PREPARATION AND PURIFICATION OF ALKYL HALIDE

N.D.S. CASTOR1 AND E.V. REYES1

1INSTITUTE OF BIOLOGY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
DATE PERFORMED: JUNE 25, 2014
_____________________________________________________________________________________________
ABSTRACT

The study aims to conduct the reaction of alcohols with hydrogen halides to produce alkyl halides which are used industrially as
solvents, inhaled anesthetics in medicine, refrigerants, and pesticides. For the experiment, tert- butyl alcohol and concentrated
hydrochloric acid underwent unimolecular nucleophilic substitution (SN1) to yield tert- butyl chloride. The reagents were placed in
a separatory funnel and were mixed gently. After 20 minutes, the organic layer was collected and was treated with NaHCO3
and anhydrous CaCl2 to remove acidic and water impurities and was decanted. The crude tert- butyl chloride was purified
through simple distillation. The condensed liquid that boiled at 40- 52o C, the boiling point of tert- butyl chloride was collected
in a cool, pre- weighed vial. The obtained product weighed 1.760 g, which is 18.007 % of the theoretical yield of 9.742 g. The
experiment successfully synthesized purified tert- butyl chloride from tert- butyl alcohol and concentrated hydrochloric acid despite
the relatively low yield.
_____________________________________________________________________________________________

INTRODUCTION
Halogen- substituted alkanes are commonly known
as alkyl halides, compounds containing halogen
atoms bonded to a saturated- sp3- hybridized
carbon atom. Halogens are elements of group 7A
which include Fluorine, Chlorine, Iodine, Bromine
and Astatine. Alkyl halides have various applications
but are primarily used industrially as solvents,
inhaled anesthetics in medicine, refrigerants, and
pesticides. Among other compounds, alcohol is
most commonly used in synthesizing alkyl halides.
One method of producing alkyl halides from
alcohol is by hydrogen halide treatment. However,
the reaction works best for tertiary alcohols,
R3COH as it is relatively more stable than
secondary or primary carbocation reactions[1].
In forming alkyl halides, alcohols and hydrogen
halides undergo nucleophilic substitution. This
mechanism involves the substitution of one
nucleophile, a species strongly attracted to a
positively charged region, with another [2] .
Specifically, the hydroxyl group of the alcohol is
replaced with a halogen in the formation of alkyl
halides as illustrated in equation 1.
ROH + HX RX + H2O (1)

Nucleophilic substitution is classified into two

different mechanisms, SN1 and SN2. In the
experiment, tert- butyl alcohol, a tertiary alcohol,
follows the SN1 mechanism of unimolecular
nucleophilic substitution in producing tert- butyl
chloride. This involves the protonation of the -OH
group by HCl. The protonated alcohol then
dissociates in a slow, rate determining step, forming
a carbocation intermediate and a byproduct, water.
The carbocation intermediate formed reacts with
the nucleophile, Cl- in a fast step to yield the alkyl
halide product, tert- butyl chloride[1]. The overall
reaction for the formation of tert- butyl chloride
from tert- butyl alcohol and HCl is shown in Figure
I.

Figure I. Overall Reaction for the formation of

tert-butyl chloride from tert-butyl alcohol and
HCl[2]
In the experiment, tert- butyl chloride is synthesized
from the reaction of tert- butyl alcohol and
concentrated HCl, which it readily reacts with. The
resulting alkyl halide product is then purified using
simple distillation.
1

METHODOLOGY
To synthesize tert- butyl chloride, 10 mL of tertbutyl alcohol and 20 mL of cold, concentrated HCl
were measured and placed in a separatory funnel.
The mixture was swirled gently with a stirring rod
and then sealed with aluminum foil. The funnel
containing the mixture was made to stand
undisturbed for 20 minutes. After such time, 3-5
mL of 6 M NaCl solution was added to the
mixture. The stopcock was opened and the denser
layer was extracted from the funnel. This layer was
determined to be the aqueous layer after adding a
minimal amount of water that dissolved and hence,
was discarded.
The remaining organic layer in the separatory
funnel was transferred to a dry flask containing a
small amount of solid NaHCO3. The flask was
swirled and the liquid was decanted into another
dry flask. The filtrate was dried with a small amount
of anhydrous CaCl2 which was continuously added
until it clumped together. The crude tert- butyl
chloride was decanted into a dry 25 mL round
bottom flask. The solution was then distilled after
the addition of 2-3 boiling chips.
The simple distillation set- up was constructed as
seen in Figure II. The water was made to flow into
the bottom and out the top of the condensers
cooling jacket. The sample was subjected to heat
until it reached a gentle boil. As the temperature
rose to 49-52o C, the condensed liquid was collected
in a pre- weighed vial which was cooled in an ice
bath prior to use. The sample was removed from
the heat source upon boiling to avoid distilling to
dryness. The distilled tert- butyl chloride was
subjected to a solubility test with water and its
percent yield was determined.
RESULTS AND DISCUSSION
The synthesis of tert- butyl chloride from tert- butyl
alcohol underwent a nucleophilic substitution
reaction, more specifically, an SN1 reaction, which
can be explained visually in Figure III.

