Synthesis of Alkyl Halides

Dizon, Gio Philip

Tablada, Sharmaine
Department of Psychology, College of Social Sciences and Philosophy, University of the Philippines, Diliman, Quezon City
Date Performed: April 24, 2014
Date Submitted: April 28, 2014

Abstract
For this experiment, alkyl halide synthesis was carried out through the use of a tertiary alcohol and a hydrogen halide.
Through the mixing of the reactants, separation of layers, decantation, and simple distillation, tert-butyl chloride was
obtained from tert-butyl alcohol and hydrochloric acid with 31.75% yield. The resultant tert-butyl chloride definitively
differentiated itself from the reactant tert-butyl alcohol through its physical properties of being translucent, insoluble in
water, and having a boiling point of 46 C. Furthermore, the experiment effectively demonstrated the mechanisms
involved in the synthesis of alkyl halides, which was nucleophilic substitution, and the advantages that the reaction of
tertiary alcohols and hydrogen halides provide in line with alkyl halide synthesis.

I. Introduction

Almost every product utilized in the world today does
not come instantly in their usable form. Most are
retrieved from nature in a raw condition having to
undergo processes in order for them to be deemed
ready for operation. Some even exist in states where
even attaining them is made difficult but through
chemical reactions have become available and through
also chemical mechanisms are possibly purified. Also,
with the use of chemical processes various products
which often come rarely could now be artificially
produced. Most of the work of organic chemists is
focused on producing these kinds of products which are
of practical use to mankind. Synthesizing new
compounds as potential drugs for the treatment of
diseases, forming agricultural chemicals such as weed
control, insecticides and fungicides in order to increase
crop yields, are just some among the practical goals that
organic chemists work on (Carey, 2011). And among the
molecules that organic chemists start with in order to
produce these valuable products are alcohols and alkyl
halides.

Alkyl halides are compounds which contain one or more
halogen atoms, they are examples of organohalides.
They themselves provide many uses for the everyday
man. They are primarily used as industrial and
household solvents. The making of more complex
molecules also involves reactions with these
compounds such as conversion of alkyl halides to
organometallic reagents which is an important tool for
organic synthesis. In the field of medicine, alkyl halides
have been proven to show importance through acting
as a general anesthesia giving rise to possibilities of
careful surgery with the patient being unconscious and
more relaxed. Freons, are fluorinated haloalkanes have
been used as refrigerant gas and foaming agents added
to plastics yielding plastic foams. Alkyl halides have also
contributed much to the health of humans through
their use as insecticides providing means for eradicating
harmful insects which have long plagued various
civilizations (Wade, 2013).

Despite the numerous practical benefits given by alkyl
halides, they are encountered less frequently compared
to their oxygen-containing relatives alcohols and ethers.
But the reactions that alkyl halides undergo are
encountered more frequently (McMurry, 2007). Given
the high importance of alkyl halides and unavailability,
they are often synthesized and purified instead of
extracted directly from nature which always comes with
high expenses.

Synthesis of alkyl halides could be done through free-
radical halogenation involving an alkane, which is a
rarely effective method for the synthesis of alkyl halides
in that it usually produces mixtures of products due to
the different kinds of hydrogen atoms than can be
abstracted (Wade, 2013). Alkyl halides can also be
prepared from alkenes through the means of allylic
bromination which is analogous to alkane halogenation
by a radical chain reaction pathway (McMurry, 2007).
Another way of synthesizing alkyl halides is through the
use of alcohol and is the most generally useful method
for preparing alkyl halides (McMurry, 2007). This is
done through reacting alcohol with hydrogen halides to
yield corresponding alkyl halides and water. Tertiary
alcohols have been observed to be the most reactive
with hydrogen halides. Within minutes on reaction with
a hydrogen chloride (a hydrogen halide), tertiary
alcohols are converted to alkyl chlorides (an alkyl
halide) in high yield even just in room temperature and
below (Carey, 2011). A halogen replaces a hydroxyl
group as a substituent on carbon when alcohols react
with hydrogen halides in a process called nucleophilic
substitution (specifically SN
1
).

This experiment aims to show the efficiency of
producing alkyl halides through the chemical reaction of
substitution by reacting a tertiary alcohol and a
hydrogen halide. In this experiment, tert-butyl alcohol
was used, for the reason that it is a tertiary alcohol
meaning it has high yield when reacted with a hydrogen
halide in a matter of minutes and within just room
temperature (Carey, 2011). The hydrogen halide used
was hydrochloric acid for the reason that it reacts
readily with tertiary alcohols as compared to primary
and secondary ones without the necessity of having the
presence of a Lewis acid (Carey, 2011). Tert-butyl
chloride was obtained as the alkyl halide product and
with water as a by-product. The alkyl chloride product
was then distilled in order to check and ensure its
purity.
III. Results and Discussion

There was obtained a total of 3.7 ml of the resulting
alkyl halide after distillation. Given that the density of
Tert-butyl chloride (resulting alkyl halide) is 0.842 ml/g,
the actual yield of 3.1154 g was collected. The
computed percentage yield of the product is 31.75%
(See Table 1 for values).

