SYNTHESIS

OF

TERT-BUTYL

CHLORIDE

THROUGH

HYDROCHLORINATION OF TERT-BUTYL ALCOHOL AND

PURIFICATION USING DISTILLATION
J. V. DE GUZMAN
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
DATE PERFORMED: FEBRUARY 27, 2015
INSTRUCTORS NAME: ALLAN KENNETH REGUNTON

ABSTRACT
Preparation of alkyl halides holds significance not only in the study of them but also
in its practical applications in the fields of medicine, agriculture and industry. The
purpose of this experiment is to synthesize t-butyl chloride through a nucleophilic
substitution reaction of t-butyl alcohol with HCl. This method employs the relative
stability of the carbocation intermediate formed and thus proceeds through S N1
reaction mechanism. The crude product obtained was then purified using fractional
distillation that makes use of the difference in the boiling points of impurities and
desired substance. The percentage yield is 47.90% implying the effectivity of
hydrohalogenation of tertiary alcohols to produce tertiary alkyl halides and the use
of distillation as a purification technique for liquids. It also shows effective removal
of water in the crude product that can convert t-butyl chloride back to alcohol and
minimized errors such as loose distillation set-up and contamination of flasks and
boiling chips.
_____________________________________________________________________________________________
_________________________________

INTRODUCTION
Alkyl halides also called haloalkanes
are class of compounds with a halogen
atom bonded to a sp3-hybridized
carbon atom [3]. Halogen atom X is
more electronegative than carbon
atom making the C-X bond polar and
alkyl halides molecule to be more
polar than hydrocarbons. However,
they are still considered insoluble in
water because it cannot form an Hbond with the water molecule.
Alkyl halides are categorized into
three, depending on the number of
alkyl substituents attached to the
carbon atom from which the halogen
is bonded. Primary alkyl halides have a

halogen atom bonded to a carbon with

one
alkyl
substituent
while
a
secondary alkyl halide has a carbon
with two alkyl substituent connected
to the halogen. Tertiary alkyl halides
have the halogen atom bonded to a
carbon atom with three alkyl groups.
Haloalkanes found many industrial and
pharmaceutical applications, including
their use as solvents, refrigerants,
pesticides, fungicides and anesthetics.
They are also indispensable in giving
important leads to new medicines. [1]
As such, methods in synthesizing alkyl
halides were developed because of its
importance not only in the study of
1

these compounds but also in their

practical applications in the fields of
medicine, industry and agriculture.
Alkyl halides can be prepared through
radical halogenation of alkanes, allylic
halogenation of alkenes, reaction with
Grignard reagents but the most
generally useful method is preparation
from alcohols. [1]
Alcohols react with hydrohalogenated
compounds such as HCl and HBr to
yield alkyl halides in a type of reaction
called nucleophilic substitution. This
method is most applicable in the
synthesis of tertiary alkyl halides from
tertiary alcohols since primary and
secondary alcohols react much slowly
in the presence of HCl or HBr. The
general reaction for synthesis of
tertiary alkyl halide is shown in the
figure below:

substitution reaction of alcohols with

hydrogen halide and the possible side
reactions that may occur during
synthesis. It also intends to evaluate
the efficiency of distillation as a
purification technique.
METHODOLOGY
In the dry 50-ml separatory funnel, 10
ml of t-butyl alcohol and 20 ml cold
concentrated HCl were combined and
allowed to react. The internal pressure
that built up in the separatory funnel
was relieved from time to time by
slowly opening the stopcock. The
mixture
was
allowed
to
stand
undisturbed in a set-up as shown in
Figure 2 for 20 minutes. To force
separation of layers, 3-5 ml of 6 M
NaCl solution was added in the
mixture.

