Preparation and Purification of an Alkyl Halide

Bryan B. Arguilles
Department of Food Science and Nutrition, University of the Philippines, Diliman, Quezon City
Date Performed: February 26, 2015
Date Submitted: March 10, 2015
Abstract
The study demonstrated the processes involved in the synthesis of an alkyl halide, particularly
tert-butyl chloride, from tert-butyl alcohol, a tertiary alcohol with the aid of cold concentrated
HCl, a hydrohalide. The process is known to be governed by unimolecular nucleophilic
substitution (SN1) reaction mechanism. 20 mL of cold concentrated HCl was added to 10 mL of
tert-butyl alcohol in a separatory funnel to yield the aforementioned alkyl halide. Simple
distillation was performed afterwards to purify the product collected. The experiment was able to
provide 6.048 g final product or 62.47% of the calculated theoretical 9.68 g tert-butyl chloride
gain. Results from this study showed that the synthesis of tert-butyl chloride may be deemed
successful. On the other hand, the 37.53% loss may have been caused by some side reactions,
errors committed by the experimenters such as inaccuracy in the proportion of reagents, and
inevitable environmental factors. Nevertheless, it has provided an accurate background
regarding the basic concepts of the S N1 reaction mechanism and the synthesis of an alkyl halide
itself.
I. Introduction
Organohalides refer to those compounds
containing one or more halogen atoms.
Good examples of these are the alkyl
halides. As the name suggests, halogen
atoms in an alkyl halide are bonded to an
alkyl group with saturated, sp3-hybridized
carbon atom. These halogen atoms are
considered
substituent
to
the
hydrocarbon parent chain. Because of the
difference in the electronegativity of
carbon and halogen atoms, alkyl halides
are classified as polar compounds. The
carbon atoms bear a slightly positive
charge while the halogens carry a slightly
negative charge. This implies that alkyl
halides act as electrophiles during polar
reactions. [1]
Alkyl halides may be classified according
to the number of alkyl groups attached to
the carbon atom bonded to the halogen.
A primary (1) carbon atom bonded to
only one other alkyl group, will yield a
primary alkyl halide while secondary (2)
carbon atom attached to two other alkyl
groups will produce a secondary alkyl
halide and a tertiary (3) carbon atom
bonded to three other alkyl groups will
give a tertiary alkyl halide. [2]

Currently, there exists several ways of

synthesizing alkyl halides. Examples are
by means of hydrohalo-genation, free
radical halogenation and allylic bromination. These reactions can be used to
produce alkyl halides from alkanes,
alkenes, alkynes and other halides. [2]

Another way is through the use of alcohol

and hydrogen halides halogens bonded
to a hydrogen atom (H-X). The said
reaction
is
governed
by
SN1
or
unimolecular nucleophilic substitution
reaction me-chanism. We know that
halogens are more electro-negative than
its hydrocarbon parent chain. Because of
this, the halogens will donate electrons to
the
electrophilic
carbocation
intermediate. In this mechanism, the
stability hierarchy is an important factor
and thus should be taken into account.
The rate of reaction is influenced by the
stability of the carbocation formed. The
greater the stability of the intermediate
formed, the faster the reaction rate. [1]
In this experiment, a tertiary carbocation
inter-mediate was formed from the
reaction of tert-butyl alcohol, a tertiary
alcohol and cold concentrated HCl, a

hydohalide (Figure 1). The chloride ion will

dissociate from HCl and bond with this
electrophilic carbo-cation producing tertbutyl chloride, an alkyl halide, which is
also the major product. This reaction also
produced water as a byproduct. Because
of this, further purification is needed to
increase the yield of tert-butyl chloride.
Simple distillation, a purifying process
that separates components of a mixture
or compound due to differences in boiling
point, was performed to produce to final
product.

Figure 1. Reaction between tert-butyl

alcohol and cold hydrochloric acid
The experiments goal is to demonstrate
the synthesis of haloalkane by mixing an
alcohol and a hydrohalide and to purify
the product using simple distillation.

separatory funnel because water has a

greater density than tert-butyl chloride.
This layer was discarded afterwards.
The organic layer was then transferred to
a dry Erlenmeyer flask containing a small
amount of solid NaHCO3 to remove traces
of excess acid. After swirling, it was
decanted to another dry flask.
A small amount of anhydrous CaCl 2 was
added to the crude tert-butyl chloride to
remove the traces of water and unreacted
alcohol. It was then transferred to a dry
25 mL round bottom flask for the
distillation process.
The
distillation
set-up
(Figure
2)
composed of two adapters, where the
sample and receiving flask was attached,
linked to both ends of a condenser, where
a pair of rubber tubes was attached to a
bucket of water with a pump, was
assembled
and
prepared
prior
to
distillation.

