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Preparation and Purification of an Alkyl Halide

ABSTRACT

Alkyl halides are halogen-substituted alkanes which are produced by reacting relative alcohols with a hydro halogen. [1] In this
experiment, tert-butyl chloride was synthesized from tert-butyl alcohol and concentrated hydrochloric acid by unimolecular
nucleophilic substitution (SN1) which was done in a separatory funnel. The purification of the tert-butyl chloride that was previously
obtained was then done using a simple distillation set-up, collecting the purified sample at the boiling point of tert-butyl chloride at
51C. The initial 5 mL of tert-butyl alcohol produced 3.905 g of tert-butyl chloride which gives a percent yield of 2.05% from its
theoretical yield of 4.88 g.

1. Introduction anhydrous CaCl2. The CaCl2 was added until the mixture is freely
swirling.
Organohalides are compounds with one or more halogen
atoms and can be typically found in nature and several marine The crude tert-butyl chloride was then decanted into a dry 25
organisms. There are several kinds of oraganohalides which mL round bottom flask along with a few boiling chips and was
differ simply by where the halogen bonds with the hydrocarbon. distilled. The first ten drops were then discarded while the fraction
One type of an organohalide is the haloalkanes which are more that boils at 49-52 C is collected in a cooled pre-weighed vial. The
commonly known as alkyl halides. In an alkyl halide, which is solubility of the purified product was then tested with water. [3]
represented by R-X (X= Cl, Br, I), the halogen atom is bonded to
a saturated sp3hybridized carbon atom. [1] Since the halogen 3. Results and Discussion
atom is more electronegative than the carbon atom, the C-X
bond is polarized where in the carbon is partially positive and In order to synthesize the tert-butyl chloride, tert-butyl alcohol
the halogen is partially negative. [2] and cold concentrated HCl were made to react through a
unimolecular nucleophilic substitution (SN1). [4] The mechanism of
The Alkyl halides are typically prepared from alcohols since their reaction is given through 3 steps, whose rate is dependent on
they are obtained easily from carbonyl compounds. The alcohol the stability of the carbocation, which can be seen in Figure 1.
can react with the hydrogen halides through a nucleophilic
substitution reaction thus producing the alkyl halide and water.
Hydrogen halides are best reacted with tertiary alcohols as they
easily react with alkyl halides. Primary and secondary alcohols
on the other hand react much slower than the tertiary which is
why they need a Lewis acid for the reaction to go into
completion. [1]

This experiment aims to synthesize tert-butyl chloride from

tert-butyl alcohol and concentrated HCl and to purify the
product obtained. The purity and solubility of the tert-butyl
produced will also be assessed in order to determine its quality.

2. Materials and Methods

Five milliliters of tert-butyl alcohol and 10 mL of cold

concentrated HCl were combined in a dry 50 mL separatory funnel.
This was then gently swirled for 10 minutes while occasionally
releasing pressure from the stopcock. This was then allowed to
stand undisturbed for 20 minutes in order to allow the layers to
separate. In order to help with the separation of the layers, 5 mL of
6M NaCl solution was added. Fig. 1. Reaction mechanism of tert-butyl alcohol [4]

The aqueous (lower layer) and organic layers (upper layer)
were then separated. In order to differentiate the two layers, 1-2
drops of water can be added to either of the separated layers. The
layer in which the drop of water dissolves is the aqueous one and is
to be discarded. The organic layer is then transferred into a dry
flask with a small amount of solid NaHCO3. This was then swirled
gently until bubble formation stopped and then decanted into
another dry flask. This was then dried with small amounts of
The first step shows the protonation of the alcohol; where in the
lone pairs of the oxygen part of the hydroxyl group attacks the
partially positive hydrogen atom of the hydrochloric atom, which
gives the intermediate t-butyloxonium ion. This step occurs quickly
since tert-butyl alcohol is a tertiary alcohol which means that it is
highly reactive. This is then followed by the slow, rate determining
step where in the C-O bond of the t-butylxonium forms a cleavage,
allowing it to release he water which then results in the production
of a tertiary carbocation. Lastly, the nucleophilic chloride attacks

