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Preparation and purification of an alkyl halide

Weand S. Ybaneza,*, Niquitta Galapa
National Institute of Molecular Biology and Biotechnology, University of the Philippines, Diliman, Quezon City, Philippines

ABSTRACT
The reaction of tert-butanol with cold, concentrated HCl to produce tert-butyl chloride was used to demonstrate the general S N1
reaction of tertiary alcohols to form tertiary alkyl halides. Organic and aqueous layers were separated, with the organic layer
subsequently distilled to isolate the tert-butyl chloride. The set of methods employed produced a relatively low percent yield =
8.33%. Assessment of the product obtained was only done quantitatively, with solubility being the basis. Purity wasnt determined.

*Corresponding author. Mobile: 09351855632

E-mail address: wsybanez@gmail.com

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1. Introduction

attacks the carbocation, forming tert-butyl chloride[3][4].

The reaction mechanism is shown in Figure 2.

Alkyl halides are typically synthesized through a

nucleophilic substitution reaction of hydrogen halides
(HX, X = Cl, Br, I) to an alcohol, with water as a common
side-product [1]. The experiment involved the formation
of tert-butyl chloride from tert-butyl alcohol.
Tert-butanol is classified as a tertiary alcohol with the
hydroxyl group (-OH) attached to a tertiary carbon. This
criterion usually makes the reaction follow the S N1
reaction mechanism, given the right environmental
conditions. The OH group depart as a leaving group and
is substituted with Cl- (nucleophile) from the acid[1].
Likewise, a tertiary alkyl halide is formed, as shown in
Figure 1.

Fig. 2. Formation of tert-butyl chloride [4]

Fig. 1. Synthesis of tert-butyl chloride from tert-butanol
[2]
After the formation the alkyl halide from the alcohol,
distillation of the organic layer was performed. This
separation technique was employed to extract a
relatively purer tert-butyl chloride from the organic layer.
The experiment aims to synthesize tert-butyl chloride
from tert-butanol and to purify it further by simple
distillation technique.
2. Materials and Methods

3.2. Reagent Analysis

The first technique to increase yield is the use of cold
concentrated HCl was used as the hydrogen halide. This
is because through the E1 mechanism, an alkene will be
formed when tertiary alcohols react with an acid at
relatively mild heat[3].
2methylpropene will be formed, as shown in Figure 3. It is
also added in excess in order to push the synthesis
reaction forward, and to avoid occurring as the limiting
reagent.

2.1. Preparation
15 mL tertbutyl alcohol was mixed with 20 mL
concentrated HCl and allowed to stand in a separatory
funnel. Saturated NaCl solution was added and after 20
minutes, the aqueous layer was discarded. The organic
layer was thereafter added with NaHCO 3 and supposedly,
with anhydrous CaCl2.
2.2. Purification
The crude tertbutyl chloride into a pre-weighed
round bottom flask for distillation. Boiling chips was
added and the solution was heated to a gentle boil. The
first milliliters of distillate was discarded and the fraction
that boils 49-52C was collected and weighed.
3. Results and Discussion
3.1. Reaction Mechanism
Tert-butyl chloride reacts with HCl through the S N1
mechanism. This involves the formation of a carbocation
intermediate with the protonated alcohol acting as a
substrate. The reaction happens in three steps, with the
first step being the protonation of the alcohol. Second,
the hydronium ion is cleaved from the molecule, forming
a carbocation in a slow step. Lastly, the nucleophile (Cl-)

Fig. 3. Formation of 2-methylpropene [5]

Another side product would be di-tert-butyl ether,
which involves the SN1 reaction from tert-butanol to ditert-ether. In contrast to the synthesis of alkyl halides,
the nucleophile that attacks the carbocation will be tertbutanol itself (the lone pairs in the O atom) instead of a
halide (Cl-) [6]. The mechanism is shown in Figure 4
below.

