Experiment 3 : Preparation of 1-bromobutane from 1-

bromobutanol

Objective

1. To produce 1-bromobutane from 1-bromobutanol.

2. Find percentage of yield of 1-bromobutanol.
3. Identify the boiling point of 1-bromobutane.

Introduction

In order to synthesize 1-bromobutane, 1-bromobutanol need to undergo nucleophilic

substitution reaction first. This reaction involved removal of OH⁻ in 1-bromobutanol
and substituted by H⁺ ion from catalyst that is sulfuric acid ( H 2 S O 4 ). 1-bromobutanol
need to be synthesize first by reacting 1-butanol with sodium bromide (NaBr)
according to the following equation:

Bromide ion is a good nucleophile and it came from the NaBr. Meanwhile OH⁻
ion is a poor leaving group. H 2 S O4 acts as a catalyst and convert OH⁻ ion into a
good leaving group or water.
In this experiment, NaBr and 1-butanol are dissolved in water. H 2 S O 4 is added
cautiously which produced hydrobromic acid then reacts with alcohol to make 1-
bromobutane.

Reagents

1. 7.5mL of 4-methylcyclohexanol
2. 2.0mL of 85% phosphoric acid, H 3 P O4
3. 30 drops (0.4mL) of concentrated sulfuric acid, H 2 S O 4
4. Saturated sodium chloride solution, NaCl
5. Bromine test reagent
6. Potassium permanganate test reagent
 Apparatus

1. 50mL round-bottom flask

2. Erlenmeyer flask
3. Glass stirring rod
4. Pasteur pipets
5. Boiling stones
6. Distillation apparatus
7. Ice-water bath
8. Heating mantle

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 a 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-bottom flask using graduated pipets.

Dehydration
The distillation temperature was maintained below 100 oC. the heating should
be regulated so that the distillation requires about 30 minutes. Continue the
distillation until no more liquid is collected. The distillate contains 4-mthylcyclohexene
as well as water.

Isolation and drying of the product

The distillate was transferred to a separatory funnel with the aid of 3ml
saturated sodium chloride solution. Allow the layer to separate and remove the
bottom aqueous layer with Pasteur pipet and discard it. Transfer the organic layer
remaining in separatory funnel to an Elenmayer flask containing small amount of
anhydrous sodium sulfate. Place stopper in the flask and set it aside and for 10
minutes to remove the last trace water. During this time, wash and dry the distillation
apparatus, using the small amounts of actone and air stream to aid the drying
process.

Distillation
Drying agent was prevented before starting with distillation process. The 25ml
round-bottom flask was used as a receiver that should be pre-weighed. The
temperature range which is most of the product distils is the boiling point of our 4-
methylcyclohexene.

    
Unsaturated tests using Bromine in CCl4 and Potassium Permanganate
3 drops of 4-methylcyclohexanol were placed in 2 separate test tubes. 6 drops
of Bromine in CCl4 were added in one of the test tube and 4 drops of potassium
permanganate were added in another test tube. Any colour change were observed.
3 drops of 4-methylcylohexene that were obtained were added in 2 separate
test tubes. 6 drops of Bromine in CCl4 were added in one of the test tube and 4
drops of potassium permanganate in another test tube. Any colour change were
observed.

Results/Calculation

Weight of 50mL flask = 64.6872 g

Weight of 50mL flask + 4-methylcyclohexanol = 55.6238 g
Weight of 4-methylcyclohexanol = 9.0634 g

Weight of Erlenmeyer flask = 53.37 g

Weight of Erlenmeyer flask + 4-methylcyclohexene = 60.2284 g
Weight of 4-methylcyclohexene = 6.8584 g (Experimental Value)

Theoretical yield of 4-methylcyclohexene

Molecular weight of 4-methlycyclohexanol = 114.07 g/mol

Molecular weight of 4-methylcyclohexene = 96.07 g/mol
mass
No of mol 4-methylcyclohexanol =
molar mass
9.0634 g
=
114.07 g/mol
= 0.0795 mol

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

0.0795 mol of 4-methylcyclohexanol = 0.0795 mol of 4-methylcyclohexene

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

= 0.0795 mol × 96.07 g /mol
= 7.6376 g

Percentage yield of 4-methylcyclohexene

Experimental yield
x 100%
Theoritical yield

6.8584 g
x 100% = 89.80%
7.6376 g

Test Reactant Observation

Br2 test 4-methylcyclohexanol
4-methylcyclohexene
KMnO4 test 4-methylcyclohexanol
4-methylcyclohexene
No. of drops = 5
Colour changes =
coulorless solution
change to red solution
No. of drops = 5
Colour changes = red
colour bromine
decolourised into
colourless solution
Colourless solution
change to purple colour
Colourless solution
change brown precipitate
formed

Discussion

This experiment was designed to understand the distillation technique,

mechanism involved in the reaction and to synthesize 4-methlcyclohexene through
acid-catalyzed elimination of water from 4-methylcyclohexanol.

In order to produce an alkene, one of the best method is the elimination

reaction. This reaction occur through a process called heterolytic bond cleavage. It
happened when one atom left a compound with electrons of the original bond, thus
ions is formed.

In this experiment, strong acid 85% phosphoric acid and concentrated sulfuric
acid were used that are poor nucleophiles and has high reaction temperature, which
suits elimination. The first step of dehydration is the proton from acid catalyst that is
85% phosphoric acid and concentrated sulfuric acid to the oxygen atom of the 4-
methylcyclohexanol resulting in the formation of conjugate acid of 4-
methylcyclohexanol, oxonium ion. The next step of dehydration is the loss of H 2 O
from the oxonium ion then form a positively-charged secondary carbocation. The last
step is the deprotonation of H 2 O from the carbocation at the adjacent carbons. The
electrons left flow towards the positive charge. Sigma bond was produced between
the carbons then forming a double bond.
 1mol of 4-methylcyclohexanol is equivalent to 1 mol of 4-methylcyclohexene.
The mass of 4-methylcyclohexene theoretically is 7.6376 g while experimental value
is 6.8584 g. The percentage yield of 4-methylcyclohexene calculated is 89.80%

In order to have a safe experiment, be really careful with phosphoric acid and
sulfuric acid used. They are strong acids and can bring injury if they come in contact
with skin. Wear gloves and if they accidently splashed on skin, wash with large
amount of water. Next, avoid adding too much anhydrous sodium sulfate. Lastly,
before beginning the second distillation, the simple distillation apparatus must be
rinsed with acetone so that it is not contaminated.

Conclusion

89.80% of percentage yield of 4-methylcyclohexene was calculated. 4-

methylcyclohexene produced from 9.0634 g 4-methylcyclohexanol and produce
6.8584 g. The theoretical value of 4-methylcyclohexene is 7.6376 g . 4-
methylcyclohexene has been produced and the mechanism involved in the reaction
was understood.

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)
2. Whitmore, F. C. (2012). Organic chemistry. Mineola, NY: Dover.
3. McMurray, J. (2012). Organic chemistry. Belmont, CA: Brooks/Cole.
Question
1. Outline a mechanisme for the dehydration of 4-methylcyclohexaol
catalysed by phosphoric acid.

2. What a major alkene product is produce by the dehydration of the

following alcohols?
a) Cyclohexanol

b) 1-methylcyclohexanol
c) 2-methylcyclohexamol

d) 2,2-dimrthylcyclohexanol

e) 1,2-cyclohexanediol
3. Compare and interpret the infrared spectra of 4-methylcyclohexene and
4-methylcyclohexanol

4. Show the complete acid-catalysed mechanisme for the dehydration of 2-

methylcyclohexanol.