SYNTHESIS OF AN ALKYL HALIDE

A. B. DIOQUINO, K.P. ISLETA, AND M.V. MONZON

1
INSTITUTE OF CHEMISTRY, COLLEGE OF SCIENCE
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
DATE PERFORMED: DECEMBER 8, 2009

ABSTRACT
Alkyl halides are generally formed from alcohols through treatment with
hydrogen halides. The purpose of this study is to illustrate the mechanisms behind
the SN1 reaction. Tert-butyl chloride is synthesized from tert-butyl alcohol using
cold, concentrated hydrochloric acid. The organic layer was obtained using a
separatory funnel and reagents such sodium bicarbonate and calcium chloride
were added. Simple distillation was conducted in order to obtain pure tert-butyl
chloride. The computed theoretical yield is 11.45mL and the obtained tert- butyl
chloride is 2.7mL, which gives a 23.58% percentage yield. This relatively low yield
may be due an inefficient methodology, and the presence of a simultaneous
elimination reaction.

INTRODUCTION
Alkyl halides, or haloalkanes,
are compounds that have a halogen
atom bonded to a saturated sp3hybridized carbon atom. They are are
nonflammable
and
nonpolar
compounds which give them various
uses. They are comercially used as
flame retardants, fire extinguishers,
refrigerants, as well as solvents for
dry
cleaning
and
degreasing
applications.
This type of organic compound
is generally formed through the
synthesis of alcohols with hydrogen
halides (HCl, HBr, or HI). The order of
reactivity increases as one goes down

the halogen group. These compounds

may be also classified according to
the number of alkyl groups attached
to the carbon. Primary alkyl halides
have a single alkyl group attached,
secondary alkyl halides have two
groups and tertiary alcohols have
three. A tertiary alcohol with the form
R3COH, should be applied for a more
effective
reaction.
Primary
and
secondary alcohols react much more
slowly
and
require
higher
temperatures. In some cases, Lewis
acids such as zinc chloride are

required for a more effective reaction.

Thionyl
chloride
(SOCl2)
or

phosphorous tribromide (PBr3) may

also be used for treatment with
primary and secondary alcohols.
In this experiment, tert-butyl
chloride is formed from the addition
of tert-butyl alcohol with concentrated
hydrochloric acid. The alcohol and
hydrogen halide are placed in a
separatory funnel which will later on
facilitate the isolation of components.
Purification of the tert-butyl chloride
is
performed
through
simple
distillation to remove excess water
from the solution. Since tert-butyl is a
tertiary alcohol, it will readily produce
an alkyl halide and water at room
temperature.
The purpose of this experiment
is to acquaint students with the
mechanisms behind alkyl halide
synthesis through the synthesis of
tert-butyl chloride from tert-butyl
alcohol. It also aims to teach
laboratory techniques such as the
usage of the separatory funnel and
simple distillation.

METHODOLOGY
Ten milliliters of tert-butyl
alcohol and 20 milliliters of cold,
concentrated hydrochloric acid (HCl)
were measured with a graduated
cylinder and placed in a separatory
funnel. The mixture was gently
swirled under the fume hood. To
relieve internal pressure, the stop
cock was opened after some time to
release
gas.
Afterwards,
the
separatory funnel was left to stand in
an iron ring for 20 minutes.

While waiting, the simple

distillation apparatus was prepared. A
cork that had been previously drilled
into was inserted with a laboratory
thermometer.
Subsequently,
the
apparatus was assembled accordingly.
After 20 minutes had passed,
about two milliliters of six molar
sodium chloride (NaCl) solution were
measured in a graduated cylinder and
placed in the separatory funnel. The
two layers were then separated by
slowly opening the stopcock. A drop
of water was placed into both layers
to determine the organic layer. The
aqueous layer was discarded.
The
organic
layer
was
transferred to a flask containing
sodium bicarbonate (NaHCO3) and
swirled gently. Afterwards, the liquid
was decanted into another flask.
Anhydrous calcium chloride (CaCl2)
was
added
until
there
was
undissolved excess solid. The liquid
was then decanted into a dry, 25milliliter round bottom flask. Two
boiling chips were added to the
distillation flask and the crude tertbutyl chloride was distilled. The heat
and rate of distillation were controlled
and the boiling point was recorded.
The first one milliliter of the distillate
was discarded, and the remaining
solution was placed in a ten-milliliter
graduated
cylinder
which
was
previously cooled in an ice bath. The
volume of the product was measured
and afterwards, it was placed in a
vial, labeled, and submitted to the
instructor.

