C.T. Alcoriza / Chemistry 31.

1 (2019) P a g e |1

Synthesis and Purification of tert-Butyl Chloride

Caesar John T. Alcoriza
Department of Chemical Engineering, University of the Philippines Diliman, Quezon City, Philippines
Performed 13 June 2019; Submitted 19 June 2019

ABSTRACT
Haloalkanes are a group of chemical organic compounds that contain one or more members of the halogen
family. Mechanisms for preparation of haloalkanes include nucleophilic substitution, free radical substitution,
and electrophilic addition. In this experiment, a haloalkane was prepared by reacting an alcohol with a
hydrohalic acid. tert-Butanol and hydrochloric acid were allowed to react via nucleophilic substitution,
following the SN1 mechanism. After performing a series of separation techniques and distillation, a purer tert-
butyl chloride product was obtained. From 7.89 g of tert-butanol, 3.0 g of tert-butyl chloride product was
obtained, which translates to 30.% yield. The boiling point of the purified product was at 78 °C which deviates
from the actual boiling point of tert-butyl chloride which is 51 °C. The obtained product exhibited other
properties similar to pure tert-butyl chloride: colorless and immiscible in water. The reaction mechanism for
the conversion of tert-butanol to tert-butyl chloride was explored.

Introduction methylpropane, commonly known as tert-butyl

The development of organic chemistry as a
scientific discipline began with the discovery that
ammonium cyanate, an inorganic compound, could be
used to synthesize urea, an organic compound which
has previously been thought to be only synthesized by
living things [1]. Since then, millions of organic
compounds have been synthesized by utilizing
various reactions.
Haloalkanes, similarly known as alkyl halides, are
one of the families of carbon compounds. These
organic compounds contain a halogen bonded to an
sp3-hybridized carbon. Due to the relatively high
electronegativities of the halogens, there is a partial
negative charge on the halide substituents and a
partial positive charge on the carbon to which the
halogens are attached.
Several applications in various industries such as
pharmaceutical, industrial, and petrochemical have
been found for haloalkanes [2]. These compounds
have been used as refrigerants, propellants,
retardants, and even precursors for the synthesis of
other organic compounds.
Preparation and synthesis of haloalkanes could be
through the radical halogenation of alkanes, allylic
halogenation of alkenes, reaction with Grignard
reagents, or reaction with alcohols—another group of
compounds that contain a hydroxyl group [3].
In this experiment, one of the objectives was to
synthesize a haloalkane. The synthesis of 2-chloro-2-
Mobile: 09156175805
E-mail address: ctalcoriza@up.edu.ph
chloride, was performed through the SN1 reaction of
tert-butanol, a tertiary alcohol, with concentrated
hydrochloric acid (HCl). Following the synthesis, the
goal was to purify the obtained crude tert-butyl
chloride product by means of distillation.
Materials and Methods
Synthesis
To a 50-mL separatory funnel, 10.0 mL of tert-butyl
alcohol and 20.0 mL of cold concentrated HCl were
added. The mixture was swirled two to three times
while venting from time to time. The mixture was left to
stand for 20 minutes; after which, two layers became
visible.
The lower, aqueous layer was discarded, and the
upper, organic layer was transferred to a dry
Erlenmeyer flask containing a small amount of sodium
bicarbonate (NaHCO3). The flask was swirled and the
liquid was decanted to another Erlenmeyer flask.
To dry the collected filtrate, small amounts of
anhydrous calcium chloride (CaCl2) were added until no
more clumping of the solid was observed.
Purification
The crude product was once again decanted into a dry
25-mL round bottom flask containing boiling chips. The

