PREPARATION AND PURIFICATION OF AN

ALKYL HALIDE
C.M. CABRERA1 AND J.J. CHUA1
DEPARTMENT OF FOOD SCIENCE AND NUTRITION, COLLEGE OF HOME
ECONOMICS
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY 1101,
PHILIPPINES
DATE PERFORMED: 25 JUNE 2015

ABSTRACT
This paper aims to describe the method of preparation of tert-butyl chloride, an
alkyl halide, through tert-butyl alcohol and concentrated hydrochloric acid, the
mechanism of the reaction that is taking place during the synthesis, and the
purification method of distillation to acquire a purer product. The said
objectives are attained by the integration of the authors current knowledge
regarding the study of Reactions of Alkyl Halides and organic synthesis, which
serves as an application of this knowledge. Through use of a separation
technique that involves the separatory funnel, the S N1 mechanism taking place,
and exposure to a simple distillation setup, 0.8 mL of tert-butyl chloride was
obtained from 10.0 mL tert-butyl alcohol. With respect to the stoichiometry of
the overall reaction, the percent yield is 6.912%.

INTRODUCTION

During Post World War I, the need of

tremendous amounts of resources;
these ranging from food and guns, to
toluene and glycerol for industrial
laboratory use are widespread over
the affected countries [1]. As an
answer to the growing necessities of
the populations, the synthesis of
organic compounds was developed.
The synthesis of any organic
compound
requires
the
accomplishment of the framework of
the desired molecule, introduction,
transformation
or
removal
of
functional
groups,
exercising
selective stereocontrol, production
of reasonable amount of pure
products and taking into account the
economical aspect of the process
[2]. Each aspect of the process is
further made efficient; allowing the
synthesis of organic compounds an
important form of experimentation;

both in the industrial and domestic

aspects.
The preparation and purification of
tert-butyl chloride (C4H9Cl) is a
preliminary trial and stepping stone
to understand the basic mechanics
of the synthesis of alkyl halides, in
the
micro
laboratory
setting.
Following the transformation or
removal of functional groups, the
general view of the process is the
conversion of a tertiary alcohol to a
corresponding halide by a reaction
with hydrohalogen acids, all under
the SN1 mechanism [3]. For this
case, the use of the reagents tertbutyl
alcohol
(C4H10O)
and
hydrochloric acid (HCl) as the
tertiary alcohol and hydrohalogen
acid
respectively
and
the
construction of a simple distillation
setup are utilized. The overall
nucleophilic substitution reaction for

the yielding of the desired product,

tert-butyl chloride, is as follows:
[4]

The aim of this experimentation is to

synthesize crude tert-butyl chloride
from the reactions of the tertiary
alcohol
tert-butyl
alcohol
and
concentrated hydrochloric acid and
to acquire a pure product by using a
simple distillation setup.
METHODOLOGY

As mentioned above, the preparation

of the Alkyl Halide tert-butyl
chloride would require two different
reagents for synthesis, namely, tertbutyl alcohol and hydrochloric acid.
In addition to these reagents,
sodium chloride (NaCl) solution,
sodium bicarbonate (NaHCO3), and
anhydrous Calcium chloride (CaCl 2)
are also used in the experiment to
aid the formation of tert-butyl
chloride.
The two main reagents, tert-butyl
alcohol
and
cold
concentrated
hydrochloric acid, were first added
together into a separatory funnel in
a 10:20 mL ratio respectively. The
funnel was then swirled gently by
using a stirring rod. After which, the
solution was left to stand in order
for the layers to settle. 3 mL 6 M
NaCl solution was added into the
funnel to facilitate the separation of
the two layers.
After the two layers have formed, a
few drops of water were added into
the funnel to determine which layer
is the aqueous layer, noting that the
water should dissolve in it. The
determined aqueous layer was
removed from the funnel carefully,
and was discarded. The organic
layer on the other hand was
transferred into a dry flask with
sodium bicarbonate. This mixture
was gently swirled to mix, and was

decanted into another dry flask;

where it was treated with anhydrous
calcium chloride for desiccation. The
indicator by which the tert-butyl
chloride should be decanted into a
round bottom flask for the next
phase of the experiment is when the
calcium chloride clumps together.
Once decanted into a 25-mL round
bottom flask, boiling chips were
added into the solution, and was
distilled through a simple distillation
set-up. The solution that boiled at
temperatures around 49-52C was
collected into a flask in an ice bath.
The distillate was measured through
a graduated cylinder to get the
volume; a step vital to the
determination
of
the
yield.
Afterwards, a solubility test with
distilled water was done to identify
whether the acquired product is
pure.
RESULTS AND DISCUSSION

The aforementioned methodology

was done to attain the goals of the
experimentation: to synthesize and
purify the alkyl halide, tert-butyl
chloride.
The general overview of the
nucleophilic substitution reaction
between tert-butyl alcohol and
hydrochloric acid is as follows:

Fig. 1. Nucleophilic Substitution Reaction of

tert-butanol and Hydrochloric acid

The synthesis of tert-butyl chloride

involves a series of elementary
steps,
which
constitute
the
mechanism of the reaction. Since
the reaction proceeds in an S N1
fashion [5], the mechanism is twofold: the loss of the leaving group to
form
a
carbocation
and
the
nucleophilic attack from either face
of the flat carbocation [6]. The
mechanism starts upon addition of

excess cold HCl to tert-butanol. HCl

is cooled before addition due to the
volatility of the other reagents;
phase change will tamper with the
concentration of the reagents and to
the yield of the experiment.

