Chemistry 31.

1 FG-1L 2BSFT Group 1

Viena G. Monterde February 3, 2014

EXERCISE 8
Synthesis of tert-Butyl Chloride

ABSTRACT

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.
The experiment aims to prepare tert-Butyl chloride from tert-Butyl
alcohol using hydrochloric acid by SN1 mechanism. The calculated
percent yield is 12.15%. The low yield can be due to the excessive
calcium chloride which caused the desired compound to adhere to
it, thus lowering the volume of the final product. The experimental
boiling point of tert-butyl chloride (TBC) is 50.5°C while that of
tert-butyl alcohol (TBA) is 80.5°C. They did not coincide with the
theoretical boiling points of TBC and TBA—82.2°C and 52°C
respectively. This can be due to the error within the apparatus
itself, inconsistent judgement in monitoring the temperature or the
external pressure of the environment where it was conducted.
 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 follow—SN1 or SN2. The former means substitution,
nucleophilic, unimolecular while the latter means substitution, nucleophilic, bimolecular.
Primary alcohols follow the SN2 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 rate-determining
step (University of Dallas, 2009).
In the experiment, tert-Butyl chloride will be 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 82.2°C. 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 51°C (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

OBJECTIVES

 To prepare tert-Butyl chloride from HCl via SN1 reaction

 To know the mechanism of the SN1 reaction
 To calculate the percent yield of tert-Butyl chloride
 To characterize the final product by boiling point determination
 MATERIALS AND METHODS

The procedure was based on the Chemistry 31.1 – Organic Chemistry Laboratory
Manual, pages 69-70. No further changes and additions were made in the materials and
methods.

DATA/RESULTS

Table 1. Initial and final volume of the sample

Sample Volume, mL
tert-Butyl Alcohol 5
tert-Butyl Chloride 0.7

Table 2. Computation of Actual yield, Theoretical yield, and Percent Actual Yield of tert-Butyl
Chloride
m
ρ=  m=ρv
v
Actual Yield
m= ( 0.84mLg )(0.7 mL)
m=0.588 gTBC
0.775 g TBA 1 mol TBA 1 mol TBC 92.57 gTBC
5 mL TBA x x x x
Theoretical 1 mL TBA 74.12 gTBA 1 mol TBA 1 mol TBC
Yield
¿ 4.84 gTBC
actual yield
actual yield= x 100
theoretical yield
Percent
Actual Yield 0.588 g
actual yield= x 100
4.84 g
actual yield=12.15 TBC

Table 3. Experimental Boiling Points of tert-Butyl Alcohol and tert-Butyl Chloride

Boiling Point, °C
Sample
Trial 1 Trial 2 Average
tert-Butyl Alcohol 81 80 80.5
tert-Butyl
52 49 50.5
Chloride

DISCUSSION
 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 alcohols favour SN1 reactions. Hydrochloric acid (HCl) 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; in this case, water (Long Island University, 2010). Sodium
bicarbonate, being a weak base, neutralized the remaining hydrochloric acid (Univeristy of
California Los Angeles, 2013). Carbon dioxide gas is given off when it reacts with HCl. Pressure
can build up in 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.

After the extraction, the garnered tert-Butyl chloride was measured. The calculated
percent yield is only 12.15%. This low yield can be caused by the addition of too much calcium
chloride. Some of the desired compound could have been lost due to the adhesion of the
molecules to the calcium chloride (Long Island University, 2010).

The experimental boiling point of tert-butyl alcohol is 80.5°C while tert-butyl chloride
has 50.5°C. The resulting values are not exactly the same with the theoretical values. This could
be due to errors in the boiling point determination—apparatus and inconsistent judgements while
monitoring the temperature. The external pressure could have also caused the inaccurate values.
Nevertheless, the acquired boiling points are still close to that of the theoretical values.
 CONCLUSION

Tert-Butyl chloride was prepared from tert-Butyl alcohol using hydrochloric acid via S N1
mechanism. This mechanism usually happens in tertiary alcohols since they produce more stable
carbocations. The reaction protonates the alcohol followed by lose of water and does
nucleophilic attack by the nucleophile on the carbocation.
The percent yield of tert-Butyl chloride is 12.15%. Addition of too much calcium
chloride could have been the cause of this low yield. The desired compound may have gone lost
by adhering to the calcium chloride. The average experimental boiling points of tert-Butyl
alcohol and tert-Butyl chloride are 80.5°C and 50.5°C respectively. The inaccurate boiling point
values can be due to the error within the apparatus itself, inconsistent judgement in monitoring
the temperature or the external pressure of the environment where it was conducted.

ANSWERS TO QUESTIONS
1. How might tert-butyl chloride be chemically converted back to tert-butyl alcohol?
Reacting tert-butyl chloride with water can convert it back to tert-butyl alcohol. It will
still undergo SN1 mechanism. Figure 4 shows the mechanism.

Figure 4. Conversion of tert-butyl chloride to tert-butyl alcohol

2. If KCL is used in the experiment instead of HCl, do we expect to produce tert-butyl chloride?
Why or why not?
KCl is not a good alternative for HCl because it is a salt, not an acid. It won’t protonate
the hydroxyl group which in turn won’t allow it to leave as a molecule of water.

REFERENCES

Alfa Aesar (2013). Tert-Butyl chloride. Retrieved January 29, 2014 from
http://www.alfa.com/en/GP100W.pgm?DSSTK=A13004

Long Island University (2010). Preparation of tert-butyl chloride. Retrieved January 29, 2014
from http://myweb.brooklyn.liu.edu/swatson/Site/Laboratory_Manuals_files/Exp3.pdf

Univeristy of California Los Angeles (2013). Extraction (part 1). Retrieved February 2, 2014
from http://www.chem.ucla.edu/~bacher/Specialtopics/extraction.html
University of Dallas (2009). Solvolysis of tert-butyl chloride. Determining the reaction
mechanism of a chemical reaction using kinetics. Retrieved January 28, 2014 from
http://www.udallas.edu/chemdept/hendrickson/3121/solvolysis.htm
Verrnier Science and Technology (2014). SN1: Synthesis of t-butyl chloride. Retrieved January
28, 2014 from http://www.vernier.com/experiments/chem-o/13/SN1_synthesis_of_t-
butyl_chloride/
McMurry, J. (2008). Reactions of alkyl halides: Nucleophilic substitutions and elimination.
Organic Chemistry. USA: Thomson Learning Inc. pp 272 - 380.