the carbocation through a substitution reaction in order to produce
the t-butyl chloride. [5]
The hydrochloric acid used was cold in order to ensure that the
reaction will proceed into SN1 since substitution reactions favor low
temperatures. The HCl must be concentrated in order to minimize
the volume and was added in excess to ensure that a forward
reaction is favored. If done in a high temperature, the reaction will
undergo an elimination reaction (E1) instead. [6] This will then
produce a side product of 2-methylpropene. Another side product
that may be produced is the di-tert-butyl ether as well as the tert-
butyl alcohol which is formed when tert-butyl chloride undergoes
hydrolysis and reverts back to its original form. [7] The mechanisms
for these side products can be seen in Figures 2-4.
Fig. 2. Hydrolysis of tert-butyl chloride forming tert-butyl alcohol [8]
Fig. 3. Formation of 2-methylpropene
Fig. 4. Formation of di-tert-butyl ether
In order to limit or prevent the formation of the side products
stated, it would be best to specifically use cold excess concentrated
HCl as the reactant. This can even prevent the volatilization of the
product. The solution may also be salted out by the addition of 6.0
M NaCl as the aqueous layer will be more inclined to dissolve NaCl
rather than the organic layer. This can reduce the solubility of the
organic substance produced in the aqueous layer thus improving
the separation of layers. [6]
After the organic layer was separated from the aqueous one,
solid NaHCO3 was added to the solution until there were no more
bubbles. This was done in order to neutralize the excess HCl that
was added in order to avoid the formation of water and carbon
dioxide since the addition of water into the product can cause it to
hydrolyze. It is important that the NaHCO3 used is solid rather than
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aqueous since the aqueous NaHCO3 may also introduce water into
the product thus defeating the purpose of its addition.
After the addition of the solid NaHCO3, the crude tert-butyl
chloride was then dried carefully with the anhydrous CaCl2 before it
was distilled. This removes the water present as well as the
unreacted alcohols. This step also serves as the prevention of the
product from hydrolyzing into an alcohol. If the crude alkyl halide is
not dried before distillation, the formation of an isobutylene may
occur.
The dried crude tert-butyl chloride is then distilled through a
simple distillation set-up. By distilling the product, the target
compound (tert-butyl chloride) is further isolated by removing the
impurities present, such as the side products that were formed.
Since the boiling points of the side products (BP of tert-butyl
alcohol: 82C, BP of di-tert-butyl ether: 107.2 C) are much higher
than that of tert-butyl chloride (51 C), distillation may be used in
order to obtain a more purified product. [10]
It is important to add boiling chips into the flask with the
sample during the distillation process in order to ensure that the
solution does not overheat as it allows for the distribution of heat
throughout the solution. They also provide sites for bubble
formation which can prevent the solution from violently boiling.
The flow of the water in the condenser is also kept continuous with
the use of either a water pump or rubber tubing connected to a
water source in order to ensure that it is kept cold so that it can
condense the vapors of the alkyl halide. If not done, the solution
may evaporate or heat up which may lead to a decrease in the
percent recovery of the purified substance. [11]
After the experiment, the following data were obtained.
Table 1
Experimental Results
Mass of tert-butyl alcohol, g 3.905
Mass of tert-butyl chloride, g 0.10
Theoretical yield 4.88 g
Percent Yield 2.05%
From the initial 3.905 g of tert-butyl alcohol, only 0.10 g of tert-
butyl chloride was obtained giving a percent yield of only 2.05%
from the theoretical yield of 4.88 g. Both the tert-butyl alcohol and
tert-butyl chloride both appeared colorless. Tert-butyl alcohol was
found to be soluble in water with a boiling point of 82.2 C while
tert-butyl chloride was only sparingly soluble in water with a
boiling point of 51 C.
The low percent yield of the tert-butyl chloride may have been
caused by several errors. One of which could have come from
random/human errors which lead the decrease in the percent yield.
Inaccuracy in the measurement of the tert-butyl alcohol from the
start of the experiment or imprecise separation of the organic
layers from the aqueous layer may have also played a role in the
very low percent yield. The addition of excess anhydrous CaCl2 may
also cause the tert-butyl chloride to adhere to it thus reducing the
product collected for distillation. Another source of error may have
come from the distillation of the crude tert-butyl chloride itself.
4. Conclusion and Recommendations
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The preparation and purification of the tert-butyl chloride yielded

0.10 g from 5 mL of tert-butyl alcohol. This gave a relatively low
percent yield of 2.05% from the theoretical value of 4.88g. The low
percent yield may have been caused by errors during the
experiment proper. It would be recommended to perform several
trials to produce more accurate results. The distillation process
must also be done carefully and accurately in order to increase the
percent yield.

References

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

2013.

[2] Rutgers University. http://crab.rutgers.edu/~alroche/Ch06.pdf.

(Accessed March 2, 2016).

[3] Organic Chemistry Lab Manual. (2008). Institute of Chemistry:

UP Diliman.

[4] Carey, F. (2006). Nucleophilic Substitution. In Organic Chemistry

(6th ed.). New York; McGraw-Hil

[5] Columbia University. http://www.columbia.edu/itc/chemistry/

c3045/client_edit/ppt/04_08_14_files/04_08_14.ppt. (Accessed
March 2, 2016).

[6] Solomons, T.W; Fryhle, C. Organic Chemistry, 10th ed. John

Wiley and Sons, Inc., US 2011.

[7] University of Toronto. http://individual.utoronto.ca/jenna/

B41/lab5_tbchl.htm. (Accessed March 2, 2016).

[8] Lab Report on Hydrolysis of tert-butyl Chloride in polar

solventshttp://www.art-xy.com/2011/11/lab-report-on-
hydrolysis-of-tert-butyl.html. (Accessed March 3, 2016)

[10] Clemson University. http://www.clemson.edu/ces/chemistry/

organic/Labs/2270Docs/ButylChloride.pdf. (Accessed March 3,
2016)

[11] University of Colorado Boulder. http://orgchem.colorado.edu/

Technique/Procedures/Distillation/Distillation.html. (Accessed
March 3, 2016).

Appendix I
Experimental Results
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Tert-butyl alcohol Tert-butyl chloride

Mass 3.905 g 0.10 g
Molecular Weight 74.12 g/mol 92.57 g/mol
Density 781 kg/m3 840 kg/m3
Mmol 52.68 mmol 1.05 mmol
Color Colorless Colorless
Solubility in Water Soluble Sparingly soluble
Boiling Point 82.2 C 51C
Theoretical Yield - 4.88 g
Percent Yield - 2.05%

Appendix II
Calculations

1 13 781 1000
5 ( )( )( 3 )( ) = 3.905 (CH)COH
1000 1000 1 1

1 (CH)COH 1000
3.905 (CH)COH ( )( ) = 52.86 (CH)COH
74.12 (CH)COH 1

92.57 4 9 Cl 1
52.86 (CH 3 )3 COH ( )( ) = 4.88 4 9 Cl
1 4 9 Cl 1000

0.10
( ) 100% = 2.05%
4.88