Page | 1

Synthesis and purification of ​tert​-butyl chloride

John Christian S. Lopez
BS in Public Health, Institute of Biological Sciences, University of the Philippines Visayas, Miagao, Iloilo, Philippines
b​
Institute of Chemistry, University of the Philippines Diliman, Quezon City, Philippines
Date performed: June 13, 2019

ABSTRACT
This experiment aimed to synthesize tert-butyl chloride via a nucleophilic substitution reaction with tert-butyl alcohol and HCl
and the purification of the crude product obtained using the fractional distillation technique. Results showed that the percent
yield was 35.113% which verified that tertiary alcohols can be synthesized to produce tertiary alkyl halides and that the
fractional distillation process was successful in purifying the crude sample obtained. The obtained product was also confirmed
as tert-butyl chloride after the water solubility test which showed that the substance was insoluble to water which is a major
characteristic of tertiary alkyl halides.

1. Introduction

Alcohols are organic compounds that contain a

hydroxyl group attached to a carbon. Alcohols can be
categorized into three (3) which highly depends on the
hybridization of the carbon to which the -OH group is
attached.​[1] Primary alcohols have their hydroxyl group
attached to a carbon attached to one (1) carbon.
Secondary alcohols are those who are attached to
carbon attached to two (2) carbons. Lastly, tertiary
alcohols are those who are attached to a saturated
hydrocarbon. [2]​
Alcohols can be synthesized to produce alkyl halides or
haloalkane, a functional group where a halogen is
bonded to a sp​3​-hybridized carbon. Generally, alkyl
halides are more polar than hydrocarbons because
halogens are more electronegative than carbon atoms.
[1]
Like alcohols, alkyl halides are classified into three
(3). Primary alkyl halides are those with halogens
bonded with a single alkyl substituent, secondary has
two (2) substituents, and tertiary has three (3).
Alkyl halides can be synthesized by processes such as
the preparation of alcohols through a reaction called
nucleophilic substitution (figure 1). The process
involves two pathways, Sn1 and Sn2. The former is
where after losing water, the alcohol gets protonated
which serves as the rate-determining step for this
pathway, whereas the latter is the attacking of the
nucleophile on the protonated carbon or carbocation.
​
The latter also produces a more stable carbocation. [6]
[3]​
Figure 1: ​General reaction mechanism for
nucleophilic substitution
When alcohol is used to synthesize an alkyl halide, a
tertiary alcohol is reacted with a hydrohalogenated
compound such as hydrochloric acid since the two (2)
other types of alcohol reaction times are much slower
compared to tertiary alcohols.​[1] An example of this is
the use of tert-butyl alcohol with HCl to produce
tert-butyl chloride.
Distillation is a technique used to identify and purify
organic compounds.​[4] It is a process that involves the
heating, condensating, and the collection of the hot
vapors. In the case of the synthesis of tertiary alkyl
halides, fractional distillation is used because
substances involved have varying boiling points.
This experiment aims to synthesize tert-butyl chloride
from tert-butyl alcohol reacted with HCl. It also aims to
purify the synthesized product using a simple
distillation technique.
2. Materials and Methods
2.1. Synthesis of tert-butyl chloride

*John Christian Lopez. Mobile: 09153433631

E-mail address: jslopez13@up.edu.ph

10.0 mL of tert-butyl alcohol together with 20.0
mL of hydrochloric acid were placed in a
separatory funnel and were left to mix and
interact. Pressure created by the reaction were
removed by opening the stopcock after swirling
the sample. The mixture was then placed
undisturbed for 20 minutes in the setup (figure
1). In order to separate the organic product
from the aqueous solution, 5.0 mL of NaCl was
added, and the determination of the layers was
conducted by placing five (5) drops of distilled
water. The aqueous layer was then drained and
the organic product was collected and placed in
a dry Erlenmeyer flask containing a small
amount of sodium bicarbonate.
Figure 2: ​Separation of layers setup
The solution was then swirled and then
decanted into another dry Erlenmeyer flask to
which it was dried using anhydrous aluminum
chloride until no clumping was observed.
After the drying process, the crude tert-butyl
chloride was placed in a 25-mL round bottom
flask with a few boiling chips added and was
then distilled using a simple distillation setup
(figure 3).
*John Christian Lopez. Mobile: 09153433631
E-mail address: jslopez13@up.edu.ph
Page | 2
Figure 3: ​Simple distillation setup
The fraction that was in between 42-59​○​C was
collected in a pre-weighed vial and was then
placed in a cold bath. The percent yield was
then determined and it was tested for its
solubility with water.
3. Results and Discussion
Tert-butyl alcohol, a tertiary alcohol, was used in this
experiment to synthesize tert-butyl chloride thus
utilizing the Sn1 pathway. ​The addition of cold HCl to
the t-butyl alcohol protonated it therefore producing a
stable carbocation. This happened when the Hydrogen
in HCl interacted with t-butyl alcohol, leaving the
chlorine negatively charged or electron-rich. Cold HCl
was added instead of room temperature to prevent the
reaction to forward as an elimination reaction where
instead of t-butyl chloride, it will yield isobutylene.
Sodium Chloride and Sodium Bicarbonate was added
during the extraction. The addition of NaCl aided in
removing the impurities that the solution contained
whereas the latter facilitated the complete
neutralization of the remaining hydrochloric acid.​[6]
Also, the 6.0M NaCl aided in the separation of layers.
The reaction causes a buildup of pressure in the
separatory funnel which made it necessary for the
release of pressure by opening the stopcock after each
swirling.

