CHM457 FUNDAMENTAL ORGANIC CHEMISTRY

EXPERIMENT 2 : PREPARATION OF 4 – METHYLCYCLOHEXENE

NAME : NUR HISMANIZA BINTI MORSIDI

MATRIC NO : 2019653874

GROUP : AS245S2

PARTNERS’ NAME : 1) ASRIN AWANG SELAN

2) SYANAYA NASYA BNTI SHAHARONY

3) NURNADZIRAH NABIHA BINTI JAMI’AN

LECTURER’S NAME : DR MOHD TAJUDIN MOHD ALI

DATE OF EXPERIMENT : 27 SEPTEMBER 2019

DATE OF SUBMISSION OF REPORT : 4 OCTOBER 2019

OBJECTIVE

To produce 4-methylcyclohexene through acid-catalysed dehydration from 4-

methylcyclohexanol

INTRODUCTION

In this experiment, 4-methylcyclohexanol undergoes acid-catalysed dehydration to form 4-

methylcyclohexene. The product is distilled from the reaction flask along with the water
generated. The distillate is washed with salt solution, dried and distilled.

One of general laboratory methods for preparing alkenes is the dehydration of alcohols
using strong mineral acids as catalysts, such as sulfuric acid or phosphoric acid. The reaction
is conducted in distillation apparatus. As the reaction mixture is heated, the lower boiling points
products (cyclohexene with boiling point = 83C and water boiling point = 100C) distil out
and are collected in the receiving flask. Any unreacted cyclohexanol (the starting material) and
phosphoric acid (the catalyst) are left in the distilling flask because of their high boiling points
(161C and 213C). Nevertheless, a small amount of phosphoric acid still appears in the
receiving flask, the product is washed with aqueous sodium carbonate to neutralize the acid.
Cyclohexene is insoluble in water. Hence, it is not lost during the washing with aqueous
sodium carbonate solution. The last traces of water are removed from the crude cyclohexene
by drying the liquid over anhydrous sodium sulfate. Sodium sulfate is a salt which forms a
hydrate. Final purification is formed by simple distillation.
PROCEDURE

 Apparatus assembly
The apparatus for simple distillation was set up first 50 mL round bottom flask was used as
distilling flask and a 25 mL round bottom flask as receiver. An ice bath was placed around
the receiver to reduce the loss of product by evaporation. An empty 50 mL round bottom
flask was weighed. 7.5 mL of 4-methylcyclohexanol was placed in that round bottom flask
using graduated pipet.
 Dehydration
The distillation temperature was maintained below 100C. the distillation was continued
until only 0.5 – 0.6 mL of the residue remains in the distillation flask or the mixture began
smoking or bumping.
 Isolation and drying of the product
The distillate was transferred to a separatory funnel with the aid of 3mL saturated sodium
chloride solution. (Erlenmeyer flask and Pasteur pipette were not necessarily used)
 Distillation
Drying agent was not used and added into the crude 4-methylcyclohexene before starting
with distillation process. The 25mL round bottom flask was used as a receiver that had been
recorded of its weight. The temperature range which was most of the product distils was the
boiling point of 4-methylcyclohexene.
 Unsaturation test
Three drops of 4-methylcyclohexanol was placed in two separate test tubes. Six drops of
bromine in carbon tetrachloride was added in one of the test tube and four drops of
potassium permanganate was added in the other test tube. Another three drops of 4-
methylcyclohexene that was obtained in the experiment was placed in two separate test
tubes. Six drops of bromine in carbon tetrachloride was added in one of the tube and four
drops of potassium permanganate in the other test tube. The result was recorded and
explained in discussion.
DATA, RESULT AND CALCULATION

Weight of empty 50mL round bottom flask = 49.2237 g

Weight of empty 50mL round bottom flask + 4-methylcyclohexanol = 56.9658 g
Weight of 4-methylcyclohexanol = 7.7421 g

Weight of empty Erlenmeyer flask = 92.2876 g

Weight of empty Erlenmeyer flask + 4-methylcyclohexene = 96.4320 g
Weight of 4-methylcyclohexene = 4.1444 g

Calculation:

Molecular weight of 4-methylcyclohexanol = 114.2 g/mol

Molecular weight of 4-methylcyclohexene = 96.2 g/mol

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

Mass of 4−methylcyclohexanol
Mol of 4-methylcyclohexanol =
Molecular weight of 4−methylcyclohexanol

7.7421 g
=
114.2 g/mol

= 0.0678 mol

Therefore, 0.0678 mol of 4-methylcyclohexanol was produced.

