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. This reaction involved removal of OH⁻ in 1-
bromobutanol and substituted by H⁺ ion from catalyst that is sulfuric acid (H2 𝑆O4 ). 1-
bromobutanol need to be synthesize 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. H2 𝑆O4 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. H2 𝑆O4 is added
cautiously which produced hydrobromic acid then reacts with alcohol to make 1-
bromobutane.

Reagents

1. 17.0g sodium bromide, NaBr

2. 10.0mL of n-butyl alcohol (1-butanol, MW = 74.1, d = 0.81g/mL)
3. 17.0mL distilled water
4. 14.0mL of concentrated sulfuric acid, H2 𝑆O4
5. 14.0 mL of 9M H2 𝑆O4
6. 14.0mL distilled water
7. 14.0mL saturated aqueous sodium bicarbonate, NaHCO3
8. 1.0g anhydrous calcium chloride CaCl2
Apparatus

1. 100ml round-bottom flask

2. 25mL round-bottom flask
3. Pasteur pipets
4. Ice bath
5. Boiling stones
6. Distillation setup
7. Reflux apparatus and trap
8. 125mL separatory funnel
9. 125mL Erlenmeyer flask
10. Weighing balance

Procedure

Preparation of n-Butyl Bromide

Placed 17.0g of sodium bromide (NaBr), 17.0g of distilled water and 10.0mL of
1-butanol in a 100mL round-bottom flask. It was swirled and placed in an ice bath.
Next, 14.0mL of concentrated sulfuric acid were added into the flask 1mL at a time
while swirling. The flask was assembled into a reflux apparatus. A trap was attached
to the top opening of the condenser. It consist of a filter funnel connected to a rubber
hose that attached to the top opening of the condenser. Boiling stones were added.
The mixture were refluxed for 60 minutes. After that, the heat were turned off and the
condensate in the condenser were allowed to drained back into the flask. After cooled,
the mixture were transferred to a separatory funnel.

Extraction
The lower layer were discarded. 14.0mL of 9M H2 𝑆O4 were added to the funnel
and shaken. Again the lower layer were discarded. Then, 14.0mL of distilled water
were added to the flask and shaken. The mixture were separated and the lower layer
were discarded and transferred back into an empty separatory funnel. 14mL of
saturated sodium bicarbonate solution were added and the flask were shaken for 1
minute. The lower layer were discarded into an Erlenmeyer flask. The product were
dried with 1.0g anhydrous calcium chloride. The flask were swirled.

Distillation
The 1-bromobutane were purified by simple distillation. The cleared and dried
liquid were pipetted into a 50mL round-bottom flask. The boiling stone was added and
the distillation started. Any forerun were discarded but the sample that distills above
90-95℃ were collected. The 1-bromobutane were continued to collect up to its boiling
point. The distillate were collected in a pre-weighed flask. The mass and volume of the
purified product were measured.
Results/Data
Weight of odium bromide 27.052 g
Weight of round-bottom flask (100ml) 74.6531 g
Weight of anhydrous calcium chloride 1.0034 g
Weight of flask (50ml) 45.9758 g
Weight flask + 1-bromobutane 46.2718 g
Product ( 1-bromobutane) = 46.2718 – 45.9758
= 0.296 g
Melting point product (1-bromobutane) 97˚C

Calculation
Molar mass Boiling point (˚C) Density (g/cm3)
(g/mol)
1-Butanol 74.1224 117.6 0.81
1-Bromobutane 137.0191 101 1276

