Preparation and Purification of an Alkyl Halide

Abstract
Alkyl halides consist of an alkyl group linked to a halogen atom (X) by a single bond. It can
be prepared by reacting it with a hydrohalogen (HX). In this experiment, tert-butyl chloride was
synthesized through the reaction of tert-butyl alcohol and concentrated hydrochloric acid
following SN1 mechanism. It was then separated from its aqueous solution using a separatory
funnel given the knowledge that is insoluble in water. A simple distillation set-up was equipped to
purify the obtained compound. The experiment was successfully able to synthesize an alkyl
halide as the end product tert-butylchloride obtained was found to be colorless, having a boiling
point of 51 C, which agrees with the theoretical boiling point of tert-butyl chloride. However, due
to some errors, only 5.26 grams of the product was obtained, giving a percent yield of 53.93 %,
suggesting a more careful execution of the procedures.

I. Introduction
Alkyl halides, also called haloalkanes,
simply have a halogen atom bonded to one
of the sp3 hybrid carbon atoms of an alkyl
group. The halogen is more electronegative
than carbon, and the C X bond is polarized
with a partial positive charge on carbon and
a partial negative charge on the halogen. A
generic formula of R-X where X = fluorine,
chlorine, bromine or iodine would be suitable
for these compounds. These are classified
according to the nature of the carbon atom
bonded to the halogen. If the halogen
bearing carbon is bonded to one carbon, it is
called primary halide (1). If there are two
carbons bonded to the halogen-bearing

carbon, then it is a secondary halide (2). If

three carbons are bonded to the halogenbearing carbon, then it is a tertiary halide
(3).
Figure1. Classification of Alkyl Halides
according to the number of carbon/s
attached to them[2].
Alkyl halides had been very useful to
us since a long time ago until now. Most
syntheses use alkyl halides as useful
reagents in making more complex molecules.
Freons, (also called chlorofluorocarbons, or

CFCs) are also alkyl halides that was once a

popular refrigerant. Alkyl halides are also
widely used as insecticides such as DDT
(DichloroDiphenyltrichloroethane),
a
chlorinated insecticide and as anesthetics
like CHCl3 or more commonly known as
chloroform[4].
These
applications wouldnt be possible without the
preparation of alkyl halides. Synthesis of
alkyl halides are of major importance in
industry as well as in the laboratory. As a
matter of fact, synthesis of alkyl halides had
been one of the three most useful classes of
organic reactions[1].
There are many different ways on how
to synthesize these compounds. These can
be prepared from alkanes through freeradical halogenation but this is useful only in
certain cases. These can also be obtained
from alkanes and alkynes through allylic
bromination and even from other halides.
But the most common laboratory method
for the preparation of alkyl halides is the
replacement of the hydroxyl group of an
alcohol with a halogen atom[2].
Alcohols react with hydrohalogen (HX)
but the reaction works well only for tertiary
alcohols. Tertiary alcohols almost react
instantaneously at room temperature, while
primary and secondary alcohols need other
reagents like SOCl2, PBr3 or HF-pyridine for
them to react and form the desired alkyl
halide[2].

This experiment aimed to synthesize

tert-butyl chloride through a nucleophilic
substitution reaction - an SN1 reaction to be
more specific - using tert-butyl alcohol and
concentrated hydrochloric acid. Other than
executing methods concerning synthesis and
distillation, methodology particulars and
elaboration of data presented from the
calculations were also given emphasis.

solid
NaHCO3
and
then swirled. This was decanted into another
dry flask. The collected filtrate was dried
using a small amount of anhydrous CaCl2. A
small amount of anhydrous CaCl 2 is still
added until it clumped together.

II. Methodology

In the distillation process, a distillation

set up was equipped as shown in Figure 3.
The water should continuously flow into the
bottom of the condensers cooling jacket and
out from the top to avoid pressure build up in
the condenser. A thermometer bulb is placed
just below the side arm of the distillation
head. The chosen round bottom flask to be
used is big enough to hold a sample that is
1/3 to 2/3 of its volume. To regulate the
temperature, water bath was used in this
experiment.

10 mL of tert- butyl alcohol and 20 mL

of cold concentrated HCl was placed in a dry
50 mL separatory funnel. It was gently
swirled. The internal pressure was safely
relieved from time to time by slowly opening
the stopcock. The mixture was allowed to
stand undisturbed for twenty minutes. It is
important for the aqueous layer to be
discarded and this can only be done through
the separation of layers in the separatory
funnel. Adding three to five mL of 6 M
sodium chloride solution facilitates this layer
separation. Afterwards, one to two drops of
water was added to any of the separated
layers. This step helped in determining which
the organic layer is.

The crude tert-butyl chloride was

decanted into a dry 25 mL round bottom
flask. Few boiling chips were added before
distilling.

