PREPARATION AND PURIFICATION OF AN ALKYL HALIDE

Farah Iman F. Deogracias

Institute of Chemistry, University of the Philippines, Diliman, Quezon City
Performed February 26, 2015
Submitted March 10, 2015
Abstract
Alkyl halides are halogen-substituted alkanes. They are found abundantly in nature and they
serve many purposes such as anaesthetics, refrigerants, and pesticides, but they are most
commonly used as a solvent. Alkyl halides can be produced from various methods but synthesis
from alcohol is most generally used. In this experiment the researchers conducted the synthesis
by reacting a tertiary alcohol with a hydrogen halide, thus producing a tertiary alkyl halide. 7.90
g tert-butyl alcohol was reacted with 20 mL concentrated hydrochloric acid in order to yield
crude tert-butyl alcohol (theoretical yield=9.87 g). Solid NaHCO 3 was added to the mixture to
prevent hydrolysis. Anhydrous CaCl2 was used to remove excess water. Steam distillation
technique was done to purify the alkyl halide. By virtue of the differences in volatilities, the
target compound (i.e. tert-butyl chloride) was isolated as it formed into steam and was
condensed. The actual yield was 6.05 g, which is a 61. 30% percentage yield. Sources of error
include the occurrence of side reactions, the misuse of the reagents (in form or amount), gaps in
the distillation set-up, and human error. The synthesis of alkyl halide is important and relevant
because it teaches the necessities in nucleophilic substitution reactions and how they proceed.
I. Introduction
II.
Alkyl halides systematically
named as haloalkanes are halogensubstituted alkanes (McMurry, 2010). In
these compounds, the halogen is a
substituent on a parent chain alkane.
Most alkyl halides we encounter are
colorless and odorless liquids that
miscible in organic solvents and only
sparingly soluble in water (Clark, n.d.).
III.
Alkyl
halides
serve
many
industrial purposes, such as their use as
anesthetics in medicine (Watrous, 1947),
reactants to produce glyme, which is a
solvent used in batteries (Tang & Zhao,
2014), as pesticides (see Hollingworth,
1976), and as refrigerants, such as the
chlorofluorocarbon (CFC) compound (see
Rowland, 2006) which is probably the
most familiar to the general population.
IV.
Among these, alkyl halides are
also mostly used as solvents, not only in
the industrial and commercial settings
but also in the academic setting. Alkyl
halides are a good family of compounds
to learn substitution and elimination
reactions from because of the nature of
their substituents (i.e. halide ions) that
are easily displaced (Bruice, 2014).

V.
There are multiple ways to
produce alkyl halides (e.g. through radical
halogenation
of
alkanes,
allylic
bromination of alkenes, using Grignard
reagents, etc.) but the most generally
used method of preparation is to make
them from alcohols (McMurry, 2010). The
general mechanism is as follows, where X
is a halogen (i.e. F, Cl, Br, or I):
VI.
VII.
|
|
VIII.
COH + HX
CX + HOH
IX.
|
|
X.
XI.
The mechanism involves the
substitution of one nucleophile by another
(McMurry, 2011). First, the hydroxyl group
detaches from the alkane (thus leaving
the alkane with a carbocation) and
attacks the hydrogen group of a hydrogen
halide, forming water and a halogen ion.
This nucleophilic halogen ion then attacks
the electrophilic alkane group (by virtue
of its carbocation), forming the alkyl
halide.
XII.
Based on current literature, the
experimenters performed the synthesis of
an alkyl halide from an alcohol in order to
supplement their knowledge of alkyl