II. Methodology
20 mL of cold concentrated HCl was
mixed with 10 mL of tert-butyl alcohol in
a dry 50 mL separatory funnel and the
mixture was gently swirled. It is important
to note not to shake the mixture to avoid
any unwanted side reactions. Since the
separatory funnel used in the experiment
doesnt have a cover, there is no need to
relieve the internal pressure because it is
already in equilibrium with the external
pressure.
The mixture was left undisturbed for 20
minutes to give way for layer formation.
3-5 mL of 6 M NaCl solution was added to
the mixture to facilitate the separation of
layers.
After the distinct separation of the two
layers, a few milliliters of water were
dropped to the mixture to determine
which the aqueous layer is. As what the
rule like dissolves like implies, the layer
in which the water dissolves is the
aqueous layer. Theoretically, the aqueous
layer will form at the bottom of the

Figure 2. Simple Distillation Set-up

The round bottom flask containing the
sample was heated using a hot plate. A
cork was used to secure the thermometer
in the adapter such that the bulb is
placed near the opening of the adapter
leading to the condenser. This is to
monitor the temperature at which the
sample boils. Since the product is highly
volatile, the receiving flask was kept
chilled using an ice bath. The fraction that
boiled at 49-52 C was collected after
discarding the first few milliliters. The

volume of the final product was then

measured dropwise using a Pasteur
pipette and recorded.

III. Results and Discussion

The experiments aim is to produce an
alkyl halide from tert-butyl alcohol and
cold concentrated HCl.
(1) (CH3)3COH + HCl (CH3)3CCl + H2O
The reaction is governed by unimolecular
nucleophilic substitution (SN1) reaction
mechanism. It involves the substitution of
the alcohols hydroxide functional group
with a nucleophile which, in this case, is
the halogen chlorine that ionized from the
cold HCl solution to yield the final alkyl
halide product. Unimolecular denotes that
the reactions rate depends solely on the
substrate which is the tert-butyl alcohol
and not the nucleophile. Tertiary alcohols
works best for this type of reaction since
a stable carbocation is formed. [1]
The mechanism of reaction is illustrated
by the following figures.

Figure 1. Protonation of hydroxyl group

by the acid

Figure 3. Reaction of chloride with

tertiary carbocation forming the alkyl
halide product
The initial step is the protonation of the
alcohol by the hydronium ion from the
hydrochloric acid. The reaction is a
Bronsted acid-base reaction with the
alcohol acting as the base or proton
acceptor. This protonation yielded a good
leaving group which is the stable halide
ion. [2]
The oxonium ion, which is the result of
the protonation, releases water molecule.
The oxygen takes with it an electron from
the carbon where it was previously
attached. This leads to the formation
stable tertiary carbocation.
The final step is the introduction of
nucleophile chlorine into the carbocation
intermediate forming the desired alkyl
halide tert-butyl chloride. This is where
the substitution occurred.

Figure 2. Dissociation of water yielding a

tertiary carbocation

The experiment required the use of a cold

concentrated hydrochloric acid to prevent
immediate evaporation of the product
because
of
the
relatively
high
temperature. Also, at high temperature,
some 2-methylpropene can be formed as
a byproduct through the reaction
mechanism
called
acid
catalyzed

elimination (E1). The process is similar to

the first two steps in the synthesis of tertbutyl chloride through substitution. On
the third step, however, instead of bond
formation
between
carbocation
intermediate and halide, the carbocation
acts as an acid, deprotonates and gives
the H+ to the water molecule producing a
H3O+ ion. The hydronium ion then binds to
the
carbocation,
forming
the
2methylpropene
byproduct.
These
eliminations
are
called
dehydrohalogenation
because
the
hydrogen halide has been removed from
the
alkyl
halide.
Substitution
and
elimination reactions often compete with
each other. [2] The step by step process is
clearly demonstrated by Figure 6.