Figure
2a.
Draining the
Lower
Layer

[8]

Figure 3. Simple Distillation Set-up[5]

Figure 2b. Holding

Separatory Funnel[8]

and

Venting

The organic layer is then transferred

into a dry flask containing a small amount of

The sample is then placed inside the

flask. Some pieces of boiling chips were
added into the flask. It is very important to
take note that it is not safe to add boiling
chips to a hot liquid because if a solution is
at or near the boiling point, then the addition
of boiling chips will cause the flask to boil up
suddenly and some of the boiling liquid will
escape uncontrollably from the flask.
The water flow through the condenser
is then checked by turning on the water
supply. All the ground glass joints are
checked, and it is necessary that they are
well
fitted.
The sample was heated in the flask to
a gentle boil. But this time, the temperature
reading on the thermometer rose rapidly.

However, it will remain constant at its boiling

point. The boiling point was taken note. The
vapors and condensate are observed to pass
through the side arm and into the condenser,
where most of the vapour condenses into a
liquid. Finally, it dripped from the adapter
into the receiving flask. The heat was
adjusted such that the distillation occurs at a
rate of 2 drops distillate per second.
The first few millilitres of the distillate
was discarded; but the fraction that distilled
at the desired temperature was collected.
The constant temperature was the boiling
point of the volatile component. It was
distilled first to dryness. After all of these
steps, the sample was waited until it started
to boil. Then, it was immediately removed
from the heat source. The whole set-up was
allowed to cool before dismanting it. Because
the boiling point of tert-butyl chloride is 51
C, only the fraction that boils at 49-52 C was
collected. This pure product is placed in a
pre-weighed vial and was cooled in an ice
bath since the product is highly volatile.
Lastly, the yield for the experiment was
calculated.
III. Results and Discussion
The
presence
of
a
strongly
electrophilic carbon center makes the alkyl
halides susceptible to nucleophilic attack
whereby a nucleophile displaces the halogen
as a nucleophilic halide ion. This is called the
nucleophilic substitution reaction one of the
major reactions undergone by an alkyl
halide.

In this experiment, the desired product

which is the tert-butyl chloride was
synthesized
via
SN1
reaction.
The
requirements for an SN1 reaction to be
possible have been met since tert-butyl
chloride is tertiary and the solvent used is an
alcohol which is a protic solvent. Protic
solvents such as alcohols and water are even
more effective solvents in the SN1 reactions
because anions form hydrogen bonds with
the OH hydrogen atom.
The SN1 reaction involves a two-step
mechanism. The first one is the slow
formation of the carbocation or the so-called
rate limiting step, and the second one is the
fast nucleophilic attack on the carbocation.

Step 1. Formation of the carbocation (slow)

[4]
.

Step 2. Nucleophilic attack

carbocation
(fast)

on

the
[4]
.

As for the experiment, we can see a

convincing evidence that for tertiary
alcohols, the reaction proceeds via S N1
(substitution-nucleophilic-unimolecular)
mechanism. For tert-butyl alcohol, the SN1
reaction with concentrated hydrochloric acid
is
illustrated
as
follows:

I.
Figure
4.
Reaction[4].

Nucleophilic

Substitution

Under this type of reaction are two

kinds of mechanism SN1 and SN2 reactions.
Under protic solvent conditions with nonbasic
nucleophiles, the SN1 mechanism is preferred
and the order of reactivity is as follows [3]:
3 > 2 > 1
It is fair to say that nucleophilic
substitution of tertiary alkyl halides will take
place under the SN1 mechanism while
primary and secondary alkyl halides will
undergo SN2 mechanism.

II.
III.

In step I, the alcohol accepts the proton to

form the protonated alcohol. This dissociates
into a carbocation and water as seen in step
II. This formation of carbocation is favoured
for tertiary alkyl halide since it relieves the
steric strain in its crowded tetrahedral
structure[3].And finally, the chloride ion is

combined with the carbocation (step III) to

form the product tert-butyl chloride.
In order for the experiment to be
carried out successfully, many particulars
were stressed out. Without these, failure of
experiment may occur and the desired
product may not be synthesized.
The first detail that needs not to be
neglected is the use of cold hydrochloric
acid. This is done to prevent the formation of
isobutylene (CH3)2C=CH2 via E1 mechanism.
This isobutylene or 2-methylpropene is
formed as a side product. This is believed to
be inevitable because for almost all cases, a
fraction of the intermediate carbonium ions
lose a proton instead of adding halide ions.
The
mechanism
is
shown
below:

Figure 5. Isobutylene as a minor product [6].

