SYNTHESIS AND PURIFICATION OF ALKYL HALIDE

FROM ALCOHOL

M. DEOLA
PHILIPPINE SCIENCE HIGH SCHOOL – MAIN CAMPUS

AGHAM RD., DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: OCTOBER 18, 2017

ABSTRACT

Alkyl halides serve many uses such as anesthetics, pesticides, and refriegerants. Alkyl halides can be synthesized by a variety of
methods but the most common method is its synthesis from alcohol. In this experiment, a tertiary alcohol was made to react with a
hydrogen halide to produce a tertiary alkyl halide via an SN1 nucleophilic substitution mechanism. 30 mL of tert-butyl alcohol was
reacted with 60 mL of cold concentrated hydrochloric acid to yield crude tert-butyl alcohol (theoretical yield=29.44g). Simple
distillation technique was used to purify the product by vaporization and condensation of the target compound. The actual yield was
1.26 g, which is a 4.27% yield. Sources of error include the misuse of equipment, and the occurrence of side reactions. Confirmatory
tests affirmed that there were halides present in the prepared and purified product. The synthesis of alkyl halide is relevant because
it easily teaches how nucleophilic substitution reactions occur and proceed.

INTRODUCTION hydrohalogens. But the reaction works well only

Alkyl halides, systematically known as
haloalkanes, are halogen-substituted alkanes
wherein a parent chain alkane has at least one
halogen atom attached as a substituent. Most alkyl
halides are colorless, odorless liquids which are
miscible in organic solvents, yet are only slightly
soluble in water.
Alkyl halides are mostly used as solvents
for commercial and industrial purposes including
anesthetics in medicine, pesticides, and refrigerants
(e.g. chlorofluorocarbons). Moreover, they are also
used for academic purposes. Alkyl halides are used
to teach substitution and elimination reactions due
to the easy displacement of their substituents.
Several ways to synthesize alkyl halides
include radical halogenation of alkanes, allylic
bromination of alkenes, etc. However, the most
common way to prepare alkyl halides is through the
use of alcohols.
Alcohols, or organic compounds in which
a hydroxyl (-OH) functional group is bound to a
saturated a carbon atom, reacts with
for tertiary alcohols (i.e. hydroxyl group attached to
a tertiary carbon) due to its high reactivity. On the
other hand, primary and secondary alcohols need
reagents such as PBr3 or HF-Pyridine in able for
them to react and produce alkyl halides.
The following reaction mechanism shows
how the alkyl halide synthesis works:
Figure 1. Mechanism for the alkyl halide
synthesis from alcohol
The mechanism involves the substitution
of one nucleophile by another. Specifically, the
hydroxyl group detaches from an alkane, leaving
the alkane with a carbocation, then attacks the
hydrogen (-H) group of a hydrogen halide. This
forms water and a halogen ion. Afterwards, the
nucleophilic halogen ion attacks the alkane group,
producing the alkyl halide.
This experiment aimed to synthesize tert-
butyl chloride from tert-butyl alcohol and
concentrated hydrochloric acid (HCl) through a
nucleophilic substitution reaction, specifically, an
SN1 reaction. It also aimed to purify the tert-butyl
chloride using simple distillation and to determine
the presence of alkyl halides using confirmatory
tests.
Figure 2. Layer separation using a separatory
funnel
METHODOLOGY
Purification of Alkyl Halide
Preparation of Alkyl Halide A simple distillation set-up as shown in
30 mL of tert-butyl alcohol and 60 mL of Figure 2 was equipped. It was made sure that water
cold concentrated HCl was placed in a dry 500 mL continuously flowed into the bottom of the
separatory funnel. It was gently swirled. The condenser’s cooling jacket and out from the top. A
internal pressure was safely relieved by the slow thermometer bulb was placed below the side arm
opening the stopcock in interval periods. The of the distillation head and a water bath was used
mixture was allowed to stand undisturbed for to regulate the temperature of the flask in this
twenty minutes, then 6mL of saturated sodium experiment.
chloride (NaCl) solution was added to the mixure.
The addition of NaCl facilitates the separation of
the organic layer from the aqueous layer. The
denser layer (aqueous layer) was discarded, while
the organic layer was transferred into a dry flask
containing a small amount of solid sodium
bicarbonate (NaHCO3) and then swirled gently.
Afterwards, the organic layer was decanted into
another dry flask where a small amount of
anhydrous (CaCl2) was added until it clumped
together to dry the filtrate.
The crude tert-butyl chloride was decanted
into a dry round bottom flask where 3 pieces of
boiling chips were added before the distillation
process. Figure 3. Simple distillation set-up
After distillation, the purified tert-butyl
chloride was transferred into a pre-weighed vial, After boiling chips were added to the
which was initially cooled in an ice bath. The vial sample in the flask, the water supply was turned on.
was weighed again, then the yield for the The glass joints were secured well and the flow of
experiment was calculated. Additionally, the the water through the condenser was checked. A
physical properties (color & solubility) were parafilm layer was added to the joints which
recorded for both reactants and products. The required reinforcements.
collected product was set aside for use in the The sample was heated in the flask to a
confirmatory tests. gentle boil. When the boiling point was reached,
the heat was adjusted so that distillation occurred
at 2 drops distillate per second. The first few
milliliters of the distillate was discarded and the
fraction that distilled around 49-52 °C, the desired
temperatures, was collected. The heat source was
removed to avoid distilling to dryness. And the set-
up was allowed to cool down first before it was
dismantled.
Confirmatory Tests for Alkyl Halides
Ethanolic Silver Nitrate (AgNO3) Test
Five drops of tert-butyl chloride and
tert0butanol were placed in separate test tubes.
2mL of ethanolic AgNO3 was added to each test
tube, then swirled gently. The time it took for
precipitate to form and its color were recorded. In
the case of tert-butanol, where no precipitate
formed, it was heated again for 5 minutes in a water
bath.
Beilstein Test
The tip of the copper wire was heated in a
burner flame until no coloration was seen in the
flame. The wire was cooled slightly, then it was
dipped in a test tube containing 0.5mL of tert-butyl
chloride. The wire was exposed to the burner flame
for a second time and color of the flame was
recorded. The same procedure was done for tert-
butanol.
RESULTS AND DISCUSSION
Preparation of Alkyl Halide
Figure 4. Mechanism for the reaction of tert-
butyl alcohol with HCl via SN1
The reaction mechanism involved between
tert-butyl alcohol and concentrated hydrochloric
acid (HCl) is a unimolecular nucleophilic
substitution (SN1). The nucleophilic hydroxyl
group of the tert-butyl alcohol will attack the H
atom of the hydrogen halide which will result to a
tert-butyl oxonium compound. Then, the carbon
will attack the electron-poor oxygen atom attached
to it, forming 2-methylpropane and water. Next,
the electrophilic Cl ion will attack the carbocation
of the 2-methylpropane, resulting in tert-butyl
chloride.
Table 1. Experimental results- Preparation of
alkyl halides
Mass of tert-butanol, g: 23.55 g
Mass of tert-butyl chloride, g: 1.253 g
Theoretical Yield: 29.44 g
% Yield: 4.26 %
Sources of error gave rise to the yield being
only 4.26%. The major source of error for this
experiment was the improper use of the separatory
funnel. A great volume of the initial mixture was
spilled during the separation of the aqueous from
the organic layer. So, it is advisable to place a beaker
at the bottom of the separatory funnel to catch any
spillage during the separation process. Another
source of error may be the formation of side
products, from the side reactions. Possible side
products include di-tert-butyl ether and 2-
methylpropene. But the synthesis of these may be
avoided by assuring the usage of high temperature
during experimentation to achieve the target
compound. Additionally, cold HCl was also used to
prevent the formation of 2-methylpropene.
Solid NaHCO3 was added in the organic
layer to neutralize the excess HCl in a moderate
manner, compared to if aqueous NaHCO3 was
used. It was also used to prevent hydrolysis in the
reaction. Anhydrous CaCl2 was used to remove the
excess water in the organic layer. This prevents
discrepancies and miscalculations between
theoretical and actual yields.
Purification of Alkyl Halide
The simple distillation process involves
vaporization and condensation of the vapor
happens, in order to further purify the alkyl halide
synthesized earlier. Keeping the flow of water
continuous in the condenser is vital to the simple
distillation set-up since the water prevents the
condenser from getting warm, therefore making
the condensation process more efficient. This also
prevents evaporation from occurring.
The addition of boiling chips ensures even
boiling and prevents bumping, or superheating of
the solvent which may lead to sudden bursts.
 tested in the past (i.e. carboxylic acid reacts and
forms precipitate).
Confirmatory Tests Consistent with the principle of this test,
the results saw no precipitate form for tert-butanol.
Table 2. Experimental results- Confirmatory Meanwhile, tert-butyl chloride, a tertiary halide,
tests produced white precipitate quickly.

