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Synthesis and Purification of Tert-butyl Chloride

Clarice Santosa
National Institute of Physics, College of Science, Diliman, Quezon City 1101, Philippines,
a

ABSTRACT

Alkyl halide preparation is not only significant in the study of them but also because of its practical applications in the fields of
agriculture, industry, and medicine. It can be prepared by acid-catalyzed substitution of alcohols. In this experiment, the
synthesis of an alkyl halide is done by reacting the corresponding alcohol with a hydrogen halide in an easy and inexpensive
SN1 reaction. tert-butyl chloride (TBC) is synthesized through a nucleophilic substitution reaction of tert-butyl alcohol (TBA)
using HCL by SN1 mechanism. The crude product obtained was purified by fractional distillation by making use of the
difference in boiling points of impurities and desired compound. The calculated percent yield is 126.98%. The high yield can
be due to impurities misrepresented as products i.e. water mass as product mass, or an error was committed when measuring
the amount of the products, etc. But this also shows the effectiveness of hydrohalogenation of tertiary alcohols to produce
tertiary alkyl halides and the use of distillation as a purification technique for liquids.

1. Introduction reaction with Grignard reagents; the reaction of

Halogen-substituted alkanes, commonly called
alkyl halides are systematically named as haloalkanes,
treating the halogen as a substituent on a parent alkane
chain. They belong to a class of compounds with a
halogen atom bonded to a saturated, sp3-hybridized
carbon atom. They are shown with the formula RX,
where R is a carbon chain and X is the halogen
representation. The halogen atom X is more
electronegative than the carbon atom making the C-X
bond polar, more polar than hydrocarbons but also
insoluble in water because it cannot form an H-bond
with the water molecule.
Alkyl halides are classified the same way as
carbocations, depending on the number of neighboring
carbons attached to the halogen. Primary (1°) alkyl
halides have one carbon bonded to a halogen atom,
while secondary (2°) alkyl halides has two carbons
connected to a halogen, and tertiary (3°) alkyl halides
have three carbons attached to a halogen. As the
neighboring carbon increases, the classification of
halide also increases; as the classification increases, its
stability also increases.
alcohols with hydrogen halides - the most common and
generally useful technique.
Alcohols react with hydrohalogenated
compounds like HCl and HBr to produce alkyl halides
through nucleophilic substitution reactions that follow
the SN1 mechanism. SN1 mechanism involves the
formation of a carbocation with the protonated alcohol
acting as the substrate; secondary, tertiary, allylic and
benzylic alcohols react through this mechanism. The
reaction of SN1 mechanism under acidic conditions
involves two steps: (1) rapid protonation of the alcohol
followed by the loss of water which generates a stable
carbocation and (2) quick nucleophilic attack by the
nucleophile on the carbocation. The general reaction
for tertiary alkyl halide synthesis is shown below:

