes until no more liquid was collected.
Isolation and Drying of the product
4-methylhexene collected was transferred into centrifuge tube and 1-2 mL of saturated NaCl was
addedThe layers are allowed to separate and the aquoeus layer (bottom) was removed using
Pasteur pipette. Next, the organic layer (top part) was removed into an Erlenmeyer flask
containing anhydrous Na₂SO₄. A stopper was placed on the flask and left for 10-15 minutes to
remove the last traces of water.
Distillation
Distillation was repeated using 4-methylcyclohexanol.
Unsaturation test
4-5 drops of 4-methylcyclohexanol was added into tweo test tubes labeled A and B. Next, 4-5
drops 0f 4-methylhexene was added into 2 test tubes labelled C and D. Br in CCl₄ was added
drop by drop into test tube A and C until no longer colour discharge. Then, 0.3 mL of 1,2-
dimethoxyethane and aqueous KMnO₄ was added into B and D.
Results and observations
Weight of empty round-bottom flask (g) = 56.499
Weight of round-bottom flask + 4-methylcyclohexanol (g) = 62.9038
Weight of 4-methylcyclohexanol (g) = 62.9038-56.499
= 6.4048
Weight of empty receiver (g) = 53.378
Weight of receiver + distillate 4-methylcyclohexene (g) = 60.2284
Weight of distillate 4-methylcyclohexene (g) = 60,2284-53.378
= 6.8504
Weight of (2nd) receiver (g) = 55.7050
Weight of (2nd) receiver + 4-methylcyclohexene (g) = 58.3270
Weight of 4-methylcyclohexene (g) = 2.622
Unsaturation tests
Br₂ test KMnO₄
4-methylcyclohexene – Red colour of 4-methylcyclohexene- colourless solution
bromine decolorises into colourless turns purple
4-methylcyclohexanol – Colourless solution 4-methylcyclohexanol – Brown percipitate
turns red formed
Calculations
Theoretical yield of 4-methylcyclohexene

Molecular weight of 4-methylcyclohexene = 114.07 gmol⁻¹

1 mol of 4-methylcyclohexanol = 1 mol of 4-methylcyclohexene
Relative molecular weight = 114.2 gmol⁻¹ Relative molecular weight = 96.07 gmol⁻¹

𝑚𝑎𝑠𝑠 (𝑔)
1. No of mol of 4-methylhexanol = 𝑀𝑟
6.4048𝑔
= 114.2𝑔𝑚𝑜𝑙−1

= 0.0561 𝑚𝑜𝑙 of 4-methylcyclohexene

2. Mass of 4-methylcyclohexene = mol × Mr
= 0.0561 mol × 96 gmol⁻¹
= 5.39 g
𝐴𝑐𝑡𝑢𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
% yield = 𝑇ℎ𝑒𝑜𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑 × 100%
2.622𝑔
= × 100%
5.39𝑔

= 48.6%
Discussion
This experiment emphasizes the distillation technique used to produce 4-methylcyclohexene.The
reaction involves in this experiment is elimination. This process occurs through heterolytic bond
cleavage where one atom leaves a compound with both electrons of the original bond, thus the
ions are formed. Water was eliminated from 4-methylcyclohexanol through acid-catalyzed
reaction is called dehydration.
In this experiment, concentrated H₂SO₄ and strong H₃PO₄ solution are used as they’re a weak
nucleophiles. The first step of dehydration is a proton will be transferred from acid catalyst to the
oxygen atom of the alcohol. This protonation forms an oxonium ion, the conjugate acid of 4-
methylcyclohexanol.The next step of dehydration is the loss of water from the oxonium ion then
formed a positively charged secondary carbocation. The last step is the deprotonation of H₂O
from the carbocation at the adjacent carbons. The electron left move towards the positively
charged carbon. Sigma bond was produced between the carbons then forming a double bond.
 1 mol of 4-methylcyclohexanol is equivalent to 1 mol of 4-methylcyclohexene. The theoretical
mass of 4-methylcyclohexene is 5.39 g while the experimental value is 2.622g. The percentage
yield of 4-methylcyclohexene calculated is 48.6%.
Precaution steps can be taken to avoid any inconveniencies. First, H₃PO₄ is a strong and
corrosive acids. Gloves should be worn to avoid any acids contact with the skin. If any of the
acid are splashed on the skin, wash with soap and water immediately. Moreover, the remaining
4-methylcyclohexene should be disposed in the fume-hood sink because its vapours are heavier
than air and can accumulate in the sink.
Conclusions
48.6% percent of yield was calculated and 2.00g of 4-methylcyclohexene was obtained
experimentally through acid-catalyzed reaction . The reaction involved is elimination. 4-
methylcyclohexene decolorises red colour of bromine solution and turn colourless solution to
purple when react with KMnO₄. Therefore it proves the presence of double bond.

Questions
1. Outline a mechanism for the dehydration of 4-methylcyclohexanol catalysed by H₃PO₄.
2. What major alkene product is produced by the dehydration of the following alcohols ?
a) Cyclohexanol
Dehydration of an alcohol removes the OH and the H on the β-carbon.

OH
H₃PO₄
+ H₂O

cyclohexanol cyclohexene

b) 1-methylcyclohexanol

OH
CH₂ H₃PO₄

c) 2-methylcyclohexanol

d) 2,2-dimethylcyclohexanol
 e) 1,2-Cyclohexanediol

3. Compare and interpret the infrared spectra of 4-methylcyclohexene and 4-

methylcyclohexanol

References

1. Pavia,Lampman,Kriz and Engel, Introduction to Organic Laboratory Techniques,2011

3rd Edition
2. Martin S. Silberberg,Patricia G.Amateis,Chemistry: The molecular nature of matter and
change,2015 7th Edition,McGraw-Hill Education, Inc. N.Y