Synthesis of Tert-Butyl Chloride

Alina May Aguilar

Diana Teresa Gatus
Ida Isabella Montesa
Aubrey Muriele Ramos
Brent Tenorio

De La Salle University-Dasmarias
Dasmarias City, Cavite, Philippines

ABSTRACT
In this experiment tert-Butyl chloride was prepared from tert-Butyl alcohol using hydrochloric
acid by SN1 mechanism. Alkyl halides can be prepared by acid catalyzed substitution reactions
of alcohols. SN1 and SN2 are the pathways that compounds can follow. In SN1 mechanism, the
rate-determining step is where the alcohol gets protonated following water loss. The second
step is the attack of the nucleophile on the carbocation. Five millilitres of t-butyl alcohol was
added to fifteen millilitres of concentrated hydrochloric acid. The aqueous layer was removed
using a Pasteur Pipette after being mixed for fifteen minutes. The organic layer was washed
with water first, then five percent of NaHCO 3 solution, then water again. The t-butyl chloride
was transferred to a dry test tube and anhydrous sodium sulfate was added. The dried off liquid
was drawn and put in a pre-weighed vial. The weight of t-butyl chloride synthesized and the
percentage yield was calculated. The calculated percent yield is twenty percent.

INTRODUCTION
Chemistry involved in alkyl halides are polar reactions with nucleophiles and bases since they are polar
with an electron-poor carbon. When they react with a nucleophile or base, such as hydroxide ion, they either
undergo substitution of the leaving group (LG) by the nucleophile or elimination of H-LG to yield an alkene. The
former process will be focused on this exercise.
Acid catalyzed substitution reactions of alcohols can be used to prepare alkyl halides. There are two
routes that alcohols followS N1 or SN2. The former means substitution, nucleophilic, unimolecular while the latter
means substitution, nucleophilic, bimolecular. Primary alcohols follow the S N2 route, tertiary alcohols follow the
SN1 route, and lastly, secondary alcohols can follow either path.
The mechanism of the SN1 reaction under acidic conditions involves two steps. The rapid protonation of
the alcohol followed by the loss of water is the rate-determining step, which generates a stable carbocation
(Vernier Science and Technology, 2014). The last step is the quick nucleophilic attack by the nucleophile on the
carbocation. First-order kinetics should be exhibited by reactions occurring by this mechanism. The rate of the
reaction will not be affected by the concentration of the nucleophile since it is not involved until after the ratedetermining step (University of Dallas, 2009).

In the experiment, tert-Butyl chloride was synthesized from tert-Butyl alcohol using the mentioned
mechanism above. Tert-Butyl alcohol (2-methyl-2-propanol) is the simplest tertiary alcohol (Figure 1). This is a
clear liquid with a boiling point of 82.2C. This can be used as a fermentation ingredient in certain alcoholic
beverages. On the other hand, tert-Butyl chloride (2-chloro-2-methylpropane), as shown in figure 2, is a highly
flammable and volatile, colorless, liquid organic compound which has a boiling point of 51C (Alfa Aesar, 2013).
This is mainly used as a starting molecule to carry out nucleophilic substitution reactions to produce substances
ranging from alcohols to alkoxide salts.

OH
Figure 1. Structure of tert-Butyl alcohol

Figure 2. Structure of tert-Butyl chloride

MATERIALS AND METHODS

The first part of the experiment was the synthesis of tert-Butyl Chloride. Fifteen milliliters of concentrated
hydrochloric acid was first placed in a large test tube. Five milliliters of t-butyl alcohol was then added drop wise
using a Pasteur pipette. The contents of the tube were mixed at room temperature for fifteen minutes. The
aqueous layer was removed using a Pasteur pipette. The organic layer was then washed with three milliliters of
water first, then with three milliliters of five percent NaHCO 3 solution and washed again with three milliliters of
water. The t-butyl chloride obtained was transferred to a dry test tube and one gram of anhydrous sodium sulfate
was added. The dried liquid was drawn off and put in a pre-weighed vial. The weight of the synthesized t-butyl
chloride and percentage yield were calculated.
The second part of the experiment is the Silver Nitrate test. Ten drops of the synthesized tert-butyl
chloride was placed in a test tube. One milliliter of one percent ethanolic silver nitrate solution was added. The
contents were mixed by swirling. The appearance of white precipitate indicated the presence of a tertiary halide.
RESULTS AND DISCUSSION
The table below shows the data recorded of the weight of t-butyl alcohol and the synthesized tert-butyl
chloride to get the percentage yield.
Table 1. Recorded pertinent data
Weight of test tube

41.56 g

Weight of t-butyl alcohol and test tube

45.46 g

Weight of t-butyl alcohol

3.9 g

Weight of vial

25.72 g

Weight of vial and t-butyl chloride

26.71 g

Weight of t-butyl chloride

0.99 g

% Yield

20 %

Tert-butyl chloride was synthesized using SN1 mechanism since its starting molecule, tert-Butyl alcohol is
a tertiary alcohol. More stable carbocations are formed with this mechanism, thus tertiary alcohol favor S N1
reactions. Hydrochloric acid was also present in the synthesis of tert-Butyl chloride. This was used because HCl
provides an acidic medium that will protonate the hydroxyl group, allowing it to leave as a molecule of water.
Figure 3 shows the mechanism for the synthesis of tert-Butyl chloride from tert-Butyl alcohol using hydrochloric
acid.

Figure 3. Mechanism for reaction of tert-Butyl alcohol with hydrochloric acid (HCl)

During the extraction, saturated aqueous sodium chloride and saturated aqueous sodium bicarbonate
were used in washing the organic layer. Sodium chloride removed the impurities from the desired compound;
water (Long Island University, 2010). Sodium bicarbonate, being a weak base, neutralized the remaining
hydrochloric acid (University of California Los Angeles, 2013). Carbon dioxide gass is given off whien it reacts with
HCl. Pressure can build up this reaction which will cause the solution in the separatory funnel to shoot out, thus it
is necessary to vent the funnel until evolution of gas subsides.

The obtained tert-Butyl chloride was measured after the extraction. The percent yield that was calculated
was only twenty percent. This low yield can be caused by the addition of too much anhydrous sodium sulfate.
Some of the desired compound could have been lost due to the adhesion of the molecules to the anhydrous
sodium sulfate. (Long Island University, 2010).

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