In order for the reaction to limit or
prevent the formation of this side product, a
cold concentrated hydrochloric acid was
used, as already mentioned. Also, these side
products can also be easily eliminated since
it has a very low boiling point compared to
the major product. Hydrochloric acid was
added in excess to ensure that an alkyl
halide will be formed in a reasonable yield.
This is possible knowing the fact that the
formation of tert-butyl chloride follows a first
order rate reaction, meaning, it is dependent
only on the concentration of tert-butyl
alcohol and not with the amount of
hydrochloric
acid
used.
The tert-butyl alcohol and hydrochloric
acid solution was separated from the
aqueous layer in a separatory funnel. After it
was done, the organic layer is transferred to
a dry flask with a small amount of solid
NaHCO3. Solid NaHCO3 was used instead of
aqueous NaHCO3 to neutralize the excess
HCl adequately. Doing another way around
will just expose tert-butyl chloride to a lot of
water and this risks tert-butyl chloride to
becoming an alcohol again.
After this, anhydrous CaCl2 was used to
dry the crude product before distillation. This

step must not be missed so that the traces of

water that may impede the formation of
desired products may be avoided [7].
In
purifying
further
the
target
compound from possible impurities, simple
distillation process was done. Here, the
separation of liquids by vaporization and
condensation of the vapor back to the liquid
phase occurs. The use of boiling chips was
emphasized in this step as it ensures even
boiling and prevents bumping. Bumping
occurs when part of the solvent becomes
superheated and leads to sudden bursts.
Without boiling chips, the process could be
dangerous and may cause some loss of the
product [7]. The continuous flow of water in
the condenser during distillation is necessary
to prevent all the liquid from evaporating and
to prevent pressure build up that may be
explosive
and
dangerous.
Cautiously following the mentioned
particulars, the purpose of the experiment
which is the
preparation of tert-butyl
chloride
from
tert-butyl
alcohol
and
concentrated
hydrochloric
acid
was
successfully employed based the following
equation:
(CH 3)3COH + HCl (CH3)3CCl +
H20
The balanced equation above shows
that hydrochloric acid and tert-butyl alcohol
has a stoichiometric ratio of 1:1. Now, it is
safe to conclude that tert-butyl alcohol is the
limiting reactant because it has a smaller
amount than hydrochloric acid. Therefore,
tert-butyl alcohol will determine the rate of
formation of tert-butyl chloride. Applying this
principle, the following data were obtained:
Table 1.
Properties of tert-butyl
alcohol
Mass
7.809 g
Molecular Weight
74.12 g/mol
Density
0.7809 g/cm3
Mmol
105.36 mmol
Color
clear/colorless
Solubility in water
Soluble
Boiling point
82 C
Table 2. Properties of tert-butyl
chloride
Mass
Molecular Weight
Density
Mmol

5.26 g
92.57 g/mol
0.84 g/cm3
105.36 g

Color
clear/ colorless
Solubility in water
insoluble
Boiling point
51 C
Table 3. Summary of Experimental Results
Mass
of
tert-butyl 7.809 g
alcohol
Mass
of
tert-butyl 5.26 g
chloride
Theoretical yield
9.75 g
Percent yield
53.93 %
Boiling point
51 C
By the end of the experiment, the desired
product was gathered and it was found that
it has a percent yield of 53.93 % and a
boiling point of 51 C, which is almost similar
with its theoretical boiling point.
IV. Conclusion
With a percent recovery of 53.93 %
and with a boiling point of 51 C, the
experiment is reckoned a success as it was
able to obtain the desired product tert-butyl
chloride via SN1 reaction of tert-butyl alcohol
and concentrated hydrochloric acid.
Improvement in the experimental
procedures such as carefully separating the
layers may help to increase the yield of the
desired product because it is possible that
some amount of the organic layer were
discarded together with the aqueous layer.
This experiments errors could be further
minimized by ensuring the completeness of
the distillation process because it is also
possible that not all of the sample compound
was converted to tert-butyl chloride.
All in all, it is always best to follow the
experimental procedures with caution to
improve the results.
V. References:

=(weight
of
vial+tert-butyl
chloride)-weight of vial
=27.52 g 22.26g
= 5.26 g
Millimole of tert-butyl chloride
The equation (CH3)3COH + HCl
(CH3)3CCl + H20 gives us a 1:1 ratio:
=

105.36 mmoltbutyl alcohol

1 mmoltert butyl c h loride

1mmol tert butyl alco h ol

= 105.36 mmol tert-butyl

chloride
VI. Appendices
Calculations:
Mass of tert-butyl alcohol

0.7809

Theoretical Yield of tert-butyl chloride

1 mol
1000 mmol

g
10 ml
ml

105.36 mmoltbutyl chloride(

= 7.809 g tert-butyl alcohol

Millimole of tert-butyl alcohol

105.36

mmol

Mass of tert-butyl chloride

=9.75 g tert-butyl chloride

Percent yield
= (actual/theoretical) x 100
= (5.26g/9.75g) x 100
= 53.93 %

1000 mmol
1 mol
)
1 mol
7.809 g (
)
74.12 g

alcohol

)
92.57 g
)
1mol

tert-butyl

Note: The datasheet is stapled together

with this paper.