Aims/Objectives of the Experiment

1) To learn the distillation technique.

2) To understand the mechanism involved in the reaction.
3) To produce 4-methylcyclohexene from the dehydration of 4-methylcyclohexanol.

Introduction
In this experiment, 4-methylcyclohexanol undergoes acid-catalyzed dehydration
to produce 4-methylcyclohexene. The dehydration reaction of alcohols to generate
alkene involve the process of heating the alcohols in the presence of a strong acid.
For example, sulfuric acid and phosphoric acid with the presence of high temperature.

In order to prepare 4-methylcyclohexene, phosphoric acid and sulfuric acid used and
acts as the catalysts to protonate the OH group to form an water molecule. As the
water molecule are leaving, a proton also lost in an elimination process and produce
alkene. A simple elimination reaction induced to produced 4-methylcyclohexene. A
simple elimination reaction is the type of organic reaction which the two substituents
removed from a molecule either in a one-step (E2 reaction) or two-step (E2)
mechanism. To prevent the alkene formed in the dehydration reaction from reforming
back the alcohol, the alkene been removed by distillation process as it is formed. This
is because it has a lower boiling point than alcohol.
Experimental Procedure
Apparatus Assembly
i. 7.5 mL of 4-methylcyclohexanol placed in a tared 50-mL round-bottom flask and
the flask was weighted to determine an accurate weight for the alcohol.
ii. 2.0 mL of 80% phosphoric acid and 30 drops (0.40 mL) of concentrated sulfuric
acid were added to the flask.
iii. The liquids mixed thoroughly with a glass stirring rod and a boiling stone was
added.
iv. A 25 mL flask was used as a receiver.
v. The receiving flask was immersed in an ice-water bath to minimize the possibility
that 4-methylcyclohexene vapors escape into the laboratory.

Dehydration
i. The cooling water started to circulate in the condenser and the mixture heated
with a heating mantle until the products began to distill and collected in the
receiver.
ii. The distillation required about 30 minutes.
iii. The distillation continued until no more liquid were collected. The distillate
contained 4-methylcyclohexene as well as water.

Isolation and Drying of the Product

i. The distillate mixture transferred to a centrifuge tube with the aid of 1 mL or 2 mL
of saturated sodium chloride solution.
ii. The layers were allowed to separate and the bottom aqueous layer was removed
with a pasteur pipet.
iii. A dry pasteur pipet was used to transfer the remained organic layer in the
centrifuge tube to an Erlenmeyer flask that contained a small amount of granular
anhydrous sodium sulfate.
iv. A stopper was placed in the flask and was set it aside for 10-15 minutes to
remove the last traces of water.
v. The distillation apparatus were cleaned and washed with small amounts of
acetone and an air stream to aid the drying process.
Distillation
i. The dry liquid were transferred to the clean and dry 50 mL round bottom flask.
ii. A boiling stone was added to the flask and the distillation apparatus were
assembled as before and a 25 mL receiving flask was used.
iii. A heating mantle was used to distill 4-methylcyclohexene and the materials that
boiled over the range of 100℃-105℃ were collected. The observed boiling-point
range were recorded.
iv. The receiving flask was reweigh to obtain how much 4-methylcyclohexene been
prepared. The percentage yield of 4-methylcyclohexene were calculated.

Unsaturation Tests
i. 4-5 drops of 4-methylcyclohexanol were placed in two small test tubes. 4-5 drops
of 4-methylcyclohexene placed in another two small test tubes.
ii. One each of the test tubes were took and a solution of bromine in carbon
tetrachloride or methylene chloride were added drop by drop to the test tubes
until the red color was no longer discharged.
iii. The results were recorded including number of drops required.
iv. The another two test tubes were tested with a solution of potassium
permanganate. 0.3 mL of 1,2-dimethoxyethane were added to each test tubes
before tested. The results were recorded.
Results and Observations
Weight of empty round-bottom flask : 66.117 g
Weight of empty round-bottom flask + 4-methylcyclohexanol : 75.259 g
Weight of 4-methylcyclohexanol : 9.142 g
Weight of empty round-bottom flask + 4-methylcyclohexene : 68.797 g
Weight of 4-methylcyclohexene : 2.680 g

Melting point range for experimental : 80℃

Melting point range for literature :65℃
Percentage yield : 34.80%

SOLUTION OBSERVATION
4-methylcyclohexanol + bromine Red
4-methylcyclohexanol + KMnO4 Purple
4-methylcyclohexene + bromine Clear
4-methylcyclohexene + KMnO4 Clear and precipitate formed
Table 1: Results for Unsaturation Tests