H-X
Figure 1. General reaction of tertiary
alcohol to yield alkyl halide
Distillation, on the other hand, is a
process of vaporizing a liquid,
condensing the vapor, and obtaining
the condensate in another container
[2]
. It can be used as a method of
purifying a substance by taking
advantage of the difference in the
boiling points of the impurities that
may be present and of the substance
to be purified. This is specifically
called as fractional distillation. The
compound to be purified is obtained
by distilling the solution and collecting
the fractions at the boiling point of the
substance of interest.
This experiment focuses on the
preparation of tert-butyl chloride from
the reaction of tert-butyl alcohol and
hydrochloric acid. After the synthesis,
t-butyl chloride is purified using
fractional distillation. This experiment
also aims to explore the mechanisms
involved
in
the
nucleophilic

[5]

Figure 2. Set-up for the separation

of aqueous and organic layer
The aqueous layer was drained. To
check that it was the aqueous layer, 12 drops of water was added to it and
positive result is shown by dissolution
of water in this layer. Impurities and
excess reactants were removed from
the product by adding solid NaHCO3 in
the obtained organic layer inside a dry
flask.
The mixture was decanted and the
collected solution was further dried by
adding small amount of anhydrous
CaCl2 until it no longer clumped
together. The resulting solution was
decanted into a dry 25-ml round
bottom flask and few boiling chips
were added.
2

A distillation set-up similar to Figure 3

was
constructed.
The
obtained
solution was then distilled.

[6]

Figure 3. Simple distillation Set-up

the new partially negative Nu-C bond

which is partly forming thereby
making this reaction stereospecific[1].
However, this does not occur at a
hindered
substrate
because
the
nucleophile cannot easily attack the
bulky and sterically hindered carbon
atom therefore it is least or very slow
to occur in tertiary or stable alcohols.
On the other hand, SN1 reaction is a
unimolecular two-step nucleophilic
substitution
which
is
nonstereospecific. The rate limiting step in
this reaction is the formation of a
stabilized carbocation intermediate,
thus, the more stable the carbocation
is formed, the faster the reaction is.
Therefore the nucleophilic substitution
of alcohols can be summarized into:

The fraction that boiled at 42-59 C

was collected in a pre-weighed vial
placed in a cold water bath. Tert-butyl
chloride percentage yield was then
determined and the purified product
was subjected to a solubility test with
water.
RESULTS AND DISCUSSION
The reaction of tert-butyl alcohol with
HCl to yield tert-butyl chloride makes
use of the stability of the intermediate
carbocation that will be formed. Based
from the general reaction shown in
Figure 1, the nucleophilic hydroxide
group of the alcohol is simply
displaced by the more nucleophilic
halogen atom. As such, this reaction is
called nucleophilic substitution. This
type of reaction can precede in either
SN1 or SN2 reaction mechanisms. The
S N2
reaction
is
a
bimolecular
nucleophilic substitution occurring at a
single step mechanism without the
formation of intermediates. In this
reaction,
a
nucleophile
attacks
opposite and takes an electron from COH bond thus giving a transition state
in which the old partially negative HOC bond is partly breaking opposite to

Figure 4. Arrangement of possible

nucleophilic substitution reaction for
alcohols
As such, tert-butyl alcohol reacting
with HCl will most probably undergo
SN1 reaction. It is also the reason why
this method works best only on
tertiary but not on secondary or
primary alcohols. Under SN1, the
mechanism for the synthesis of tertbutyl chloride is shown in Figure 5
H Cl
below:
+
Cl-

Figure 5a. Protonation of OH group

by HCl
3

, H
Cl

Cl+

+
H 2O

SN1

Figure 5b. Rate determining step to

form carbocation intermediate
Cl

Figure 6b. Dissociation of protonated

t-butyl alcohol yielding carbocation
intermediate
,

Figure 5c. Fast step reaction of

carbocation with Cl- yielding t-butyl
chloride
The hydroxide group of the t-butyl
alcohol is first protonated by the
hydrogen of HCl leaving the chlorine
electron rich. The protonated alcohol
then undergoes a slow, rate-limiting
step of spontaneous dissociation to
yield
a
tertiary
carbocation
intermediate and water which is a
good leaving group. Good leaving
group lowers the energy level of the
transition state thereby increasing the
reaction rate of carbocation formation.
The carbocation intermediate then
reacts with the nucleophilic chloride
ion to form t-butyl chloride in a fast
step reaction. However, this reaction
may not necessarily occur if the
formation of side products is not
prevented. Instead of bonding with the
carbocation like in Figure 3c, the
chloride ion can also attack the
hydrogen in the C-H bond shown in
this mechanism:
+
Cl-