Alkyl halides have a wide range of applications

in the fields of agriculture, industry, and medicine.
Examples of these are their use as solvents, refrigerants,
pesticides, fungicides, and anesthetics. They are also
very important in giving important leads to new
medicines. Because of their benefits, systematic
techniques have been formulated to synthesize them.
Alkyl halides can be prepared from alkanes by radical Figure 1. General reaction of tertiary alcohol to
halogenation; from alkenes by allylic halogenation; produce an alkyl halide.
 Organic Chemistry Laboratory Manual
Distillation, in contrast with the synthesis of
alkyl halides, is a process of separating components of
a mixture based on different boiling points. It is a
technique of heating a liquid to create vapor which is
collected when cooled separately from the original
liquid that can aid in purification. It takes advantage of
the difference in boiling points of impurities and
substance of interest.
In this experiment, tert-butyl chloride (TBC)
will be synthesized from tert-butyl alcohol (TBA) using
the mechanism mentioned above. Tert-butyl alcohol (2-
methyl-2-propanol) is the simplest tertiary alcohol. It is
a colorless liquid with a boiling point of 83°C. It is used
in food as flavoring agents and on the industry as fuel,
solvents, plasticizer, and many more. On the other hand,
tert-butyl chloride (2-chloro-2-methylpropane), is also
a colorless liquid with a boiling point of 51°C. It is a
highly flammable and volatile liquid that is produced
industrially as a precursor to other organic compounds.
Figure 2: TBA (left) and TBC (right)
After the synthesis, TBC is purified using
distillation. This experiment aims to understand and to
do properly the mechanism involved in the
nucleophilic substitution reaction of alcohols with
hydrogen halides, and the possible side reactions that
may happen during synthesis. possible side products
may also happen. This also evaluates the efficiency of
distillation as a purification method.
2. Materials and Methods
2.1 Synthesis of TBC
Tert-butyl chloride and cold concentrated HCl
were combined in a separatory funnel and allowed to
react. It was left undisturbed until separation layers
were visible. NaCl solution was added to improve the
separation of layers. The aqueous layer was discarded,
and the organic layer was added with drops of water
and solid NaHCO3 to remove impurities and excess
reactants. The mixture was decanted and the solution
of interest was collected and dried with CaCl2. The
resulting solution is decanted to be distilled.
2.2 Distillation
The resulting solution was distilled. The
fraction that was distilled at around 50-55°C was
collected with a pre-weighed round bottom flask. The
purified TBC's percentage yield was then determined.
3. Results and Discussion
The reaction between TBA with HCl to produce
TBC uses the stability of the intermediate carbocation.
The nucleophilic hydroxide is replaced with a more
nucleophilic halogen, which is attracted from the
formation of the carbocation intermediate. This is
called nucleophilic substitution and follows the SN1
mechanism.
Cold HCl was added to prevent volatilization of
products and to minimize the production of side
products. HCl was in excess to favor forward reaction.
During the experiment, the boiling point of the
product showed that the experimentally produced
alkyl halide was TBC with the boiling point range of 50-
55°C. This boiling point agrees with the theoretical data
and therefore met the objective of synthesizing TBC.
The calculated percent yield 126.98% is relatively high
suggesting that side and backward reactions are
prevented but this result of above 100% suggests also
of errors. This may have resulted from both systematic
and random errors. The glassware that were used may
not have been properly cleaned and dried, introducing
water and other impurities to the experiment. Another
source of error was that the mixture was allowed to
boil at higher temperatures causing impurities to also
vaporize. The surrounding temperature and pressure
might have also contributed to these errors.
4. Conclusion and Recommendations
The synthesis of alkyl halides is very important
not just because it needs to be studied but also because
of its practical and industrial uses. The most common
technique of preparing alkyl halides is through
hydrohalogenation of alcohols. Synthesis of tert-butyl
chloride, a tertiary alkyl halide, from tert-butyl alcohol
with HCl follows the SN1 mechanism rather than the
SN2. Because a relative stable carbocation intermediate
was formed. But, at high temperatures, elimination
reaction happens and this causes tert-butyl alcohol to
produce isobutylene. Tert-butyl chloride produced was
dried to remove any water that might hydrolize the
 Organic Chemistry Laboratory Manual

product back into tert-butyl alcohol. The crude product Synthesis of tert-Butyl Chloride. Retrieved from:
was purified through distillation. http://www.rsc.org/suppdata/books/184973/
9781849739634/bk9781849739634-
Distillation has an advantage on boiling point chapter%202.1.pdf (accessed March 4, 2019)
differences of the impurities and the substance of
interest. The percent yield calculated was 129%. This Appendices
result is relatively high, showing that the
hydrohalogenation of tertiary alcohols to produce A. Set-ups
tertiary alkyl halides was efficient and that the
purification through distillation process was also
effective. But this also shows that errors were not
minimized, resulting in above 100% yield. These errors
were mostly systematic and can be minimized and/or
corrected if the experiment was properly done.

References

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Shoemaker BA, Thiessen PA, Yu B, Zaslavsky L,
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improved access to chemical data. Nucleic Acids Figure 3: Set-up for separating aqueous and
Res. 2019 Jan 8; 47(D1):D1102-1109. organic layer
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30371825]

McMurry, J. (2015). Organic Chemistry 9th ed. Chapter

10: Organohalides. Brooks/Cole, Cengage
Learning: Belmont, pp. 287-307.

Pavia, D., Lampman, G., Kriz, G. and Engel R. (1995).