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layers may also not be separated well due to variance in

assessing the interphase, and some of the organic layer
may be disposed. Losses can also be accounted to
decantation, and also on the distillation process. 1-2
drops of water was added to the distillate, determining
that tert-butyl chloride was most likely the composition
since water was immiscible. It must be noted that no
further characterization technique was used in order to
determine the purity of the tert-butyl chloride product.
Fig. 4. SN1 mechanism of the formation of di-tert-butyl
ether [6]
Saturated sodium chloride was added during the
separation step in order to promote salting out. This
increases the polarity difference between the aqueous
and organic layers thereby increasing the purity of the
organic layer by removing water and other polar
compounds[7].
Thereafter, NaHCO3 was added to neutralize the
unreacted acid in the organic layer. Effervescence was
observed as carbonic acid, which is formed from the
previous neutralization reaction, readily dissociates into
CO2 and H2O. Solid NaHCO3 was used instead of aqueous
NaHCO3 because more water would be introduced into
the organic layer, reducing its purity [8]. Then,
anhydrous CaCl2 was then added as a drying agent. CaCl 2
forms hydrated complexes with water, disabling water to
vaporize in the subsequent distillation step and thereby
increasing the purity of the extracted tert-butyl
chloride[9].
Then, distillation was used to extract the tert-butyl
chloride from the organic layer. Boiling chips was added
beforehand in order to promote bubble formation and
even boiling. This prevents superheating, bumping and
subsequent loss of solution. This method is dependent on
the volatilities of the compound of interest. Therefore,
the organic layer was boiled around the boiling point of
tert-butyl chloride (51.2C). Continuous flow of water in
the condenser is needed in order to ensure the
liquefaction of the vapor into the receiving flask, thus not
escaping from the vacuum adapter[10].

It is possible to synthesize tert-butyl from tert-butanol

through the reaction with HCl. However, the method for
the synthesis employed in the experiment produced low
yields. Also, the purity of the product from the distillation
process cant be ascertained. It is recommended that the
formation of tert-butyl chloride from tert-butanol should
proceed completely and that the losses during
separation, decantation and distillation should be
minimized. Also, a separate step should be done in order
to determine the purity of product.
References
[1] Organic Chemistry Group. 2014. Organic Chemistry:
Laboratory Manual. 2014 Edition. Institute of Chemistry.
[2]
Falcone, J. 2007. Keystone College: Dr. Joe Falcones
Homepage.
Retrieved
from
http://academic.keystone.edu/JFalcone/tBuClPrepv2_files/image0
02. gif , on September 21, 2016
[3] Solomons, T.W.G., Fryhle, C., Snyder, S. 2014. Organic
Chemistry. 11th Edition. John Wiley and Sons. Print
[4] Klein, D. 2015. Organic Chemistry. 2 nd Edition. John Wiley
and Sons. Print
[5] Norris, P. n.d. Youngstown State University. Elimination
Reactions.
Retrieved
from
http://www.hyperconjugation.com/teaching/3719files/me
chanisms/elimination_files/elim1.gif, on September 21, 2016
[6] Kruse, A., Dinjus, E. 2006. Hot compressed water as reaction
medium and reactant: properties and synthesis reactions.
Journal
of
Supercritical
Fluids.
Retrieved
from
https://www.researchgate.net/publication/2225
99477_Hot_compressed_water_as_reaction_medium_and_reacta
nt_Properties_and_synthesis_reactions, on September 21, 2016
[7] Hey, M., Jackson, D. Yan, H. 2005. The salting-out effect and
phase separation in aqueous solutions of electrolytes and
poly(ethylene
glycol).
Polymer.
Retrieved
from
http://www.sciencedirect.com/science/article/pii
/S0032386105001515, on September 21, 2016

3.3. Experimental Results

Table 1
Experimental results
mass

4. Conclusion and Recommendations

(CH3)3COH

(CH3)3CCl

11.8 g

1.23 g

theoretical

14.8 g

%yield

8.33%

The experiment had low yield, with the extracted

tert-butyl chloride reaching only 8.33% of the theoretical
yield. A possible cause for this may be the incomplete
reaction of tert-butanol to form tert-butyl chloride. The

[8]
Analytical Chemistry Group. 2013. Analytical Chemistry
Lab Manual. Quezon City: University of the Philippines Institute
of Chemistry. Print
[9]
Department of Chemistry & Biochemistry. Drying Agents.
University
of
California.
Retrieved
from
http://www.chem.ucla.edu/~bacher/Speci
altopics/Drying
%20Agents.html, on September 21, 2016
[10]
Department of Chemistry. Distillation of liquid mixtures.
University
of
Wisconsin.
Retrieved
from
http://www.chem.wisc.edu/deptfiles/OrgLab
/distillation/CHEM

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%2520344%2520Distillation%2520handout.pdf, on September
21, 2016