RESULTS AND DISCUSSION

Synthesis of tert-butyl chloride
from tert-butyl alcohol involved the
reaction of the alcohol with a
hydrogen halide. In this case, cold,
concentrated hydrochloric acid was
used as the hydrogen halide. Cold HCl
was used to hasten the reaction, and
avoid side products. Excess HCl was
added to further stimulate product
formation and to ensure that all the
alcohol will be used in the reaction.
The
reactants
underwent
a
nucleophilic
substitution
reaction
involving
unimolecular
ratedetermining step, also known as the
SN1 reaction. Tertiary substrates are
the most favored substrates in this
type of reaction. In treating an alcohol
with
hydrogen
halides,
tertiary
alcohols react rapidly as compared to
primary and secondary alcohols. By
this principle, tert-butyl alcohol, a
tertiary alcohol, reacted rapidly via
SN1 and E1 pathways with HCl, its
acidic nucleophile. During the SN1
reaction,
the
tert-butyl
alcohol
dissociates to form a carbocation,
which
then
reacts
with
the
nucleophile. The mechanism is shown
below.

Figure I. Mechanism for the

reaction of tert- butyl alcohol with
HCl via SN1
At first, the OH group is
protonated by HCl which is a fast
reaction. Then the protonated alcohol
dissociates
spontaneously,
which
occurs in a slow, rate-determining
step. This dissociation gave rise to a
carbocation intermediate plus water.
Afterwards, the chloride ion attacks
the stable carbocation, and the water
(H2O) leaves the resulting product.
Water, in this part of the reaction, is
called the leaving group. In tert-butyl
alcohol, OH is considered as the
leaving group. However, this leaving
group is not at its most stable form. In
order for it to be at its most stable
form, the OH group is protonated.
The hydrogen atom from HCl is

ionized and transformed into water.

The chloride ion then attaches itself
to the carbocation to yield the neutral
substitution
product,
tert-butyl
chloride.

product. The reaction mechanism of

2- methylpropene is shown below.

Unlike in an SN2 reaction,

where displacement of leaving group
and the attack of the incoming
nucleophile happen at the same time,
an SN1 reaction occurs first with the
spontaneous loss of the leaving group
then the incoming nucleophile. In
between,
a
stable
carbocation
intermediate is formed. This two-step
mechanism is the reason why tertiary
alcohols react with HCl must faster
than the primary and secondary
alcohols. More stable carbocation
intermediates involve a faster SN1
reaction.
It can be seen in the reaction
that the substrate is the only species
involved in the rate- determining step.
This is because the rate of an SN1
reaction
depends
only
on
the
substrate concentration, and not with
the nucleophile concentration (firstorder process).
In the synthesis via SN1
reaction, by-products can be formed
as consequences of the synthesis. This
is because an opposite reaction
occurs with SN1 reaction. This
reaction is called the unimolecular
elimination reaction, or E1. E1
reactions
have
the
same
characteristics as that of SN1, but it
involves loss of H+ from the
intermediate carbocation following
the dissociation of process. A neutral
alkene is formed from this step. SN 1
and E1 reactions normally occur in
competition when alkyl halides are
treated with a nonbasic nucleophile.
In the synthesis of tert- butyl chloride,
2- methylpropene is formed as a by-

Figure II. Mechanism for the

formation of 2- methylpropene as
a by- product via E1
The reaction mechanism above
implies that the formation of 2methylpropene is a first- order
process. This reaction proceeds
because not all tert-butyl alcohol may
have reacted via SN1. After the
protonation, the hydroxide ion leaves
the substrate and forms water. The
water can act as a base and it can
remove an H+ from the carbocation. A
bond will result from the C-H bond.
2-methylpropene is then formed.
In the elimination reaction,
there is heat required for the reaction
to proceed. As the temperature
increases, the rate of E1 reaction
increases as well. Therefore, by
adding cold HCl, the formation of a
stable tertiary carbocation, through
the SN1 mechanism, is maximized and