Figure 6a. Protonation of OH group

by HCl

Figure 6c. Formation of isobutylene

from carbocation intermediate
The reaction will proceed as shown in
Figure 3a and 3b, however, the
nucleophilic chloride will instead
attack the hydrogen in the C-H bond
and the electron of the bond will be
donated to the carbocation to yield
isobutylene (Figure 6c). This is called
elimination
reaction
since
the
hydroxide group is expelled instead of
being substituted with the chloride
ion. This can happen when the
reaction
is
made
at
a
high
temperature since this encourages
elimination
reactions.[1]
As
a
precaution, cold concentrated HCl
solution is used in order to ensure that
the reaction will proceed towards an
SN1 reaction instead of an elimination
reaction in order to yield t-butyl
chloride instead of isobutylene. Excess
HCl solution is also added to further
drive the reaction towards the
formation of t-butyl chloride via Le
Chateliers principle.
When t-butyl alcohol is reacted with
HCl in a separatory funnel, it is
necessary to slowly open the stopcock
from time to time to relieve the
pressure that developed from the
mixing of the two reagents since this
pressure can force the stopper out of
the separatory funnel and can also
make the draining of the layers
difficult. [2]

In separating the organic and aqueous

layer, 6 M of NaCl solution was added
since this increases the ionic strength
of the aqueous layer. Organic layer is
usually not compatible with a solution
of high ionic strength and forces the
separation of it from the aqueous layer
[2]
. After the organic layer is separated,
solid NaHCO3, a weak base, is added in
order to neutralize the excess HCl that
may still be present in the organic
layer. Water adhering in the mixture is
removed by drying the organic layer
with anhydrous CaCl2 that absorbs the
water present. Water must be
removed completely from the crude
product before purifying through
distillation. If it is not completely
removed, water can serve as a weak
nucleophile that can convert back tbutyl chloride into t-butyl alcohol when
the product is heated in the distillation
process
via
an
S N1
reaction
mechanism.
+
Cl-

Figure 7a. Rate-determining step to

yield carbocation intermediate from
alkyl chloride dissociation
H 2O

Figure 7b. Fast step reaction of water

with carbocation to yield protonated
alcohol

Figure 7c. Proton loss of alcohol to

form neutral alcohol and hydronium
ion
This is also the reason why solid
instead of aqueous NaHCO3 solution is
used in neutralizing the excess acid.
Aqueous NaHCO3 introduces much
water in the product and thus presents
a risk of hydrolyzing the fresh t-butyl
chloride and converting it back to tbutyl alcohol.
To purify the t-butyl chloride obtained,
the crude product is subjected to
distillation. Distillation as a purification
technique, takes advantage of the
difference in the boiling points of the
substance of interest, impurities and
side products present. The possible
compounds that may be present in the
crude product are isobutylene, t-butyl
alcohol, HCl, water and of course, tbutyl chloride. Isobutylene has a very
low boiling point, -6.9C, and as such,
it will simply vaporize even at room
temperature. Tert-butyl alcohol on the
other hand has a boiling point of
82.2C while t-butyl chloride is 51 C.
Water and HCl has a relatively high
boiling point because of their polarity,
100C and 105.58C respectively. [4] As
such, at a temperature range of 4259C, all of isobutylene have already
vaporized and t-butyl alcohol, HCl and
water are still not starting to become
vapors. On the other hand, t-butyl
chlorides boiling point is under this
temperature range and as such, the
fraction that boils off at this
temperature is purely t-butyl chloride.
On the other hand, in the distillation
set-up, boiling chips are placed inside
the distilling flask in order to prevent
bumping. Bumping is characterized by
formation of very large bubbles that
sometimes erupt violently when the
solution becomes superheated. It must
be avoided because it brings the risk
of breaking the glassware and loss of
5

