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Title

Preparation of 4-methylcyclohexene

Objective

1. To learn distillation technique


2. To understand the mechanism involved in the reaction
3. To produce 4-methylcyclohexene through the acid-catalyzed elimination of
water from 4-methylcyclohexanol

Introduction

In this experiment, 4-methylcyclohexene is formed through the acid-catalyzed


dehydration of 4-methylcyclohexanol. The product which is
4-methylcyclohexene is distilled from the reaction flask along with the water
generated. The distillate is washed with salt solution, dried and distilled.

For dehydration to be possible,the OH group on 4-methylcyclohexanol must


be converted into H2O through acid-catalyzed dehydration using a strong acid
catalyst such as phosphoric acid and sulfuric acid. The reaction is conducted in
a distillation apparatus. The H2O molecule will then become the favored
leaving group and leave on its own resulting in the formation of a carbocation
in excess water. The water will remove the acidic hydrogen on the carbocation
producing the desired alkene as well as regenerating the acid catalyst. The time
effective way to collect th 4-methylcyclohexene is to heat the reaction to reflux
as it is taking place. This allows the product to be separated from the starting
materials by means the boiling point discrepancy between the isolated alkene
(101-102℃) and the starting alcohol (171-173℃).Any unreacted cyclohexanol
(the starting material) and phosphoric acid (catalyst) are left in the distilling
flask because of their high boiling points (161℃ and 213℃ ). However, a
small amount of catalyst stil appears in the receiving flask, the product is then
washed with saturated sodium chloride to neutralize the acid.After the distillate
is collected any impurities of water and phosphoric acid can be extracted by
adding anhydrous sodium sulfate.Sodium sulfate is a salt which forms a
hydrate. Final purification is achieved by simple distillation. The product
formed is then identified using unsaturation test which is using bromine test
and Baeyer’s test.

Procedure

An apparatus for simple distillation was set up. 100 ml round-bottom flask and 50
ml round-bottom flask was used as the distilling flask and receiving flask. An ice
bath was placed around the receiver to lessen the loss of product by evaporation.
Then, an empty 100 ml round-bottom flask was weighed. 7.5 ml of
4-methylcyclohexanol was placed using graduated pipets and the flask was
reweighed again to get the mass of alcohol. 2.0 ml of 85% phosphoric acid and 30
drops of concentrated H2SO4 along 2 boiling chips was added in the distillation
flask and mix thoroughly. The mixture was heated with a heating mantle and
distilled slowly with maintain the distillation temperature below 100℃.
Distillation was continued untill only 0.5-0.6 ml of residue remains in the flask or
the mixture began to smoke or bump. Next, the distillate was mixed with 3ml of
saturated NaCl and the mixture was transfered into a test tube. The test tube was
closed with the cork tightly and the layers was mixed by swirling and shaking.
This step was repeated to allow the layers to separate. The bottom aqueous layer
was drawn off with a Pasteur pipet and discarded. The crude of
4-methylcyclohexene was transfered using pasteur pipet to an Erlenmeyer flask. A
small amount of anhydrous Na2SO4 was added and a stopper was placed. The
liquid was dried for at least 15 minutes while gentle swirling. The simple
distillation was cleaned,dried and reassambled with acetone during drying interval.
A receiver of 50 ml round-bottom flask was weighed and transfered the dried
cyclohexene with pasteur pipet into 100 ml round-bottom flask. 2 boiling chips
was added and distilled and repeated the step as above for distillation process.after
that,the flask was reweighed and calculate the percentage yield of
4-methylcyclohexene.
Unstaturation test using Br2 in CCl4 and KMnO4

3 drops of 4-methylcyclohexanol was placed into 2 separate tset tubes. 6 drops of


Br2 in CCl4 in one of the test tube and 4 drops of KMnO4 was added in other test
tubes. Any colour changes was observed. Next, 3 drops of 4-methylcyclohexene
that was obtained was placed in 2 separate test tubes. 6 drops of Br2 in CCl4 was
added in one of the test tube and 4 drops of KMnO4 was added in other test tubes.
Any colour changes was observed.