Introduction to Organic Laboratory Techniques.
Part Five: The Techniques. Saunders
College Publishing: Orlando, pp. 573-574, 641-
642, 657, 659.

Reusch, R.[Online]. 2013. Mechanisms of Nucleophilic

Substitution Reactions. Mechanisms of
Nucleophilic Substitution Reactions. Retrieved Figure 4: Distillation set-up
from:
https://www2.chemistry.msu.edu/faculty/reus B. Answers To Questions
ch/virttxtjml/alhalrx2.htm (accessed March 4, 1. What is the mechanism of the reaction between
2019) tert-butyl alcohol and HCl?
SN1 reaction mechanism, a unimolecular
Roche, A. Alkyl Halides. Rutgers University -Camden. nucleophilic substitution that uses the stability of the
[Online]. 2014. Retrieved from: formed carbocation intermediate.
http://crab.rutgers.edu/~alroche/Ch06.pdf
(accessed March 4, 2019). 2. What are the possible side products in the synthesis?
Show the mechanism for the formation of these side
Royal Society of Chemistry. [Online]. 2017. products.
Supplementary information for Comprehensive SN1 and E1 mechanisms occur simultaneously
Organic Chemistry Experiments for the and competitively with one another in a reaction. This
Laboratory Classroom. A SN1 Reaction: competing reaction produces side products like 2-
 Organic Chemistry Laboratory Manual

methylpropene for the synthesis of alkyl halide as 5. Why is solid NaHCO3 used instead of aqueous
shown below: NaHCO3?
See answer in question no. 2.

6. What is the importance of drying the crude alkyl

halide product with anhydrous CaCl2
before distillation?
See answer in question no. 2.

7. Discuss how the target compound was isolated from

possible impurities.
The target compound was isolated by using a
separatory funnel by separating the organic layer from
Hydrolysis of alkyl halide can also happen as the aqueous layer that can be a source of impurities.
shown below: Then, desiccation was done to get the crude product.
Finally, distillation was done to remove other
impurities that have other boiling points that the
desired product.

8. What is the purpose of adding boiling chips?

Boiling chips were added in order to prevent
uneven heat distribution in the solution that may cause
it to boil violently.

And the reverse reaction of TBA to TBC can also
happen since water is present as shown below:
9. Discuss the importance of the continuous flow of
water in the condenser during distillation.
Continuous flow of water makes the condenser
cold in order for it to condense vapors and to make
sure that no vapor can escape from the distillation
process.

C. Datasheet
Reaction Scheme

3. What precautions were made to limit or prevent the

formation of side products?
The use of cold HCl to avoid the volatilization of
the product, it also in excess to favor forward reaction Mass ____7.8___ __8.51____
and lastly it was concentrated to ensure it was in
excess and to minimize the amount o usage. NaCl was molecular wt _74.12 g/mol 92.57 g/mol
added to enhance separation of layers between
aqueous and organic layers. Solid NaHCO3 was added to Density __0.78 g/mL _0.851 g/mL
remove excess acid still present in the crude product. mmol __105.23__ __91.93___
Lastly, anhydrous CaCl2 was added to remove excess
water to avoid hydrolysis. Experimental Results

4. Why is it necessary to use cold concentrated HCl? Mass of tert-butyl alcohol, g ____7.8___
Why is it added in excess?
See answer in question no. 2. Mass of tert-butyl chloride, g __12.37___

Theoretical yield 9.74 g TBC

 Organic Chemistry Laboratory Manual

% yield _126.98 %

Properties Tert-butyl Tert-butyl

alcohol chloride
Color clear clear
Solubility soluble Slightly soluble
in
water
Boiling 83°C 51-52°C
point

D. Sample Calculations
0.81 g
10ml TBA x  8.1g TBA
ml

mol 1000 mmol

8.1g TBA x x  109.282245mmol
74.12 g 1mol

1mol
Theoretical yield  109.28mmol TBA x
1000 mmol
1mol TBA 92.57 g TBC
x x  9.741581219 g TBC
1mol TBC mol

actual yield
% yield  x100%
theoretical yield
12.37 g TBC
 x100%  126.989016%
9.74 g TBC