halide preparation. The experimenters

also related the produced yield to the
procedures and processes done.
XIII. In this study the experimenters
opted to use for the simplicity of analysis
a tertiary alcohol (i.e., wherein a hydroxyl
group is attached to a tertiary carbon)
because this type of alcohol has a
relatively high reactivity and thus reacts
readily to form a tertiary alkyl halide
(McMurry, 2010).
XIV. After
the
preparation,
the
experimenters
also
performed
a
distillation technique in order to purify the
alkyl halide. This is a necessary step
when determining the yield.
XV.
XVI. Methodology
XVII.
Materials and Apparatus used:
XVIII.
tert-butyl alcohol
separatory funnel
XIX.
concentrated HCl
distillation set-up
XX.
solid NaHCO3
Erlenmeyer flask
XXI.
ice bath
thermometer (max. 100 C)
XXII.
hot plate
water
bath
XXIII.
rubber tubing
aluminum foil
XXIV.
round bottom flask
anhydrous CaCl2
XXV.
XXVI.
Procedure done:
XXVII. First, 10 mL tert-butyl alcohol
was placed in a 50 mL separatory funnel.
Twenty milliliters of concentrated HCl was
added and afterwards the mixture was
swirled. Internal pressure was relieved
from time to time by opening the
stopcock (see Figure 1).
XXVIII.

XXIX.

Figure 1. Holding and Venting a Separatory

Funnel King

XXX. The
mixture
was
left
undisturbed for 20 minutes. Layers

eventually formed. To determine which

the organic layer is, two drops of water
was added. The water dissolved in the
layer that was aqueous this layer was
then discarded (see Figure 2).
XXXI.
XXXII.

XXXIII. Figure 2. Layer Separation and Draining

El-Fellah

XXXIV.The organic layer was then

transferred into a dry flask containing a
small amount of solid NaHCO3 and was
gently swirled. The mixture was decanted
into another dry flask.
XXXV. The collected filtrate was dried
with a small amount of anhydrous CaCl2.
This was added until clumps were formed.
This was done in order to remove the H 2O
produced in the reaction. The crude tertbutyl chloride was then decanted into a
dry 25 mL round-bottom flask.
XXXVI.
A simple distillation setup was prepared (as shown in Figure 3).
The experimenters made sure that the
water flowed from the bottom of the
condensers cooling jacket and out from
the top. A thermometer was placed in the
3-way distilling adapter, its bulb placed
just below the side arm of the distillation
head.
XXXVII.
A round bottom flask
was chosen, big enough for the sample to
fit in two-thirds of its volume. A water
bath
was
used
to
regulate
the
temperature.

XXXVIII.

XLVIII.

LI.

color

LIV.
solubil
ity
LVII. boiling
point

XLIX. t
ert-butyl
alcohol
LII.
c
olorless
LV.
m
iscible
LVIII. 8
3C

L.
tertbutyl chloride
LIII.

colorles
s
LVI.
slightly
miscible
LIX. 51C

LX. Figure 4. Properties of tert-butyl

alcohol and tert-butyl chloride

LXI.
The balanced equation
for the reaction is the following:

LXII.
LXIII.
XXXIX. Figure 3. Simple Distillation Apparatus
Nimitz

XL.
The crude tert-butyl chloride
previously decanted inside a flask was
then installed to the distillation set-up.
The water pump was turned on.
XLI. The sample in the flask was
heated to a gentle boil. The temperature
reading on the thermometer rose rapidly
and when the reading remained constant
the boiling point was recorded. The
recorded boiling point was 80C.
XLII. The vapors and condensate
passed through the side arm and into the
condenser (where most of the vapor
condensed into liquid). The experimenters
made sure that when the mixture started
boiling, the heat source was adjusted
accordingly.
The
condensate
then
eventually poured into the receiving flask.
The experimenters watched for drops
disregarding the first five drops.
XLIII. The experimenters determined
the collected fraction by using a Pasteur
pipette. The total number of drops was
then converted into milliliters, garnering a
7.2 mL yield of tert-butyl chloride.
XLIV. The wastes were disposed into
the appropriate waste containers: the
aqueous solutions diluted and poured into
the sink, and the organic compounds
disposed in appropriate organic waste
jars.
XLV.
XLVI. Results and Discussion
XLVII. To complement the results, the
following table (Figure 4) shows a
summary of the properties of tert-butyl
alcohol and tert-butyl chloride:

(CH3)3COH + HCl (CH3)3CCl

+ H2O

LXIV.
LXV. This implies that 1 mmol of
(CH3)3COH is equivalent to 1 mmol of
(CH3)3CCl.
In
the
experiment,
ten
milliliters of tert-butyl alcohol was
prepared. This is equivalent to 7.90 g
which is equal to 106.58 mmol, as shown
in the following equation:
LXVI.