The
positive
charge
of
the
carbocation made it susceptible to
nucleophilic attack, which results to
the nature of organic reactions; the
interaction of electrophiles and
nucleophiles.
The
attraction
between the opposing charges
brings about the formation of tertbuyl chloride.

Fig. 2. Movement of electrons and

Protonation

The reaction above is basically an

acid-base reaction. The strongly
acidic character of HCl made it act
as a Bronsted-Lowry acid; therefore
protonates the OH- attached to the
tert-butanol.
The
transfer
of
electrons resulted in the bond
breakage of the H-Cl bond and
formed the O-H bond at the side of
the tert-butanol. The OH- is now
assigned as the leaving group, and
the time by which this takes place
determines the rate of the reaction.
Although adding HCl will not
increase the rate of the reaction, it
ensures that all tert-butanol are
reacted to form the desired product
[7].

Fig. 3. Transition State

The generation of positive charges

brought about by protonation of the
OH- group introduced the highest
energy, with respect to the reactants
and productsthe transition state.
This part of the mechanism is least
stable. It leads to the formation of
the carbocation and water.

Fig. 4. Formation of desired product

Fig. 5. Reduction of solvation of tert-butyl

chloride through differences in polarities

By this time, an emulsion of the

water-insoluble produce, tert-butyl
chloride and excess HCl is present
in the separatory funnel. The
pronounced separation of layers is
facilitated by addition of the
saturated NaCl solution, a process
that is referred to as salting-out
[8]. Since there are ions that are
introduced,
the
differences
in
polarity will be more evident; thus,
more distinct layers.
Fig. 6. Reaction of Sodium bicarbonate and
Hydrochloric Acid

Addition of solid Sodium bicarbonate

reacts with excess concentrated HCl
in
an
acid-base
neutralization
reaction. The salt is added in solid
form due to the aim of desiccation. If
aqueous sodium bicarbonate is used,
more water will be introduced to the
set-up. Once the reaction above has
taken place, anhydrous CaCl2 that
was added next will dry solution up
of water. Since it is seen in the
general reaction (Fig. 1.) that water
is in the products side, introduction
of water generates the formation of
the reagents, which is not favorable
for this experiment. Le Chtelier's
Principle reverses the equilibrium
towards the formation of reagents
which will lower the yield of the
experiment [5].

insolubility of tert-butyl chloride in

water.

Fig. 7. Formation of isobutylene

Although it is only in small portions,

if present, the reagents of the
experiment may react in a different
way; the formation of the alkene,
isobutylene, is plausible. As a
hydrocarbon that is gaseous in room
temperature, it is presumed that
isobutylene is already expelled out
of the separatory funnel during the
swirling actions [5]. This formation
will tamper with the yield of the
experiment.
Once the aqueous layer has been
filtered out, the organic layer was
subjected to distillation. Through
distillation, where selectivity for the
fraction at which the species at a
certain temperature that is within
the range of the boiling point of the
substance to be isolated is practiced,
it can be ensured that the substance
being
collected
at
a
certain
temperature is mainly the tert-butyl
chloride. This is certain due to the
boiling point of the solvent used is
highly different with the desired
product.
Through the distillation
process, boiling chips were added
into the sample to make the boiling
gentler; ensuring no droplets would
go directly into the condenser. If
drops were to be delivered to the
condenser, impurities to the product
might occur. In order to achieve the
maximum yield of the purified
product, continuous water flow must
also be enforced in order to have
maximum
cooling.
After
the
distillation process, it is expected
that the distillate acquired is purer
than the organic layer acquired from
the separatory funnel. The distillate
is also added to water to test its
solubility, which turned out to be
immiscible. This step will somehow
ensure the presence of a waterinsoluble compound; considering the

After the distillation process, the

vital experimental data are taken
into account (Table 1.).
Table 1. Volume and Mass of the Limiting
reactant and product

Volume, mL
Mass, g

t-Butanol

t-Butyl
chloride
[experimental]

10.00
7.886

0.8000
0.6808

With respect to the overall reaction,

the mole relationship of the reagents
to the products is 1:1. This fact
implies that the number of moles of
tert-butanol should be equal to the
yielded tert-Butyl chloride. After
computation of stoichiometry, the
following data are acquired:
Table 2. Experimental and Theoretical
results

mmol
Mass, g
Percent
Yield

Theoretical

Experiment
al

106.4
9.849

7.354
0.6808

6.912%

The possible reasons for a low

percent yield that the authors
suggest
are
the
possible
overproduction of isobutylene and
the incomplete desiccation of the
system. It is already mentioned that
the side-product isobutylene is
derived from the reagents that were
used in the synthesis, which means
that
with
respect
to
the
concentration of the reagents used,
there will be a drop in the percent
yield. This can also be held true for
the incomplete desiccation. Excess
water will reverse the equilibrium
process to the left, which is the
formation of the reagents.
SUMMARY AND CONCLUSIONS

In conclusion, the synthesis of tertbutyl chloride through nucleophilic

substitution by the SN1 mechanism

from
tert-butyl
alcohol
and
hydrochloric acid was successful,
however the percent yield presented
to be greatly below the theoretical
yield computed, falling at only
6.912% out of the ideal 100%, or
only 0.6808 g out of the theoretical
9.849 g. The low yield may be due to
the production of the side product,
isobutylene, or the excess of water
in the system which may have cause
the reaction to move in a backward
manner converting the tert-butyl
chloride back to tert-butyl alcohol.
However, despite the low yield the
compound produced demonstrated
high purity as it fulfills one of the
characteristics of pure tert-butyl
chloride
with
regard
to
its
immiscibility in water.
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