In order to ensure that there would be no
contamination of water, since this has the potential to
revert the process back from t-butyl chloride to t-butyl
alcohol via Sn1 pathway when it will undergo the
distillation process, to CaCl3 was added.​[7]
The product taken from the extraction is crude t-butyl
chloride which contains impurities. This must be
purified in order to accurately determine the pure
compound percent yield. Purification was conducted
through a simple distillation setup which utilizes the
different boiling points of substances.​[5] Boiling chips,
specifically broken capillary tubes, were added prior
the distillation setup to control the boiling process.
When boiling, a process called bumping may occur.
This is where bubbles form and erupt in locations
where the temperature is above the boiling point.
Bumping may expel extremely hot materials and may
even cause the glassware to explode. [8] ​
The purpose of the condenser is to condense the hot
vapour leaving the top of the distillation column. Hot
vapor goes into the inner tube, the water located
outside aids in cooling the vapor therefore condensing
it. The receiving flask is placed in an ice bath to prevent
the t-butyl chloride vapor from vaporizing. [4]​ Finally, to
determine whether the substance obtained was t-butyl
chloride, it was subjected to a water solubility test
since tertiary alkyl halides are insoluble in water since
it cannot form hydrogen bonds with water.
Table 1 shows the property of the compound retrieved
after the distillation process:
Table 1​. ​Properties of product obtained
Boiling point, ○​
​ C: 51
Color : Colorless
Solubility in H​2​O : insoluble
Table 2 shows the percent yield or the yield retrieved:
Table 2​. ​Properties of product obtained
Weight of t-butyl alc., g: 7.8
Weight of t-BuCl, g : 3.42
Theo. Yield, g : 9.74
% yield : 35.113
*John Christian Lopez. Mobile: 09153433631
E-mail address: jslopez13@up.edu.ph
Page | 3
The obtained yield was low, but despite this result, it
proved that t-butyl chloride can be synthesized from
t-butyl alcohol. It also proved that distillation is an
efficient method of removing impurities. When tested
for solubility in water, the results showed that the
retrieved compound was indeed a tertiary alkyl halide,
specifically tert-butyl chloride since it was insoluble in
water. The low turnout of the percent yield may be
attributed to multiple possible factors such as the
glasswares and materials used may not have been fully
dried which could have brought impurities. The
addition of too much CaCl3 can also attribute to the low
turnout since the possible adhesion of the molecules to
the anhydrous CaCl3. The distillation setup itself can be
the source of the result garnered. A decrease in the
yield and the material retrieved can be attributed to the
improper setting up of the distillation setup such as
loose stopcocks and joints.
4. Conclusion and Recommendations
Based on the result, it can be concluded that the
method for synthesizing tert-butyl chloride from the
nucleophilic substitution reaction of tert-butyl alcohol
and HCl and the purification process of the crude
compound was successful although there was a low
percent yield.
It is highly recommended that preventive measures
such as ensuring the cleanliness and dryness of the
materials used be ensured so that impurities may be
reduced or avoided. Also, the proper setting up of the
setup is highly encouraged to reduce material loss that
may lead to a low percent yield.
References
[1] Alroche, C. ​Alkyl Halides.​ Rutgers
University-Camden. [Online]. ​2014​.
[2] McMurry, J. (2015). ​Organic Chemistry 9​th ed​.
Chapter 10: Reactions of Alkyl Halides:
Nucleophilic Substitutions and Eliminations
Chapter 17: Alcohols and Phenols​. Cengage
Learning: Belmont, pg. 309-334 & 525.
[3] (2013) The SNAr Reactions: Mechanistic
Aspects. Modern Nucleophilic Aromatic
Substitution 1–94.
 Page | 4

[4] The University of Colorado at Boulder. Organic

Chemistry. Distillation. ​[Online]. Retrieved
from:https://orgchemboulder.com/Technique/
Procedures/Distillation/Distillation.shtml

[5] The University of Sydney Faculty of Science.

Experiment 28: Extraction. [Online]. 2014.
Retrieved from:
https://scilearn.sydney.edu.au/fychemistry/pr
elab/images/E28extractionimage1.gif
(accessed March 9, 2015).

[6] Munyemana, F., Frisque-Hesbain, A.-M., Devos,

A., & Ghosez, L. 1989. Synthesis of alkyl halides
under neutral conditions. Tetrahedron Letters,
30(23), 3077–3080.
doi:10.1016/s0040-4039(00)99407-3

[7] (2016) Drying Agents. University of California

Los Angeles. Retrieved from:
http://www.chem.ucla.edu/~bacher/Specialto
pics/Drying%20Agents.html

[8] Nichols, L. (2019) Controlled boiling. Chemistry

- LibreTexts. Retrieved from:
https://chem.libretexts.org/Bookshelves/Orga
nic_Chemistry/Book%3A_Organic_Chemistry_L
ab_Techniques_(Nichols)/1%3A_General_Techn
iques/1.3%3A_Heating_and_Cooling_Methods/
1.3B%3A_Controlled_Boiling

*John Christian Lopez. Mobile: 09153433631

E-mail address: jslopez13@up.edu.ph