10 mL

0.79 g
=7.90 g
mL

LXVII.

mol
1000 mmol
7.9 g

=106.58 mmol
74.12 g
mol
LXVIII.
LXIX. The yield of the tert-butyl
chloride was 7.20 mL. This is equivalent
to 6.05g, and thus 65.36 mmol produced,
as calculated in the following equation:
LXX.

7.20 mL

0.84 g
=6.05 g
mL

LXXI.
LXXII.

6.05 g

mol
1000 mmol

=65.36 mmol
92.57 g
mol

LXXIII.
LXXIV. A summary of the reaction
scheme is shown below (Figure 5), along
with the experimental results:
LXXV.
LXXVI. (CH3)3COH 1)HCl; 2)NaHCO3>
(CH3)3CCl
LXXVII.
LXXVIII.
LXXIX.tert- LXXX. ter
butyl
t-butyl
alcohol
chloride

LXXXI.Mass
LXXXIV.
m
olecular
weight
LXXXVII.
d
ensity
XC.
mmol
XCIII.

LXXXII.
7.90g
LXXXV.
74.12g/mo
l
LXXXVIII.
0.79g/mL
XCI. 106.
58 mmol

LXXXIII.
6.05g
LXXXVI.
92.57g/m
ol
LXXXIX.
0.84g/mL
XCII. 65.
36 mmol

various sources of error. One source of

error could be due to the formation of
side products (from side reactions). One
of the possible side reactions of the
synthesis is di-tert-butyl ether, as shown
by the mechanism below:
CIII.

Figure 5. Experimental Results

XCIV. The theoretical yield of tertbutyl chloride, when limited by the

reagent tert-butyl alcohol, is 9.87g, as
shown in the following equation:
XCV.

106.58 mmol

mol
92.57 g

=9.87 g
1000 mmol
mol

CIV.

Figure 7. Di-tert-butyl ether Mechanism

CV.
Another possible reaction is 2methylpropene,
as
shown
in
the
illustration below:
CVI.

XCVI.
XCVII.
The percent yield is
therefore 61.30%, as calculated below:
XCVIII.

6.05 g (obtained)
100=61.30
9.87 g (theoretical)

XCIX. The mechanism involved in the

reaction between tert-butyl alcohol and
HCl is a unimolecular nucleophilic
substitution (SN1), where the reaction
occurs in a step-wise manner. This means
that the nucleophilic hydroxyl group of
the tert-butyl alcohol will attack the
hydrogen atom of the hydrogen halide.
This will give rise to a tert-butyl oxonium
compound. The electron-poor oxygen
atom will then be attacked by the carbon
attached to it. This will give rise to 2methylpropane
and
water.
The
carbocation of the 2-methylpropane will
be attacked by electrophilic Cl ion and will
thus form tert-butyl chloride. This is
illustrated below:

C.
CI.

Figure 6. Tert-butyl chloride Mechanism

CII.
The yield was only 61.30%. It is
possible that this number was caused by

CVII.