since the salt reduces the amount of

water in contact with the tert-butyl
chloride, the possibility of occurrence of
solvolysis is lowered. [3]
Once the organic layer was collected, a
small amount of solid NaHCO3 was added
to the solution. The sodium carbonate
removes traces of HCl that may initiate
the E1 reaction mentioned earlier.[4] The
solid form was used instead of the
aqueous one in order to reduce the
amount of water around the organic
compound and prevent hydrolysis of the
alkyl halide back to the original alcohol.[5]
Prior to distillation, the organic compound
was treated with anhydrous CaCl2. This is
also in line with minimizing the amount of
water in contact with the organic layer.
CaCl2 is preferred because Calcium (II) ion
forms complexes with many oxygen
containing organic compounds. CaCl2 also
removes untreated alcohol from the tertbutyl chloride. [6]
The addition of boiling chips to the
organic solution before distillation process
is to prevent overheating and decrease
chances of bumping. Boiling chips are
small pieces of porous materials that are
able to give off a stream of air bubbles
when heated. [7]
The rationale behind the purification by
distillation is the differences in boiling
points of the components of compound to
be separated. [8] The boiling point of water
is 100oC, tert-butyl alcohol is 82oC and
tert-butyl chloride is 51oC.

Figure 4. Formation of alkene byproduct

2-methylpropeme
The acid should be added in excess
(HCl:t-BuOH 2:1) to ensure that all of the
alcohol would be consumed. It also
pushes the reaction to the product side or
to proceed (Le Chateliers Principle).
After the two layers have separated, 6M
NaCl was added to the solution. The salt
aids the separation of layers by breaking
the intermolecular forces of attraction
between the organic and aqueous parts
since sodium chloride has a higher affinity
for water than the organic layer. Also,

The vapor of the tert-butyl alcohol will

come in contact with the thermometer
thus reading the boiling point of that
component. The vapor will then travel
through the condenser where cold water
is continuously flowing. This is where the
vapor will reliquify. The water should be
continuous to ensure that all of the vapor
will be reliquified before reaching the
receiving flask or else, the percent yield
of the experiment will decrease. [8]
The first few drops of the distilled product
was discarded because since it boiled and
evaporated at temperature lower than

that of the tert-butyl chloride, it is not the

desired product.
Tert-butyl chloride is volatile in nature.
That is why the collecting flask is
submerged in an ice bath: to prevent
unwanted evaporation of components.
Although this purification process is fast
and relatively straightforward, it also has
its
disadvantages
or
limitations.
Separation of heat sensitive compounds
cannot be aided with this process since
side reactions might occur during
procedure. Another limitation is that
compounds whose components boiling
points are relatively close cannot be fully
separated.[9]
After all the steps have been followed
subsequently, pure tert-butyl chloride has
been isolated. The following table shows
the experi-mental results.
Table 1. Experimental Results
Weight of tertbutyl alcohol
Weight of tertbutyl chloride
Theoretical
yield
Percent yield

7.75 g
6.05 g
9.68 g
62.47%

The experiment was able to provide 6.048

g tert- butyl chloride. Based on the data
from Table 1, this lead to a quite high
percent yield (62.47%) using the following
equation
(1)

yield=

actual yield
x 100
theoretical yield

The 37.53% loss may be attributed to

some
errors
committed
by
the
experimenters. One example would be
the distillation set up may not have been
properly prepared. Some parts may have
been loosely connected allowing the
escape of vapors that should have been
reliquified as a final product. Also, the
discarded initial distillate may have
exceeded the advisable amounts, leading
to lower percent yield.

Occurrence of side reactions also lowers

the percent yield. The SN1 and E1 reaction
are both competitive reactions. 2methylpropene, a side product whose
formation was discussed earlier in this
paper may have been produced.
Lastly, the effects of anhydrous calcium
chloride are not instantaneous. For the
drying to have been surely maximized, a
waiting time of around twenty minutes
should have been strictly followed. But
due to time constraints, unfortunately,
this was not the case. Water molecules in
contact with tert-butyl chloride were not
completely removed and thus, solvolysis
may have occurred.