favored. In addition, based on Le

Chateliers Principle to help favor the
forward reaction, more reactants
(HCl) must be added.
As the cold HCl is mixed with
tert-butyl
alcohol,
the
gas
2methylpropene (BP:-6.9oC) formed
from the E1 reaction is released by
opening the stopcock. This is done to
prevent the build up of internal
pressure. However, this release of gas
may result in a loss that could lead to
a lower yield.
The mixture was allowed to
stand for 20 minutes and then
separated. Sodium chloride (NaCl)
solution was added to make the layers
more visible since it can draw out the
water from the organic layer to the
aqueous layer. Crude tert- butyl
chloride is obtained. Since it still has
impurities, solid sodium bicarbonate
(NaHCO3) is added in small amounts
to neutralize any excess HCl. This
addition will cause effervesence of
carbon dioxide (CO2). Solid NaHCO3 is
used rather than the aqueous NaHCO3
to ease the separation of NaHCO3.
Drying the collected filtrate
with a small amount of anhydrous
calcium chloride (CaCl2) followed.
This was done before distillation to
remove traces of water left and
unreacted
alcohol
which
may
interfere in the process.
The solution was decanted and
boiling chips were added before
distillation. Boiling chips are small,
insoluble, porous objects made of
calcium carbonate or silicon carbide
that can trap air and provide spaces
where bubbles of solvent vapor can
form. When a boiling chip is heated in
a solvent, it releases tiny bubbles that
ensure even boiling and prevent
bumping and boiling over. It does not

make the boiling faster and avoids

product loss by preventing the
bumping of the solution during
boiling.
Subsequently,
simple
distillation was conducted. Distillation
of the solution was done to purify the
tert-butyl chloride by separating the
impurities through their different
boiling points. Continuous flow of
water on the condenser during
distillation is important to properly
cool and condense the hot product
vapors. It affects the cooling capacity
of the condenser which would affect
the product recovery.
Table I. Experimental Results
: 7.80
Weight of tert-butyl alcohol,
: 2.70
g
: 7.80
: 11.45
Volume of tert-butyl alcohol,
g
:
23.58%
2.7
Theoretical yield, mL
: 11.45
% yield
: 23.58%

The synthesis via SN1 and E1

resulted in a tert-butyl chloride with a
volume of 2.7ml. Pure tert-butyl
chloride has a colorless appearance
and our result yielded a similar
substance. However, impurities may
still be present, such as minute traces
of HCl. It would be difficult to detect
these errors because they come from
different sources. A possible source of
these errors is the addition of the
NaHCO3 and CaCl2. It is possible that
not enough NaHCO3 was added to
neutralize the excess HCl, or the
addition of anhydrous CaCl2 was not
enough to react with all the unreacted
alcohol and water. These errors would
lead to an impure product.
Tert-butyl chloride is a volatile
substance which can cause the loss of
product. The way the process was

conducted may have resulted in

reagent loss. During separation of
layers, the separatory funnel is not
covered and some tert- butyl chloride
may have vaporized. The separation of
the layers through the stopcock is
another source of error. Some
aqueous layer might have been
retained with the organic layer due to
improper
separation.
Also,
the
decantation and distillation of the
solution may contribute to product
loss. Inadequate drying of the filtrate
may have lead to backward reaction
and heating the distillation system too
abruptly and erratically will cause a
sudden increase in temperature.
These possible errors may have
accounted for the low yield.
CONCLUSION AND
RECOMMENDATION
With a percent yield of 23.58%,
it can be concluded that not all of the
tert-butyl alcohol reacted to form the
desired product, tert-butyl chloride.
As expected, some of the product
formed 2-methylpropene, which was
released in a gaseous form and
resulted in a lower yield. However,
the results show a relatively low
percent yield despite precautions.
After adding certain reactants to favor
the forward reaction, the SN1 was not

effectively maximized and the

reaction was favored instead.

E1

For further improvement, the

usage of a very cold concentrated
hydrochloric acid is recommended.
More anhydrous calcium chloride
should also be added until there is
undissolved
CaCl2.
Careful
observation should also be observed
in the steps that could result in side
reactions.
REFERENCES
[1] McMurry, J. Organic Chemistry 6th
edition.
Brooks/Cole-Thomson
Learning., USA. 2004
[2]

Mackenzie, C.A. Experimental

Organic Chemistry. Prentice hall,
Inc., New Jersey. 1967

[3] March, Jerry. Advanced Organic

Chemistry. 4th edition. John Wiley
& Sons. Inc.
[4] Organic Chemistry Group. Organic
Chemistry
Laboratory
Manual.
Institute of Chemistry, College of
Science,
University
of
the
Philippines, Diliman, Quezon City.
2008.
APPENDIX (see attached)