Table 1. Experimental Results

The substance collected was also then compared to the
properties of the tertiary alcohol reactant so as to make
sure that there was a different compound obtained (see
Table 2 for comparison).

Table 2. Comparison of the properties of tert-butyl
alcohol and of synthesized tert-butyl chloride

In reacting tertiary alcohols with halogen halides,
specifically Hydrochloric acid it is expected to have a
yield a high percentage of the resulting alkyl halide
(Carey, 2011). It is assumed that for how many moles of
tertiary alcohol reacted there would be almost, if not
the same resulting moles of alkyl halide obtained. Given
that at the start of the reaction 0.106 mol of Tert-butyl
alcohol (corresponding to 10 ml) was reacted with HCl,
theoretically speaking a product of 0.106 mol of Tert-
butyl chloride should have been obtained. There is a far
difference between the theoretical yield and the actual
yield of the product showing that there was an
inefficiency in the methods of synthesis employed. The
collected product was much lower than expected.

To explain how these results came about, it can be said
that the reaction between tert-butyl alcohol and
hydrochloric acid is a nucleophilic substitution which
occurs in three steps. The first step is the protonation of
tert-butyl alcohol, obtaining the H from the
Hydrochloric acid. Alcohols have basic and acidic
properties much like water, in that it can produce and
accept protons on its oxygen part. The proton transfer
to the alcohol results in an alkyloxonium ion (Carey,
2011). The first step produces two products which are
both ions, the tert-Butyloxonium ion which is positively
charged and a Chloride ion from the hydrochloric acid
which is negatively charged. This step also takes place
relatively fast compared to the other steps, proton
transfers from strong acids to water and alcohols are
ranked among the fastest chemical processes and occur
almost at the time the molecules make contact with
one another. The rapid rate at which proton transfer
occurs is contributed by its concerted nature. The
energy cost it would take to break the bond between
HCl is overcome by the energy released in forming the
new bond between the transferred proton and the
oxygen of the alcohol. With the HCl being a stronger
acid than the alkyloxonium ion, the first step is known
to be exothermic (Carey, 2011).

Figure 1. (Step 1: Protonation of tert-butyl alcohol to
give an alkyloxonium ion)

The second step involved in the reaction is the
dissociation of the alkyloxonium ion yielding both a
carbocation and water. This step is classified as
unimolecular since only one species undergoes a
chemical change. This is also the slowest step relative to
the others having the highest activation energy and is
therefore considered the rate-determining step of the
reaction. The formed carbocation is a relatively unstable
species and the process of its formation is endothermic
(Carey, 2011). The instability of the carbocation
intermediate makes them difficult to isolate. This
instability is simply reasoned by the fact that the
positively charged carbon contains only six electrons in
its valence shell, not satisfying the octet rule. The
positively charged carbon contained in the intermediate
is sp
2
hybridized. There is the presence of an
unhybridized 2p orbital on the positively charged
carbon and it contains no electrons, the combination of
this vacant p orbital and positive charge on the carbon
make the carbocation strongly electrophilic (Carey,
2011). With the second step being the rate-determining
step and is unimolecular, the entire reaction is classified
as an SN
1
mechanism.

Figure 2. (Step 2: Dissociation of tert-butyloxonium ion
to give a carbocation)

The last step is the reaction of the tert-butyl cation with
the chloride ion produced in the first step. The chloride
ion acts as a nucleophile having an unshared electron
pair that it is capable of using to form a covalent bond.
This step is classified as bimolecular in that two species,
the carbocation and the chloride ion react together. The
occurrence of this step is also quite fast because of the
small activation energy required for the reaction to
happen. A bond formation between a positive ion and a
negative ion occurs rapidly.


Figure 3. (Step 3: Capture of tert-butyl cation by chloride
ion)

The nucleophilic substitution reaction and the
subsequent separation of product reagents that
occurred was made possible through the use of cold
concentrated HCl, which was added in excess and solid
Sodium Bicarbonate. Before proceeding with the
experiment, it was assured that concentrated HCl was
cold because HCl is highly volatile and can react
instantaneously, even before being placed in the flask.
Lowering of temperature may cause lowering of the
Energy of activation of any reaction, thereby hindering
the fast instantaneous reaction of HCl. Also, the use of
HCl, if not cold, could lead to a vigorous reaction
resulting to too much fumes and less of the desired
product. Furthermore, it was added in excess to ensure
the completeness of reaction. In addition to that, the
experimenters made us of solid Sodium Bicarbonate,
instead of its aqueous counterpart, because the
existence of the -OH group in the aqueous form of
Sodium Bicarbonate poses a threat of reaction with the
organic layer obtained which contains the product.
Reaction of this can cause a reversion to the alcohol
instead of collecting the desired halide form.