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 C.T. Alcoriza / Chemistry 31.1 (2019)
crude tert-butyl chloride was distilled according to the
setup shown in the Appendix. The drops that were
collected below the desired temperature were
discarded. A purer tert-butyl chloride product was
obtained.
Results and Discussion
The reaction of tert-butanol with concentrated HCl to
form tert-butyl chloride involves a nucleophilic
substitution wherein the hydroxyl group is replaced by
chlorine. The overall reaction is shown below.
Figure 1. Overall reaction from tert-butanol to tert-
butyl chloride.
The reaction proceeds through an SN1 mechanism,
which involves the formation of a carbocation. This is
unlike the SN2 mechanism which does not involve the
formation of intermediates [4].
Figure 2. Reaction mechanism for the nucleophilic
substitution from tert-butanol to tert-butyl chloride.
In the first, rapid step, HCl protonates the alcohol,
which creates a positive formal charge on the oxygen
atom. A heterolytic bond cleavage occurs, and a good
leaving group forms, which is water. This rate-
determining step leaves a relatively stable tertiary
carbocation, which is a feature of reactions involving the
SN1 mechanism [4]. The nucleophilic chlorine anion
resulting from the heterolytic bond cleavage of HCl
quickly attacks the electrophilic carbon, forming tert-
butyl chloride.
The bulky sterically hindered tertiary carbon makes
it difficult for the SN2 reaction to occur, which involves
the formation of a transition state without the formation
of intermediates [3]. Extending the idea, tertiary
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P a g e |2
alcohols follow the SN1 route; primary alcohols, the SN2
route; and secondary alcohols, either path.
It was necessary to cool HCl prior to mixing it with
tert-butanol as a precaution to limit the formation of
side products. Adding hot acid to alcohol would favor an
elimination reaction rather than substitution [1]. The
dehydration of tert-butanol, which happens through an
E1 mechanism, would produce 2-methylpropene or
isobutylene rather than tert-butyl chloride. Further, the
first step in the mechanism is a fast equilibrating step
[6]; thus, addition of HCl in excess would favor the
formation of products by Le Chatelier’s principle.
Figure 3. Formation of butylene, a side product, from
the carbocation intermediate.
The addition of NaHCO3 to the separated organic
layer served to neutralize any unreacted acid. Solid,
rather than aqueous, NaHCO3 was used since water
present in aqueous NaHCO3 could hydrolyze the tert-
butyl chloride product and convert it back to tert-
butanol. Similarly, the HCl used was concentrated
because water present in dilute HCl would promote the
formation of undesired side products.
Anhydrous CaCl2 absorbed any water present in the
crude tert-butyl chloride product, thus reducing any risk
of product loss due to conversion back to alcohol.
Venting the separatory funnel from time to time while
mixing was essential as it helped avoid the buildup of
pressure inside the funnel, which, if left unvented would
cause the funnel to shoot out.
Boiling chips were added to ensure that the solution
would not boil violently and to prevent superheating. A
more controlled boil would decrease the risk of product
loss due to boil over. Placing the receiving flask in an ice
bath suppressed the re-volatilization of the liquid
product; otherwise, the portion of tert-butyl chloride
that volatilized would translate to product loss. The
continuous flow of water in the condenser during
distillation was necessary for continuous heat transfer.
The water inlet being at the side farther from the heat
source ensured that the water entering the condenser is
cool; further, compared to concurrent flow,
countercurrent flow of water in the condenser results to
a greater amount of heat transfer [5].
The first few drops that was collected on the receiving
flask before reaching the desired temperature were
discarded, as these were the more volatile components
in the solution that boiled below the expected boiling
 C.T. Alcoriza / Chemistry 31.1 (2019)
point of tert-butyl chloride. At some point, the
temperature remained constant at 78 °C, which was
taken to be the boiling point of the tert-butyl chloride
product. This deviates from the actual boiling point of
around 51 °C [6], and this difference between the actual
and experimental boiling points could be attributed to
the presence of impurities such as unreacted reagents
and side products.
Table 1. Experimental results.
Mass of tert-butyl alcohol 7.89 g
Mass of tert-butyl chloride 3.0 g
Theoretical yield 9.85 g
% yield 30.%
In this experiment, 3.0 g of tert-butyl chloride was
synthesized from 7.89 g (10.0 mL) of tert-butanol. This
translates to about 30% yield, knowing that there is a
1:1 ratio between tert-butyl chloride and the limiting
reactant, which is tert-butanol. The final product was
colorless, and was shown to be immiscible with water,
which, to an extent, agrees with the properties of tert-
butyl chloride [6]. Thus, the final purified product can be
considered as relatively pure compared to the crude
product prior to distillation.
Table 2. Properties of final tert-butyl chloride product.
Color colorless
Solubility in water immiscible
Boiling point 78 °C
Reasons for low yield include the time that was
allotted for the separation of the organic and aqueous
layers in the separatory funnel. If the solution had been
given more time, the two layers would have attained a
better separation. Product loss within this step was
expected due to the possibility of a small portion of the
tert-butyl chloride product remaining in the aqueous
layer.
Product losses were also present in decanting the
solution from one Erlenmeyer flask to another. Some of
the tert-butyl chloride product adhered to the glass
walls and remained in the Erlenmeyer flasks. Some of
the product also adhered to the solid reagents such as
NaHCO3 and CaCl2. Amounts of these solid reagents that
are too much in excess than the necessary amount
provide more surface area to which the liquid product
could adhere, which is why it was necessary to moderate
the amounts of these solid reagents especially if no
washing of the solid is involved.
The low percent yield could also be attributed to the
formation of the side product, butylene, in which the
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P a g e |3
carbocation left behind by the leaving group loses a
proton and forms a C-C double bond.
Water that was present prior to the addition of
anhydrous CaCl2, which was due to the imperfect
separation of the organic and aqueous layers and due to
the reaction of NaHCO3 with HCl, could have also reacted
with tert-butyl chloride, hydrolyzing the product and
converting it back to tert-butanol; thus, this has also
affected the product yield.
Conclusion and Recommendations
Through the experiment, an alkyl halide, tert-butyl
chloride was synthesized from a tertiary alcohol, tert-
butanol, by reacting the alcohol with HCl that followed
the SN1 mechanism owing to the relative stability of the
carbocation formed. The process for synthesis and
purification was relatively straightforward, and relied
on employing various techniques that increase yield,
such as the suppression of any side reactions and side
products. By synthesizing an alkyl halide from the
reaction of an alcohol and a hydrohalic acid, the
unimolecular nucleophilic substitution mechanism was
explored.
Overall, the synthesis and purification of the alkyl
halide was a success. However, there are specific aspects
of the experiment that could have been better. The
product, which represents a 30.% yield, displayed
properties similar to pure tert-butyl chloride except for
the boiling point, which deviates from the actual boiling
point of tert-butyl chloride by 27 °C.
The mixture in the separatory funnel could be given
more time to allow a better separation of the layers. For
a better separation of the aqueous and organic layers,
NaCl solution could be added. It is recommended to be
careful in adding NaCl solution, and it is also
recommended to use a slightly less saturated NaCl
solution to avoid the formation of NaCl solid which could
clog the separatory funnel.
Further, it is recommended to use a reagent, if
possible, that could be used to wash the flasks which the
crude tert-butyl chloride was decanted from. One of the
reasons for product loss is the adherence of the product
on the glass walls. If the flask could be washed with an
appropriate reagent, the product that remained in the
flask could be recovered. It is important that the reagent
does not react with tert-butyl chloride, and that it could
be separated from the product by means of distillation
or other purification techniques.
 C.T. Alcoriza / Chemistry 31.1 (2019) P a g e |4