material. Boiling chips produce a

steady stream of fine air bubbles when
heated in a solvent. It prevents
bumping from occurring since the
stream of bubbles and turbulence
produced breaks up the large bubbles
of gases in the solution being heated.
It thus promotes smooth boiling of the
solution. Boiling chips must be added
in the liquid before heating has begun,
otherwise, the boiling chips suddenly
placed in a superheated solution will
cause the liquid to boil at once. As a
result, the solution will splash entirely
out of the flask violently. [2]
The condenser in the distillation set-up
prevents any material loss. Water
continuously circulates in the outside
of the condenser and thus this
condenser is called a water-jacketed
condenser. As the vapor rises in the
inner tube, the water circulating
outside removes the heat from the
vapor and condenses them. Airjacketed condenser can also be used
but water-jacketed is most effective
when handling vapors that are difficult
to condense or substances that are
volatile like the case of t-butyl
chloride. The receiving flask is also
kept in a cold water bath to prevent tbutyl chloride from vaporizing. [2]
To test if the obtained distillate is tbutyl chloride, it is subjected to
solubility test with water. Alkyl halides
are water-insoluble, thus negative test
result signifies the presence of t-butyl
chloride. It also tests if t-butyl alcohol
is obtained instead since alcohol with
less than five carbons such as t-butyl
alcohol is relatively soluble in water.
Shown in Table 2 are the observed
properties of the product obtained
which are also nearly the same as the
properties of t-butyl chloride thus
Table 1:positive
Properties
of product obtained
implying
yield.

Boiling point, C :
Color
:
Solubility in H2O :

50
White,
opaque
insoluble

On the other hand, summarized in

Table 2 is the yield obtained for the
synthesis of t-butyl chloride.
Table 2: Yield for the synthesis of tbutyl chloride

Weight of t-butyl alc., 7.780

g
:
Weight of t-BuCl, g 4.654
:
Theo.
Yield,
g 9.716
:
%
yield 47.90
:
The percentage yield of t-butyl
chloride is relatively high implying that
side and backward reactions are
mostly prevented. It also proves the
efficiency of distillation as a method of
purifying a substance. However, this
result still had suffered from various
errors. The glasswares used in the
synthesis such as the separatory
funnel and flasks may not have been
all dry and clean. The use of slightly
wet glasswares can introduce water
and
other
impurities
that
can
hydrolyze the formed t-butyl chloride
or hinder the synthesis reaction from
occurring which can all result to a
lower percentage yield. The cold
concentrated HCl solution prepared
may have been allowed to stand at
room temperature before reacting it
with t-butyl alcohol, thus isobutylene
may have been formed as illustrated
by Figure 6. As such, the HCl reagent
to be used should be kept cold as
possible to prevent any side reactions
from occurring. Though the product
from the side reaction, isobutylene, is
very volatile and can easily be
removed from the mixture, formation
of it still lowers the yield of the
synthesis. It must also be ensured that
6