Beilstein Test
Properties/Reaction tert-butanol tert-butyl This test detects the presence of halides in
chloride the reaction of copper compounds at high
temperatures. A green flame indicates the presence
of chlorine, bromine, or iodine. Fluorine is not
color clear clear
detected due to copper fluoride not being volatile.
Consistent with the principle of this test,
solubility in H2O soluble insoluble the results saw that green flame was not produced
with tert-butanol, which does not contain halides.
Tert-butyl chloride produced a green flame since it
contains chlorine ions.
Ethanolic AgNO3 Cloudy, no 19s, white
precipitate precipitate
after 5 min CONCLUSION AND
in bath RECOMMENDATION

The formation of alkyl halides is a good

Beilstein Test No Green flame
difference
Ethanolic AgNO3 Test
The presence of a tertiary alkyl halide may
be confirmed by adding ethanolic AgNO3 to the
product. In doing so, tertiary alkyl halides should
react rapidly with AgNO3 in a unimolecular
nucleophilic substitution (S 1 mechanism) to form
N
silver chloride (AgCl) precipitate.
experiment to use for one to be able to understand
the mechanisms that occur in each step of its
synthesis. In this experiment, tert-butyl chloride
was successfully produced from tert-butyl alcohol
and concentrated HCl through the acid-catalyzed
nucleophilic substitution reaction. A small yield of
product (4.27%) was obtained due to a collection
of errors. However, the prepared and purified
product was confirmed to contain halides via the
AgNO3 test and the Beilstein test.
For future experiments, knowing the
proper procedures and techniques in the synthesis
of a product is recommended. Familiarizing one’s
self with safety procedures is also a must to prevent
harmful incidents.

REFERENCES
Figure 5. Mechanism for the reaction in
AgNO3 test
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This test allows for the identification of
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respectively. However, false positives have been Properties_of_Alkyl_Halides.
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