Figure 8. 2-methylpropene Mechanism

CVIII. To limit the formation of these

side-products
however,
the
experimenters made sure that the
temperature was regulated to high
temperatures to ensure that only the
target compound will be achieved. Also,
cold HCl was used to prevent the
formation of 2-methylpropene.
CIX. In line with this, the HCl used
was cold so as to prevent volatilization
and to avoid the sudden release of heat
(this is important because in the
experiment boiling chipsused to prevent
sudden heatingwere not used). The HCl
used was also concentrated so that all of
the alcohol sample will be solvated.
Another reagent used was NaHCO 3. It was
important to use the solid and not the
aqueous form so as to neutralize the
excess HCl in a moderated manner. Also,
it is to prevent the introduction of water
(i.e. hydrolysis) in the reaction. These
measures were done in order to reduce
the error.
CX.
Another source of error could be
from the distillation process (before and
after) and set-up. In the experiment,

anhydrous CaCl2 was incorporated to

remove the excess H2O. This is a
necessary step before proceeding to
distillation because if the excess water
was not removed, there would be a huge
discrepancy between the theoretical and
actual yields.
CXI. In terms of the set-up, one
crucial part was keeping the flow of water
continuous in the condenser. This is
important because the water in the
condenser will prevent it from getting
warm. The removal of the heat will aid
the condensation process. This is why the
experimenters made sure that the water
flowed continuously.
CXII. In line with this, a possible
source of error is the experimenter. She
may not have been able to read the
temperature correctly, there must have
been an error in the amount of reagents
used, etc. Some experimenter variables
such as fatigue and distraction may have
also caused inaccurate findings.
CXIII. Due to the various combinations
of these sources of error, that probably
occurred during the experiment, the
actual yield was not close to the
theoretical yield, but good enough to
exhibit the synthesis of tert-butyl
chloride.
CXIV.
CXV. Conclusion
CXVI. The formation of an alkyl halide
is important to perform so that one is able
to understand the mechanisms and
reactions that occur in each step of the
synthesis. The experiment also serves as
a good starting point when learning about
nucleophilic substitution reactions. In the
synthesis of an alkyl halide the
importance of following the procedures
carefully and also in choosing the correct
form (e.g. solid or aqueous) and amount
of reagents can also be observed.
Knowing the proper procedures and
techniques in the synthesis will serve as
an aid and a guide in future experiments.
CXVII.
CXVIII. References
CXIX.
Bruice,
P.
2014.
Organic
Chemistry 7th ed. Pearson, New York.

CXX.
Clark, J. n.d. Properties of Alkyl
Halides. Retrieved March 7, 2015 from
http://chemwiki.ucdavis.
edu/Organic_Chemistry/Alkyl_Halides/P
roperties_of_Alkyl_Halides.
Licensed
under CC BY-NC-SA 3.0 US.
CXXI.
El-Fellah, M. 2012. Laboratory
Course in Organic Chemistry. Organic
Chemistry Lab I 5332. Accessed March
6,
2015.
http://www.elfellah.com/Organic Chemistry Lab. I
5332.htm.
CXXII.
Hollingworth,
RM.
1976.
Chemistry, biological activity, and uses
of
formamidine
pesticides.
Environmental Health Perspectives.
14, 57-69.
CXXIII.
King, C. n.d. Preparation of TButyl Chloride. Accessed March 6,
2015.
http://christopherking
.name/Organic%20I
%20Labs/Preparation%20of%20t-butyl
chloride.htm.
CXXIV.
McMurry,
JE.
2011.
Fundamentals of Organic Chemistry
7th ed. Brooks-Cole, New York.
CXXV.
McMurry, JE. 2010. Organic
Chemistry 8th ed. Brooks-Cole, New
York.
CXXVI.
Nimitz, JS. 1991. Experiments
in Organic Chemistry. Prentice Hall:
New Jersey.
CXXVII. Rowland,
FS.
2006.
Stratospheric
ozone
depletion.
Philosophical Transactions of the Royal
Society
B:
Biological
Sciences.
361(1469), 769-790.
CXXVIII. Tang, S & Zhao, H. 2014.
Glymes as versatile solvents for
chemical reactions and processes:
From the laboratory to industry. RSC
Advances. 4(22), 11251-87.
CXXIX.
Watrous, RM. 1947 Health
hazards
of
the
pharmaceutical
industry. British Journal of Industrial
Medicine. 4 (2), 111-125.
CXXX.
CXXXI. Appendices
CXXXII. Attached is the data sheet for
this experiment.