Aside from that, other methodological information that
is worthy of noting is use of anhydrous CaCl
2
, of boiling
chips, and of continuously flowing in the condenser
during distillation. Before distillation, the tert-butyl
chloride must be carefull dried with anhydrous CaCl
2

because without this step in the process, the water that
may still be present in the product could possibly
catalyze the product to undergo hydrolysis as the
temperature rises, affecting percent yield. Moreover,
the boiling chips were used because of their ability to
provide an area for bubble adhesion and prevent
vigorous boiling due to the bumping of gases. Lastly, it
was assured that cold water was continuously flowing
into the condenser during the distillation process
because in distillation, wherein a solution is heated to a
temperature in which one component will become a
vapor while another component stays as in liquid form
to separate them, condensation is needed to collect the
vaporized component. In order for condensation to
occur with a vaporized reagent, the reagent must be
put into a system whose temperature is below its
boiling point and above its freezing point. This means
that the condenser in the distillation set-up must be
able to cool the vaporized reagent so that its
temperature will be brought down from its boiling
point. Therefore, a cooling agent is needed, which in
this case is cold water. This water should have a
continuous flow because if left stagnant in the
condenser, the heat transfer occurring among the
water, condenser, and vapor will heat the water and
thus rid it of its ability to cool down the condenser.

All in all, the results show that, though the collected
product is much lower than expected, it is still possible
to synthesize an alkyl halide even in room temperature.
This reaction, which took just a few seconds, supports
the literature that the reaction between an hydrogen
halide and a tertiary alcohol is rapid and does not need
very rigorous conditions in order to occur.

However, having only been able to gather 31.75% of the
theoretical yield it could be inferred that there were
many rooms for error in the experiment. One of the
possible causes of this very low outcome is the high
volatility of the desired alkyl halide, tert-butyl chloride.
It should be noted that there were circumstances during
the experiment that the product was left in open air
making the occurrence of evaporation highly possible.
The separatory funnel used in separating the two layers
showed also to have a minor defect with liquid still
dropping even if it was closed tightly.

Furthermore, the low percent yield of tert-butyl
chloride could also have been caused by the formation
another product, a side product called 2-
methylpropene. Tert-butyl carbocation formed can
undergo elimination of a beta hydrogen to give 2-
methylpropene as a side product (Alcohols and Ether,
n.d.). The mechanism involves the same three steps of
forming an alkyl halide but with the third step varying.
Instead of being captured by the chloride ion the
carbocation undergoes elimination leading to the
formation of an alkene polymer of the carbocation.

Fig. 1

Fig. 2

Figure 4. Elimination of a Beta-Hydrogen
The alkene has a much lower boiling point compared to
that of the desired alkyl halide (Carey, 2011). To remove
this side product during purification, discard whatever
distills are formed before the boiling point range of the
alkyl halide and collect only that which distills at the
boiling point range.

IV. Conclusion

The experiment was successful in fulfilling its aim of
synthesizing an alkyl halide, which in this case is tert-
butyl chloride, from tert-butyl alcohol with a 31.75%
yield and a product reagent that definitively
differentiates itself from the reactant reagent through
its tested physical properties. However, the same level
of success cannot be said in relation to the experiments
efficiency in alkyl halide synthesis.

In line with this, as students, it can be said that the
experiments importance lies in its demonstrative ability
of showing chemical reactions at work as a supplement
to the students theoretical knowledge of these
reactions. Furthermore, the experiment verifies the
mechanism proposed by various studies regarding how
the nucleophilic substitution process works.

For future researchers who would like to attempt the
experiment, we would like to suggest that they make
sure that their laboratory materials are in full working
order before proceeding with the experiment and that
they make sure that they will follow the methodology
without any deviation, accidental or otherwise. Lastly,
we would like to propose that they perform more than
one trial of the experiment to produce more accurate
results.


V. References
Carey, F. A. (2011). Organic Chemistry (8th Ed.). New
York, NY. McGraw-Hill.

McMurry, J. (2007). Organic Chemistry (7th Ed.).
Belmont, CA . Thomson Learning, Inc.

Wade, L.G. Jr. (2013). Organic Chemistry (8th Ed.).
Glenview, IL. Pearson Education, Inc.

Alcohols and Ethers (n.d.). In Caltech Authors. Retrieved
April, 26, 2014, from
http://authors.library.caltech.edu/25034/16/BPO
Cchapter15.pdf

VI. Appendices

Please refer to attached Data Sheets.