Mass of 4-methylcyclohexene = 0.0678 mol × 96.2 g/mol

= 6.5224 g

4.1444 g
Percentage yield of 4-methylcyclohexene = × 100%
6.5224 g

= 63.5%

Boiling point range for experimental = 79C

Boiling point range for literature = 104C

Table 1. Unsaturation Test

Test tube Unsaturated test Observations

1 4-methylcyclohexanol + Br in CCl4 Colourless to yellow
2 4-methylcyclohexanol + KMnO4 Colourless to dark purple
3 4-methylcyclohexene + Br in CCl4 Colourless to cloudy
4 4-methylcyclohexene + KMnO4 Colourless to brown
DISCUSSIONS

The dehydration reaction of alcohol in this experiment is called the elimination reaction.
Elimination reaction includes the loss of a small molecule (H-X) from adjacent carbon atom,
resulting in pi-bond formation. Thus, elimination reaction is a good synthetic method for
producing alkenes.

Based on the experiment done, acid-catalysed dehydration is proved to be able to

produce significantly good amount of alkenes. The percentage yield shows that more than half
of the alcohols is able to produce alkenes. The treatment of 4-methylcyclohexanol with
phosphoric acid and sulphuric acid resulting in loss of water and formation of 4-
methylcyclohexene.

The unsaturation test also helped to show that the synthesis was successful. The colour
change can be observed in Table 1. The colour change of 4-methylcyclohexene with bromine
in carbon tetrachloride indicates that the double bond is present.

There were a few precaution steps that should be taken during the experiment. When
handling the highly concentrated acid such as phosphoric acid and sulfuric acid, it is best to
make sure that the transfer of those acids is done in the fume-hood. The other step is the
remaining of product which is 4-methylcyclohexene should be disposed carefully into the
organic wastes bottle instead of pouring it into the sink to avoid clogging.

CONCLUSIONS

4-methylcyclohexene is able to be synthesized from 4-methylcyclohexanol through acid-

catalysed dehydration reaction which is the elimination method.
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?
Elimination reaction.

3. Why is the receiving flask supposed to be kept on ice during the preparation of cyclohexene?
To keep it at low temperature during the reaction and distillation because the resultant
alkene has a low boiling point as to which it can evaporate easily. Hence, it is to reduce
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
REFERENCES

(4R)-4-Methylcyclohexene. (n.d.). Retrieved October 4, 2019, from

http://www.chemspider.com/Chemical-Structure.21428309.html.

McMurry, Susan.McMurry, John. (2011) Study guide and solutions manual, Fundamentals of
organic chemistry, seventh edition, John McMurry /Belmont, CA : Brooks/Cole

Alkenes: Preparations. (2016). Retrieved October 4, 2019, from

https://www.cliffsnotes.com/study-guides/chemistry/organic-chemistry-i/structure-and-
properties-of-alkenes/alkenes-preparations.

Libretexts. (2019, June 5). Alkenes from Dehydration of Alcohols. Retrieved October 4, 2019,
from
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_(Organi
c_Chemistry)/Alkenes/Synthesis_of_Alkenes/Alkenes_from_Dehydration_of_Alcohols.
PROCEDURE

1. Apparatus for simple distillation was set up. 50 mL round-bottom flask was used as the
distilling flask and 25 mL round-bottom flask as a receiver.
2. An ice bath was placed around the receiver to reduce the loss of product by evaporation.
3. An empty 50 mL round-bottom flask was weighed.
4. 7.5 mL of 4-methylcyclohexanol was placed by using graduated pipette in the round-
bottom flask. The flask was reweighed again to get the mass of the alcohol.
5. Then, 2.0 mL of 85% phosphoric acid and 30 drops of concentrated sulfuric acid was added
along with 1 or 2 boiling chips in the distillation flask and thoroughly mixed. Mixture was
heated using a heating mantle and distilled slowly while maintaining the distillation
temperature below 100⁰C. Distillation process was continued until only 0.5-0.6 mL of
residue remained in the distillation flask or when the mixture began smoking or bumping.
6. Afterwards, the distillate was mixed with 3 mL of saturated NaCl solution and the mixture
was transferred to a test tube. The test tube was cork tightly and the layers was mixed by
swirling and shaking gently.
7. The layers was allowed to separate.
8. The apparatus was cleaned, dried and reassembled.
9. 25 mL round-bottom flask was used as a receiver that has been weighed while capped.
10. The cyclohexene was transferred with a Pasteur filter pipette into the distillation apparatus.
11. 1 to 2 boiling chips was added and distilled, the portion was collected with a boiling range
of 100⁰C-105⁰C in the flask, chilled in an ice bath.
12. The flask was reweighed.
13. The percentage yield of 4-methylcyclohexene was calculated.
 CHM457 FUNDAMENTAL ORGANIC CHEMISTRY

EXPERIMENT 2 : PREPARATION OF 4 – METHYLCYCLOHEXENE

NAME : SYANAYA NASYA BINTI SHAHRONY

MATRIC NO : 2019608156

GROUP : AS245S2

PARTNERS’ NAME : 1) ASRIN AWANG SELAN

2) NUR HISMANIZA BINTI MORSIDI

3) NURNADZIRAH NABIHA BINTI JAMI’AN

LECTURER’S NAME : DR MOHD TAJUDIN MOHD ALI

DATE OF EXPERIMENT : 27 SEPTEMBER 2019

DATE OF SUBMISSION OF REPORT : 4 OCTOBER 2019