Figure III. Mechanism of synthesis of TertButyl chloride from Tert-butyl alcohol[1]

A C-OH bond is severed by protonation using an
HCl molecule producing a stable and reactive
tertiary carbocation and a water molecule.
Immediately after, the positive charge attracts a
chloride anion, effectively stabilizing the molecule[3].
The immediate progression after the first step,
symbolized by the transition state present in the
mechanism, is indicative of a reaction whose rate is
dependent on the nucleophile alone.
A nucleophilic substitution reaction dependent on
the nucleophile alone is called an SN1 reaction. Its
counterpart, the SN2 reaction, is dependent on both
the nucleophile and the substrate. The SN1
mechanism is preferred by the tert- butyl chloride
synthesis used in the experiment due to a tertiary
carbocation in the intermediate formed after the
protonation of the -OH group as seen in Figure III.
SN1 reactions favor both tertiary carbocations and a
highly polar, protic medium as both contribute to a
relatively fast rate-determining step[4]. Highly polar,
protic media such as the HCl used in the
experiment are able to produce an abundance of
H+ protons which causes the C-OH bond to break,
forming a carbocation[5]. Tertiary carbocations are
more stable than primar y and secondar y
carbocations, and therefore react more quickly than
either of the two.

In the experiment, an excess of cold HCl was used

to prevent loss of product due to the relatively low
boiling point of tert- butyl chloride, and the
prevention of side reactions such as E1 dehydration
reactions that produce alkenes[6], both reducing the
amount of tert- butyl chloride formed. The cold
HCl was added in excess to make sure that all of
the tert- butyl alcohol would completely react with
the HCl acid, which maximized the yield.
The mixture of tert- butyl alcohol and HCl was then
transferred to a separatory funnel and gently mixed
with a stirring rod before finally sealing the funnel
with aluminum foil. This was done to prevent the
loss of any volatile product. After letting the
mixture stand for the allotted time, concentrated
NaCl was added to the mixture to facilitate the
separation of the aqueous and organic layers[7]. The
stopcock was then opened to let the denser layer
out of the funnel, effectively separating the two
immiscible layers. A few mL of water was added to
the denser layer to determine its identity as water
should be miscible only in the aqueous layer.
The organic layer was then transferred to a dry flask
containing solid NaHCO3. Solid NaHCO3 was used
instead of its liquid state for easier separation with
the liquid organic compound through decantation.
Water soluble salts were produced by the reaction
of acidic impurities present in the organic layer and
NaHCO3, a weak base.
Anhydrous CaCl2, a drying compound, was used to
further remove liquid impurities such as water from
the sample[3]. Clumping indicated the reaction of
CaCl2 with water[3][8]. This was done before
distillation to ensure a minimal amount of
impurities in the final product.
In the purification of the crude tert- butyl chloride,
simple distillation was the chosen method due to
the relatively low boiling point of tert-butyl chloride.
This allowed it to be separated from the impurities
which generally had higher boiling points. Boiling
chips were added to the sample to ensure even
boiling and to prevent bumping. Bumping occurs
when part of the mixture is superheated, causing
the mixture to boil in sudden and violent bursts[3].
This must be avoided in order to keep the
sputtering liquid from entering the condenser and
straight to the receiving flask, contaminating the
pure distillate. Note that a continuous flow of water
must be introduced from the bottom and out the

top of the condensers jacket. This regulated the

low temperature of the condenser which
guaranteed condensation.
The receiving flask used was a cool and preweighed vial. This was done to keep the product in
its liquid form. Distilling to dryness was avoided as
this would have caused some impurities to be
distilled into the receiving flask. To ensure accurate
measurement of the temperature, the thermometer
was kept below the mouth of the 3-way distilling
adapter[3].
Table I. Experimental Results
Mass of tert-butyl alcohol, g