Result and Observations

Weight of empty round-bottom flask = 53.9557g


Weight of empty round-bottom flask + 4-methylcyclohexanol = 60.1959g
Weight of 4-methylcyclohexanol = 6.2402g

Weight of empty round-bottom flask = 53.4680g


Weight of empty round-bottom flask + 4-methylcyclohexene = 54.5099g
Weight of 4-methylcyclohexene = 1.0419g
Boiling point observed from experiment = 80℃
Literature boiling point of 4-methylcyclohexene = 104.3℃

Unsaturation test

Observations
Reagent used
4-methylcyclohexanol 4-methylcyclohexene

Br2 in CCl4 The yellowish brown The yellowish brown


solution turns pale yellow solution turns colourless

KMNO4 The solution contains


double layer. The purple
The purple solution
solution turns to brown
remains unchanged.
colour and there are
brown precipitate present.

Calculations

No of moles of 4-methylcyclohexanol = mass = 6.2402 g


Molar mass 114.2g/mol

= 0.0546 mol
1 mol of 4-methylcyclohexanol ≈ 1 mol 4-methylcyclohexene
0.0546 mol 4-methylcyclohexanol ≈ 0.0546 mol 4-methylcyclohexene

Mass of 4-methylcyclohexene = no of mol x molar mass


= 0.0546 mol x 96.2 g/mol
= 5.25 g

Percent yield (%) = actual yield x 100 %


theoretical yield
= 1.0419 g x 100%
5.25g
= 19.85%

Discussion

Elimination reactions are good synthetic methods to produce alkene.In this


experiment, we eliminate water molecules,H2O from alcohol to produce alkene.
The elimination of H-OH from 4-methylcyclohexanol to produce
4-methylcyclohexene is also known as dehydration reaction. In many cases,
alcohol dehydration is acid-catalyzed reaction that proceeds by an elimination
mechanism.

The mechanism is cyclohexyl cation,which can undergo substitution as well as


elimination. In this experiment, the substitution reaction are the use of strong acids
with anions that are relatively poor nucleophiles and a high reaction
temperature,which favors elimination. The anion of phosphoric acids in this
experiment is poor nucleophile, which substitution reaction are not favored. The
first step of dehydration is a proton transfer from the acid catalyst to the oxygen
atom of the alcohol. Weak base are good leaving groups, so changing the leaving
group from hydroxide to water favors the reaction. The second step of the
dehydration reaction is loss of water from oxonium ion forming a positively
charged secondary carbocation. This step of mechanism is rate determining. The
third and final step, a molecule of water deprotonates the carbocation at either of
the adjacent carbons. The remaining electrons flow towards the positive charge
producing a sigma-bond between the carbons and forming a double bond.
For unsaturation test, 4-methylcyclohexanol and the product which is
4-methylcyclohexene has been tested with Br2 in CCl4 and KMnO4. All the test
conducted is succesful. When 4-methylcyclohexene was put with Br2 in CCl4 the
yellowish brown colour of solution turns to colourless while for
4-methylcyclohexanol the yellowish brown colour turns to pale yellow.
4-methylcyclohexene is an alkene that will turn brown bromine water colourless
as the bromine atom will break the carbon-carbon double bond. Next, both of the
solution was react with KMnO4 solution which is called as Baeyer’s test. For
4-methylcyclohexanol,there is no reaction in the solution as it remains purple in
colour while for 4-methylcyclohexene the reaction that takes places is oxidation
which causes the purple solution to turn brown colour. There is also brown
precipitate formed and the surface of the solution has double layers. The purple
solution changes colour to brown because potassium permanganate is reduced to
manganese dioxide, which is the brown precipitate.The double layer formed is due
to the oil present in the benzene ring of the cyclohexane.

There are some precautions steps that we should be careful of. Firstly, Phosphoric
acids are strong and corrosive acid. If the acids splashed on our skin or clothes,
wash it immediately with plenty of water. Next, 4-methylcyclohexene is not
particularly dangerous but are highly flammable. Both are quite painful if splashed
into eyes and must be removed it by immediately wash it with plenty of water.
Lastly, remaining 4-methylcyclohexene should be disposed in the fume-hood sink
because 4-methylcyclohexene vapors are heavier than air where they will
accumulate in the sink.

Conclusion
19.85% of percent yield was calculated, which 1.0419g of 4-methylcyclohexene
was produced experimentally. We has produce 4-methylcyclohexene through
acid-catalyzed elimination of water and the mechanism that involved in the
reaction was understood.

References

1. https://www.scribd.com/doc/97566630/CHEM-LAB-II-3

2. http://www.passmyexams.co.uk/GCSE/chemistry/test-for-alkenes.html

3. https://studymoose.com/synthesis-of-4%E2%80%90methylcyclohexene-essay

4. http://fareastzareul1994.blogspot.com/2016/03/preparation-of-4-methylcyclohe
xene.html