The percentage yield of 1-bromobutane

𝟏𝟎 𝒈
No of mol 1-butanol = 𝟕𝟒.𝟏 𝒈/𝒎𝒐𝒍

= 0.135 mol

1 mol of 1-butanol = 1 mol of 1-bromobutane

0.135 mol of 1-butanol = x mol of 1-bromobutane

X = 0.135 mol 1-bromobutane

Mass of 1-bromobutane = 117 g/mol × 0.135 mol

= 15.795 g
𝑬𝒙𝒑𝒆𝒓𝒊𝒎𝒆𝒏𝒕𝒂𝒍 𝒚𝒊𝒆𝒍𝒅
Percentage yield (%) = 𝑿𝟏𝟎𝟎%
𝑻𝒉𝒆𝒐𝒓𝒆𝒕𝒊𝒄𝒂𝒍 𝒚𝒊𝒆𝒍𝒅

𝟎.𝟐𝟗𝟔 𝒈
= 𝑿𝟏𝟎𝟎%
𝟏𝟓.𝟕𝟗𝟓 𝒈

= 1.87 %

The boiling point of n-butyl bromide = 97.0 ℃

Discussion

In every chemical reaction, there is a direct relationship between the rate at

which the reaction occurs and the concentrations of the reactants. When we measure
this relationship, we measure the kinetics of the reaction. With the given temperature,
solvent, and concentration of reactants, the substitution occurs at a certain rate. The
second-order reaction which this reaction in which the rate is linearly dependent on
the concentration of two species. A mechanism that accounts for both the inversion of
configuration and the second-order kinetics that are observed with nucleophile
substitution reactions was SN2.

The boiling point of this product in this experiment is 97˚C, so the boiling point
is close to 1-bromobutane which has 101˚C as it boiling point. As we already know
alcohol do not undergo nucleophile substitution reactions because hydroxide ions are
strongly basic and poor leaving group. The leaving group is a group of atom which
depart with the electron pair used to bond them with the substrate. However, alcohols
readily undergo SN2 because the sulphuric acid was added which protonate the
hydroxyl group in the presence of the bromide ions to react with it in the same mixture.

Based on the calculation we has been calculated, the percentage yield for our
experiment is 1.87%. So this percentage yield small because we got the small amount
of product so that we cannot get the actual mass of the product produced. This is
because maybe we using the large volume of round-bottom flask that actually are not
suitable for the small amount product that we got, then the process of reflux cannot be
running well.

For this experiment make sure use glove, face mask, and always washing hand
after handling the substance this because the substance which is fluid itself is very
high flammable that can irritate our skin. Besides, we must handling the high
concentration acid so wearing the suitable glove and mask is a must.

Conclusion

For this experiment it is involved second order nucleophile substitution, S N2.

The 1-Butanol was used to prepare 1-Bromobutane. The theoretical yield obtained
for this experiment is 15.795g and the actual yield is 0.296g. The percentage yield is
1.87%. The melting point is 97˚C close to the boiling point of 1-bromobutane which is
101˚C, so the product in our experiment is 1-bromobutane.

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. What are the formulas of the salts that may precipitate when the reaction
mixture is cooled?
- Butyl alcohol, sodium bromide and sulphuric acid
-

2. Why does the alkyl halide layer switch from the top layer to the bottom
layer at the point where water is used to extract the organic layer?
- This is because the density of alkyl halide is higher than water. Thus, water
was added, the lower layer would be an alkyl halide.

3. An ether and alkene are formed as by-products in this reaction. Draw the
structure of these by-products and give mechanisms for their formation.

4. Aqueous sodium bicarbonate was used to the crude n-butyl bromide.

a) What was the purpose of this wash? Give equation.
- To naturalize the trace amount of HBr present in the solution due to
elimination by product or hydrolysis of alkyl halide.

HBr + NaHCO3 H2CO3 + NaBr

b) Why would it be undesirable to wash the crude halide with aqueous

sodium halide?
- Because it is very polar and will act as base by giving an elimination product
or a nucleophile by giving substitution reaction.
5. Look up the density of n-butyl chloride (1-chlorobutane). Assume that
this alkyl halide was prepared instead of the bromide. Decide whether
the alkyl chloride would appear as the upper or lower phase at each
stage of the separation procedure; after the reflux, after the addition of
water, and after the addition of sodium bicarbonate.
- After a reflux: upper layer
- After the addition of salt: lower layer
- After the addition of sodium Bicarbonate: lower layer

6. Why must the alkyl halide product be dried carefully with anhydrous
calcium chloride before the distillation?
- Because if its not dried, you are likely to get some water vapour in your
distillate.