IV. Conclusion
Having able to purify 7.2 mL or 6.95 g of
tert-butyl chloride which is 62.47% of the
theoretical 9.73 g, the experiment is can
be considered a bit successful. However,
37.53% of the product was lost. This may
be due to several factors mostly
committed
by
the
experimenters
themselves. But still, the objective of the
experiment is to synthesize and purify
tert-butyl chloride from tert-butyl alcohol
and this was properly achieved in the
experiment. It has provided basic
background regarding the concept of alkyl
halide
and
purification
by
simple
distillation.
To increase the percent yield, it is
recommended that the waiting time for
drying reagents such as NaHCO 3 and
CaCl2 to absorb water be longer. Also, the
distillation set-up should be assembled
properly to avoid the escape of vapors
from the system.

V. References

/carey/student/olc/ch15hydrolysisofalkylh
alides.html>

[1] McMurry, John. Organic Chemistry, 8th

ed.; Edited by Lisa Lockwood. Cengage
Learning: Belmont, CA, 2010; pp. 344-346

[6] Organic Chemistry Laboratory Manual

2008 ed. Institute of Chemistry,
University of the Philippines Diliman,
Quezon City, 1101.

[2] Leory G. Wade, Jr. Organic Chemistry,

8th ed,; Prentice Hall: New Jersey, USA,
2011; pp. 220. PDF file.
<http://www.pearsonhighered.com/wade8
einfo/assets/pdf/wade-ch06.pdf>

[7] University of Colorado. Boiling Chips.

July 14, 2013. Web
<http://orgchem.colorado.edu/Technique/
Procedures/Distillation/Boilingchips.html>

[3] University of Colorado. Drying Organic

Solutions. July 14, 2013. Web
<http://orgchem.colorado.edu/hndbksupp
ort/drying/drying.html>.
[4] WiseGEEK. What Happens When
Sodium Bicarbonate and Acid Meet in the
Stomach?. July 14 2013. Web
<http://www.wisegeek.com/whathappens-when-sodium-bicarbonate-andacid-meet-in-the-stomach.htm>
[5] The McGraw-Hill Companies.
Hydrolysis of Alkyl Halides. July 14, 2013.
Web
<http://www.mhhe.com/physsci/chemistry

[8]Wake Forest University. Simple

Distillation. July 14, 2013. Web
<http://www.wfu.edu/chem/courses/organ
ic/distill/distillation.htm>
[9] Brennan, John, The Disadvantages of
Simple Distillation. July 14, 2013. Web
<http://www.ehow.com/info_8490343_dis
advantages-simple-distillation.html>

VI. Appendices

Reaction scheme

Limiting
Reagent

Excess
Reagent

Volume

10 mL

20 mL

7.2 mL

Mass

7.75 g

29.8 g

6.05 g

Molecular weight
Density

74.12 g/mol

0.775 g/mL

Mmol

104.56 mmol

36.46 g/mol

92.57 g/mol

1.49 g/mL

0.84 g/mL

817.33 mmol

65.33 mmol

Calculations
Mass = Volume x Density
a.

10 mL (C H3 ) 3 COH

0.775 g (C H3 )3 COH
= 7.75 g (C H3 ) 3 COH
1 mL (CH3 ) 3 COH

b.

7.2 mL (C H3 ) 3 CCl

0.84 g (C H 3 )3 CCl
= 6.048 g (C H3 )3 CCl
1 mL (C H3 ) 3 CCl

Millimoles = Mass x Molecular weight x 1000 mmol

a.

7.75 g (C H3 )3 COH

1 mol (CH3 ) 3 COH

1000 mmol = 104.56 mmol (C H3 )3 COH
74.12 g (C H3 ) 3 COH

b.

6.048 g (C H 3 )3 CCl

1 mol (C H3 ) 3 CCl
1000 mmol = 65.33 mmol (C H3 )3 CCl
92.57 g (C H3 )3 CCl

Theoretical yield:

10 mL (C H 3 ) 3 COH
Actual yield:

0.775 g (C H3 )3 COH
1 mL (C H3 ) 3 COH

1 mol (C H3 ) 3 COH
74.12 g (C H3 ) 3 COH

1 mol (C H3 ) 3 CCl
1 mol (C H3 ) 3 COH

92.57 g (C H
1 mol (C H3

7.2 mL (C H3 ) 3 CCl

0.84 g (C H3 )3 CCl
= 6.048 g (C H3 )3 CC l
1 mL (C H3 ) 3 CCl

Percent yield:

% yield =

6.048 g (C H3 ) 3 CCl
100 = 62.47 %
9.68 g (C H3 ) 3 CCl