INTRODUCTION

Chemistry involved in alkyl halides are polar reactions with nucleophiles and
bases sincethey are polar with an electron-poor carbon. When they react with a
nucleophile or base, such ashydroxide ion, they either undergo substitution of the
leaving group (LG) by the nucleophile orelimination 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

S
N
1 or S
N
2. The former means substitution,nucleophilic, unimolecular while the latter
means substitution, nucleophilic, bimolecular.Primary alcohols follow the S
N
2 route, tertiary alcohols follow the S
N
1 route, and lastly,secondary alcohols can follow either path.The mechanism of
the S
N
1 reaction under acidic conditions involves two steps. The
rapid protonation of the alcohol followed by the loss of water is the ratedetermining step, whichgenerates a stable carbocation (Vernier Science and
Technology, 2014). The last step is the quicknucleophilic attack by the nucleophile
on the carbocation. First-order kinetics should beexhibited 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-determiningstep (University of Dallas, 2009).In the experiment, tert-Butyl
chloride will be synthesized from tert-Butyl alcohol usingthe mentioned
mechanism above. Tert-Butyl alcohol (2-methyl-2-propanol) is the simplesttertiary
alcohol (Figure 1). This is a clear liquid with a boiling point of 82.2C. This can be
usedas 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 mainlyused as a starting molecule
to carry out nucleophilic substitution reactions to produce substancesranging from
alcohols to alkoxide salts.Figure 1. Structure of tertButyl 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

4
VI. AppendicesAnswers to Questions:
1. Why is it necessary to use cold concentrated HCl?Why is it added in excess?
Cold concentrated HCl is added in excess to ensure theformation of an alkyl
halide. Placing it first in an ice bathbefore mixing with alcohol help prevent
thedehydration of alcohol to isobutylene.2. Why is solid NaHCO
3
used instead of aqueousNaHCO
3
?Solid NaHCO
3
is used instead of aqueous NaHCO
3
because it neutralizes the excess acid in the crudeproduct.3. Why must the crude
alkyl halide product be driedcarefully with anhydrous CaCl
2
before distillation?To absorb the excess water in the product and to avoidthe
hydrolysis reaction of the alkyl halide back toalcohol.4. What is the purpose of
boiling chips?Boiling chips avoid overheating of the liquid beingdistilled, which
signifies that there is more control in
theboiling process. It provides surfaces in which bubblescan form and ensure a
constant flow of heat to thesample.5. Discuss the importance of the continuous
flow ofwater in the condenser during distillation.The continuous flow of cold water
in the condenserduring distillation will absorb the heat from the vaporfor it to
condense. If the water is not running, it willincrease in temperature, reducing its
ability to absorbheat.6. Explain why some 2-methylpropene can be formed inthe
reaction as a byproduct. Give a mechanism for itsproduction. How can it be
removed during purification?The carbocation intermediate can also lose a proton
toa water molecule
or alcohol to yield an alkene. Thats
why some methylpropene is formed in the reaction as abyproduct. To remove this,
when the reaction mixture isbeing shaken in the separatory funnel, the
stopcockshould be vented frequently to release the gas. Thestopper of the
separatory funnel sitting in an iron ringmust also be removed to allow the gas
escape

When tert-butyl alcohol and HCL were mixed, itcan be noticed that the mixture is
homogenous at firstbut immediately after swirling, two layers were formed.The
organic layer was the resulting water insoluble tert-butyl chloride from the
reaction. The difference insolubility in water between alcohol and alkyl halide
isdue to the hydrogen bonding between the alcohol andwater while between the
alkyl halide and water, nogroups would be able to hydrogen bond.Tertiary alcohols
like tert-butyl alcohol reactwith HCl or HBr by an S
N
1 mechanism through acarbocation intermediate. The first step
includesprotonation of the hydroxyl group of the alcohol, aLewis acid-base
reaction. Slow ionization then occursand a water molecule is expelled to produce
acarbocation. The nucleophilic halide ion attacks thiscarbocation forming the alkyl
halide product. Themechanism can be seen in the figure shown below.
Figure 4.
Mechanism for the reaction of tert-butylalcohol and HCl
(Solomons & Fryhle, 2011, p. 515)However, the carbocation intermediate can
alsolose a proton to a water molecule or alcohol forming analkene, which is
methylpropene. Placing theconcentrated HCl in an ice bath before mixing with
thealcohol helps prevent the formation of the alkenebecause elimination reactions
preferred hightemperatures. Since methylpropene is a gas, it canevaporate
throughout the reaction. Opening thestopcock from time to time and letting the
separatoryfunnel stand undisturbed with its stopper removedrelease and let
the unwanted gas escape.After the reaction, two layers are formed. Theupper
layer is the tert-butyl chloride produced since it isless dense than water while the
lower one is composedof excess acid and water and was discarded after.
Thecollected tert-butyl chloride was then put in a vesselwith solid NaHCO
3
to neutralize and remove extra H
+
inthe product. Also, the excess water was absorbed byanhydrous CaCl
2.
If it is not removed from the product, it
3will react with the tert-butyl chloride and will result totert-butyl alcohol and HCl
returning from the start.Distillation of the crude alkyl halide was done topurify the
final product and remove methylpropenewhich is a byproduct since it has a lower
boiling pointthan tert-butyl chloride. The fraction that boils at 49-52
0
C was the one collected because it is the tert-butyl
chlorides boiling point range.
The receiving flask wasput in an ice bath to regulate temperature and
minimizethe evaporation during distillation. Evaporationdecreases the yield of the
recovered t-butyl chloride.Since the product is extremely volatile, its
containershould be tightly covered.The synthesis of tert-butyl chloride from tertbutyl alcohol yields the following results.