Figure 1: Results for Unsaturation Tests

DISCUSSIONS
By using an elimination reaction, 4-methylcyclohexene successfully formed from
the process of dehydration of 4-methylcyclohexanol. This reaction performed by
strong and concentrated mineral acid of sulfuric acid and phosphoric acid as the
catalyst. In the presence of strong catalyst, 4-methylcyclohexanol can be dehydrated
to form alkene. Distillation process used to perform alkene because it will prevent
alkene formed in the dehydration reaction from reforming back to
4-methylcyclohexanol. Distillation process used to removed the products from the
reaction mixture. During the distillation process the color of the solution change and it
prove that there was a successful acid-catalyzed dehydration of the alcohol to create
the carbocation. The weight obtained for 4-methylcyclohexanol and
4-methylcyclohexene are 9.142g and 2.680g respectively. It show that
4-methylcyclohexanol have higher weight than alkene product. While for the melting
point range for experimental and for literature are 80℃ and 65℃ respectively.
For the unsaturation tests for 4 different test tubes resulted 4 different colors of
the solution when added with bromine in carbon tetrachloride and KMnO4. When
bromine in tetrachloride added to 4-methylcyclohexanol, it produce red solution. But
when bromine in tetrachloride react with 4-methylcyclohexene it produce clear
solution. Double bond of alkene react with with bromine to form alkane. For KMnO4
solution, when added to 4-methylcyclohexene it remained clear and precipitate
formed after 4 drops added. KMnO4 react with double bond of the alkene to form
clear solution along with the precipitate. For 4-methylcyclohexanol it turned to form
purple solution when added with KMnO4 because of the alcohol does not have double
bond.
To minimize the errors, the observers should clean all the flask that gonna used
with distilled water to avoid any contamination caused from the previous users. The
volume of the solution used should be measured exactly especially for the
unsaturation test. It is because when the observer added less or more drops of the
solution it will resulted different color of solutions. The precaution step that should be
care is the remaining alkene must be disposed off in the fume hood sink because it’s
vapor heavier in the air. This experiment enhance the skills on how to handle the
distillation apparatus correctly. It also gain the understanding on how alkene product
formed by the dehydration of 4-methylcyclohaxanol.
CONCLUSIONS
As the conclusion, it can be conclude that 4-methylcyclohexene can be produced
from 4-methylcyclohexanol by acid-catalyzed dehydration. This reaction involved E1
reaction because OH is a poor leaving group and protonated to form water. Alcohol
were dehydrated by sulfuric acid and phosphoric acid. There are 34.80%
percentage yield that calculated from 2.680 g of 4-methylcyclohexene.

CALCULATIONS
Theoretical yield = 9.142g 4-methylcyclohexanol / 114.2g/mol
= 0.08 mol of 4-methylcyclohexanol
0.08 mol (96.2g/mol)
= 7.701 g 4-methylcyclohexene
Percentage yield = actual yield /theoretical yield X 100%
= 2.680 / 7.701 X 100%
=34.80%
QUESTIONS
1) Outline the mechanism for the dehydration of 4-methylcyclohexanol catalyzed by
phosphoric acid.

2) What the major alkene product is produce by the dehydration of the following
alcohols?
Cyclohexanol

1-Methylcyclohexanol
2-Methylcyclohexanol

2,2-Dimethylcyclohexanol

1,2-Cyclohexanediol
4) In this experiment,1-2mL of saturated sodium chloride is used to transfer the crude
product after the initial distillation. Why is the saturated sodium chloride,rather than
pure water used for this procedure?
Sodium chloride is used to remove the remaining phosphoric acid found in the product
after distillation. Saturated sodium chloride used over pure water because the use of
water would shift the equilibrium toward our reactants. Saturated sodium chloride
gives the water more polar tendencies and decreases the solubility of organics in
water.

REFERENCES
1) https://www.chemicalforums.com/index.php?topic=39749.0
2) https://study.com/academy/answer/explain-the-process-of-product-isolation-and-p
urification-of-the-dehydration-of-4-methylcyclohexanol-to-4-methylcyclohexene.ht
ml
3) http://www.chem.ucla.edu/~bacher/faqs/LabWriteup/example.html
4) https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modul
es_(Organic_Chemistry)/Alkenes/Synthesis_of_Alkenes/Alkenes_from_Dehydrati
on_of_Alcohols