References

[1] McMurry, J. Organic Chemistry, 8th ed.; Cengage

Learning, 2010.

[2] Felder, R.; Rousseau, R.; Bullard, L. Elementary

Principles of Chemical Processes, 4th ed.; Wiley, 2016.

[3] Klein, D. Organic Chemistry, 3rd ed.; Wiley, 2012.

[4] Solomons, G.; Fryhle, C.; Snyder, S. Organic Chemistry,

12th ed.; Wiley, 2016.

[5] Smith, J.; Van Ness, H.; Abbott, M. Introduction to

Chemical Engineering Thermodynamics, 8th ed.; McGraw-
Hill, 2018.

[6] Perry, R.; Green, D. Perry’s Chemical Engineers’

Handbook, 9th ed.; McGraw-Hill, 2018.

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 C.T. Alcoriza / Chemistry 31.1 (2019) P a g e |5

APPENDICES

Appendix A. Distillation Setup

Appendix B. Reaction Scheme

tert-Butanol tert-Butyl Chloride

Mass 7.89 g 9.85 g
Molecular weight 74.123 g/mol 92.556 g/mol
Density 0.7886 g/mL 0.851 g/mL
mmol 106 mmol 106 mmol

Appendix C. Calculations

mtert-butanol = (10.0 mL) (0.7886 g/mL) = 7.886 g ≈ 7.89 g

ntert-butanol = (7.886 g) (1 mol / 74.123 g) (1000 mmol / 1 mol) = 106.390 mmol ≈ 106 mmol

mtert-butyl chloride = (106 mmol) (1 mol / 1000 mmol) (92.556 g/mol) = 9.847g ≈ 9.85 g

% yield = (3.0 g / 9.85 g) (100) = 30.%

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