7.809

Mass of tert-butyl chloride, g

1.760

Theoretical Yield

9.742

% Yield

18.077

The sample was weighed after the end of

distillation. The theoretical yield for the production
of tert- butyl chloride from 10 mL of tert- butyl
alcohol is 9.742 g, while the experimental product
weighed in at 1.760 g, which translated into an
18.077 % yield. This deviation from the theoretical
value can be attributed to a number of factors, one
of which is the loss of the product which may have
evaporated due to its volatility during solvent
extraction. Additionally, it may also have seeped out
of the apparatus during the distillation process
while in its gaseous form. Other possible causes of
the low yield is the premature termination of the
collection of the distillate, the incomplete mixing
of the reagents causing a reduced amount of
product. Not all of the organic layer may have been
decanted, causing a reduced amount of product.

Table II. Physical Properties

Properties

Tert- Butyl
alcohol

Tert- Butyl
chloride

Color

Colorless

Colorless

Solubility in
Water

Soluble

Insoluble

Theoretical
Boiling Point (C)

82.2

51

The distillate then gave a negative result in its test

for solubility in water. Since tert- butyl chloride is
only partially soluble in water, the negative result in
the solubility test is a positive indicator of the
identity and purity of the product. The temperature
during the distillation process was then found to be
at a steady 50 C, indicating the boiling point of the
product, one degree away from the theoretical.
Both these results meant that the product had
relatively high purity.
CONCLUSION AND RECOMMENDATION
In the production of tert- butyl chloride from 10
mL of tert-butyl alcohol and 20 mL of cold HCl,
1.760 g of tert-butyl chloride with a boiling point
of 50C was produced. This translated to a product
with a relatively low yield of 18.077 %, but with
high purity. Therefore, the experiment was
successful in synthesizing pure tert-butyl chloride,
however the quantity of the product was not up to
par with the theoretical value of 9.742 g.

[3] Preparation of tert-Butyl Chloride. n.d. Retrieved

June 27, 2015, from http://myweb.brooklyn.liu.edu/
swatson/Site/Laboratory_Manuals_files/Exp3.pdf
[4] Solomons TWG. 2003. Fundamentals of Organic
Chemistry. Tenth Edition. John Wiley and Sons, Inc.
USA.
[5] Raveendran, G., & Neelakumari, S. 2012. Effect of
added Dimethyl sulphoxide on the Solvolysis of
Cinnamoyl Chloride in Aqueous Acetone and
Acetonitrile. Retrieved June 27, 2015, from http://
www.orientjchem.org/dnload/G-RAVEENDRAN-andS-NEELAKUMARI/OJCV028I03P1371-1378.pdf
[6] Feng, C. n.d. Organic Chemistry Lecture 2 Hydrocarbons, Alcohols, Substitutions. Retrieved June
27, 2015, from https://fenguin.s3.amazonaws.com/
mcat/outlines/OrganicChemistry2.pdf
[7] Organic Chemistry academic group of the Institute
of Chemistry. 2014. Organic Chemistry Laboratory
Manual. 2014 Edition. Institute of Chemistry, University
of the Philippines Diliman. Quezon City.
[8] Drying agents. 2013, December 28. Retrieved June
27, 2015, from http://www.chem.ucla.edu/~bacher/
Specialtopics/Drying Agents.html

In order to improve the results, a better

environment to reduce loss of volatile product may
be taken into consideration. Other things to
consider may be the use of a better purification
technique which minimizes the loss of product, and
a more accurate and efficient way of separating the
aqueous and organic layer.
REFERENCES
[1] McMurry J. 2008. Fundamentals of Organic
Chemistry. Eighth Edition. Thomson Brooks/Cole.
USA.
[2] Clark, J. 2000. What is nucleophilic substitution?
Retrieved June 27, 2015, from http://
www.chemguide.co.uk/mechanisms/nucsub/whatis.html

APPENDIX

Figure II. Reaction Scheme

Table III. Properties of the Organic
Compounds in the Experiment
Properties

T-BA

T-BC

Mass

7.809

1.760

Molecular Wt. 74.120

92.570

Density

0.781

0.840

Mmol

105.356

19.013