the boiling chips added are clean and

free from impurities. Loose stopcocks
and joints in the distillation set-up can
also be a source of error since it
results to material loss and lowers the
percentage yield. To lessen this, the
joints must be keenly secured with
Parafilm to prevent vapors from
escaping. Another source of error is
when the mixture is allowed to boil
above the given temperature range
causing other impurities to vaporize as
well. Though incomplete conversion of
reactants to products is expected for
any
reactions
given
that
the
temperature and pressure of the
surroundings
can
affect
the
equilibrium of the reaction, reducing
these sources of errors can help in
increasing the yield in synthesis
reaction.
But
given
that
the
percentage yield can be considered
high, these sources of errors are
nearly minimized throughout the
conduction of synthesis.
CONCLUSION
Synthesis of alkyl halides is important
not only in the study of them but also
in the fields of industry, medicine and
agriculture because of their practical
uses. The commonly used method of
preparation
of
alkyl
halides
is
hydrohalogenation of alcohols. Tertbutyl chloride, a tertiary alkyl halide, is
synthesized from tert-butyl alcohol
through SN1 reaction with HCl rather
than SN2 because of the relative
stability
of
the
carbocation
intermediate formed. However, at high
temperature condition, elimination
reaction is encouraged and thus tbutyl alcohol may also undergo
elimination
reaction
to
yield
isobutylene.
Tert-butyl
chloride
obtained is carefully dried in order to
remove any water that can hydrolyze
the product back to t-butyl alcohol.
The obtained crude product is further
purified through fractional distillation

which
takes
advantage
of
the
difference in boiling points of the
impurities and desired substance. The
obtained percentage yield is 47.90%.
This relatively high yield shows the
efficiency of using hydrohalogenation
of tertiary alcohols in preparing
tertiary alkyl halides. It also implies
the effectivity of distillation as a
purification
technique
given
the
differences of the boiling points of the
compounds present in the substance
to be purified. It shows that sources of
error such as contamination from
flasks and boiling chips are nearly
minimized and water is mostly
removed from the fresh t-butyl
chloride synthesized.
REFERENCES
[1]

McMurry, J. (2008). Organic

Chemistry 7th ed. Chapter 10:
Organohalides,
Chapter
11:
Reactions of Alkyl Halides:
Nucleophilic Substitutions and
Eliminations & Chapter 17:
Alcohols
and
Phenols.
Brooks/Cole, Cengage Learning:
Belmont, pg. 344, 362-380 &
618.

[2] Pavia, D., Lampman, G., Kriz, G.

and
Engel
R.
(1995).
Introduction
to
Organic
Laboratory Techniques. Part
Five: The Techniques. Saunders
College Publishing: Orlando, pp573-574, 641-642, 657, 659.
[3] Alroche, C. Alkyl Halides. Rutgers
University-Camden.
[Online].
2014.
Retrieved
from:http://crab.rutgers.edu/~al
roche/Ch06.pdf
(accessed
March 8, 2015).
[4] ScienceLab. Material Safety Data
Sheet.
ScienceLab.Com:
Chemicals
&
Laboratory
Equipment.
[Online].
2005.
7

Retrieved
from:
http://www.sciencelab.com/msd
s.php? (accessed March 9,
2015).
[5] The University of Sydney Faculty of
Science.
Experiment
28:
Extraction.
[Online].
2014.
Retrieved
from:
https://scilearn.sydney.edu.au/fy
chemistry/prelab/images/E28ext

ractionimage1.gif
March 9, 2015).
[6]

(accessed

Erowid
Organization.
Simple
Distillation Set-Up. Erowid.Org.
[Online]. 2014. Retrieved from
https://www.erowid.org/archive/r
hodium/chemistry/pictures/sdist
.setup.gif (accessed March 9,
2015).

Appendix
Calculation of Percentage Yield

wt of vial with pdctwt of empty vial=20.657 g16.003 g=4.657 g : wt of tbutCl obtained

wt of tbutyl chloride x

wt of tbutyl alcohol x

1 mol tbutyl chlorid e

1 mol tbut Cl
=4.657 g x
=0.04873 mol of tbutCl
MW of tbutyl chloride
92.562 g

1mol tbutyl alcohol

1 mol tbutOH
=7.780 g x
=0.1050 mol tbutOH
MW of t butyl alcohol
74.12 g

Theoretical conversion:

0.1050 mol of tbutOH x

1 mol tbutCl
92.562 g
x
=9.716 g t butCl=theoreti cal yield
1mol tbutOH 1 mol tbut Cl

Actual yield:

amt of tbutylCl obtained

4.654 g
x 100 =
x 100 =47.90 : Percentage yield
theoretical amt of tbutCl yield
9.716 g