SN1 AND SN2 REACTIONS: Synthesis of n-butyl bromide and t-butyl

chloride
Traya, Levie Grace M.

INTRODUCTION
Alkyl halides can be synthesized
when alcohols react with hydrogen
halides. An alkyl halide is a
hydrogen-substituted alkane, and a
hydrogen halide is a compound
consisting of hydrogen bonded to a
halogen. Alkyl halides are classified
as primary, secondary and tertiary
depending on the number of alkyl
substituents directly attached to
the carbon bearing the halogen
atom. The mechanism of acid
catalyzed substitution of alcohols
are termed SN1 and SN2, where S
stands
for
substitution
while
sub-N
stands for nucleophilic,
and the numbers 1 and 2 describes
the
first
and
second
order
respectively. The 1 and 2 also
represents whether the reaction is
unimolecular
or
bimolecular
reaction. The secondary alcohols
favor the react with hydrogen
halides by SN1 and SN2 mechanism.
For primary or methyl alcohol, both
molecules undergo SN2 mechanism
while tertiary alcohols undergo SN1
mechanism.
In SN1 reaction, the protonated
alcohol, or oxonium ion losses
water molecule and forms a

carbocation intemidiate in the ratedetermining step. The carbocation

is then rapidly attacked by halide
ion to form the alkyl halide. On the
other hand, SN2 reaction happens
when the nucleophile assists in the
expulsion if water from the

oxonium
ion
via
bimolecular
transition rate. The SN2 process is
expected to be especially slow and
is not observed in tertiary alcohols
due to the transition state being
crowded
as
the
degree
of
substitution decreases at the
reating
center,
SN2
reaction
becomes
dominant
over
SN1
reaction.
The
main
purpose
of
this
experiment is to prepare n-butyl
bromide from n-butyl alcohol via
SN2 and t-butyl chloride from tbutyl alcohol via SN1 reaction. Also
this experiment aims to understand
the SN1 and SN2 mechanism
involved in the reaction and to
determine the yielded percentage
of the experiment.

METHODOLOGY

Materials for synthesis of n-butyl

bromide
This experiment will make use of
the following: (a) sodium bromide,
(b) anhydrous calcium chloride, (c)
n-butanol, (d) conc. sulfuric acid,
(e) sodium hydroxide, (f) beaker,
(g) thermometer, (h) boiling chips,
(i) boiling flask,
(j) reflux, (k)
condenser, (l) rubber tubing, (m)
hot plate, (n) iron stand, (o) iron
ring, (p) iron, (q) iron holder, (r)
wire gauze, (s) stirring rod, (t)
pipette,
(u)
aspirator,
(v)
separatory
funnel,
(w)
glass
stopper and (x) simple distillation
set-up.
Materials for synthesis of t-butyl
chloride
This experiment will make use of
the following: (a) t-butanol, (b)
conc.
hydrochloric
acid,
(c)
aqueous sodium bicarbonate, (d)
anhydrous calcium chloride, (e)
separatory funnel, (f) glass stopper,
(g) iron stand, iron ring, (h) pipette,
(i) aspirator, (j) Erlenmeyer flask,
(k) boiling chips, (l) distilling
apparatus, (m) dry-apparatus setup and (n) steam bath set-up.
Procedure for synthesis of n-butyl
bromide

Figure 1. Reflux setup

Place 24.0 g of sodium bromide in

a 250-mL round bottomed flask and
add 25-mL of water and 17-mL of
n-butanol. Cool the mixture in a ice
bath and slowly add 20-mL of conc.
sulfuric
acid
with
continuous
swirling in the ice bath. Add several
boiling stones to the mixture.
Assemble the reflux set-up in an
iron stand as shown in fig 1. with
the use of a round bottom flask s
reaction vessel. The inverted funnel
in the beaker acts as a trap to
absorb the HBr gas evolved during
the reaction period. Heat the
mixture with the heating mantle,
an oil bath, or a flame until the
mixture begins to reflux gently.
Heat the mixture under reflux for
30 mins. Two layers will form
during this time.
At the end of this reflux period,
remove the heating source and
allow the mixture to cool. Remove
the condenser and reassemble for
simple distillation. Add several new
boiling stones to the roundbottomed flask. Distill the mixture
and collect the distillate in a
receiver cooled by an ice bath. The

alkyl halide co-distills with water

and then separates into two phases
in the receiver. Distill the mixture
until the distillate appears clear.
The temperature should reach 110115 by that time. While the
distillation is going on, remove the
receiver and collect a few drops of
distillate in a test tube containing
some water. Check to see whether
the distillate is completely soluble.
If it is, no alkyl halide present and
the distillation may be stopped. If
the distillate produces insoluble
droplets in the water, then the
distillation must be continued until
the distillate becomes completely
water-soluble.
Transfer the distillate to a
separatory funnel, add 25-mL of
water to it, and shake the mixture.
Drain the lower layer. Discard the
aqueous layer after making certain
that the correct layer has been
saved. Return the alkyl halide to
the funnel and add to it 15-mL of
cold sulfuric acid. Swirl the mixture
until it is thoroughly mixed.
Stopper the funnel and shake it
thoroughly. Allow several minutes
for the phase to separate. Drain
the lower layer from the funnel.
Allow several minutes for further
separation and drain again. Wash
the n-butyl bromide with 15-mL of
10%NaOH solution.
Carefully
separate the layer and be certain
to save the organic layer. Dry the
crude n-butyl bromide over 1.5 g

anhydrous
calcium
chloride.
Stopper the flask and swirl the
contents until the liquid is clear.
Decant the clear liquid into a
drying distilling flask. Add boiling
stones and distill the crude n-butyl
bromide in a dry apparatus. Collect
the material that boils between 98

and 102 . Weigh the

product
and
percentage yield.

calculate

the

Procedure for synthesis of t-butyl

chloride
In a 125-mL separatory funnel,
place 22-mL of t-butyl alcohol and
50-mL of conc. hydrochloric acid.
Do not stopper the funnel. Gently
swirl the mixture in the separatory
funnel for about 1 minute. Stopper
the separatory funnel and carefully
invert it with occasional venting.
Shake the funnel for 2-3 minutes.
Allow the mixture to stand in the
separatory funnel until the two
layers have completely separated.
Wash the organic layer with one
25-mL portion of water. Again,
separate the layers and discard the
aqueous layer. Wash the organic
layer with 25-mL portion of 5%
aqueous
sodium
bicarbonate.
Gently swirl the funnel until the
contents are thoroughly mixed.
Stopper the funnel, and carefully
invert it from time to time with
venting for 1 minute. Allow the
layers to separate, and drain the

lower aqueous bicarbonate layer.

Wash the organic layer with on 25mL portion of water, and again
drain the lower aqueous layer.
Transfer the organic layer in a
small dry erlenmayer flask. Pour it
from the top of separatory funnel.
Dry the crude t-butyl chloride over
anhydrous calcium chloride until it
is clear. Swirl the alkyl halide with
the drying agent to aid the drying.
Decant the clear material into a
small distilling flask. Add boiling
stones and distill the crude t-butyl
chloride in a dry apparatus, using
steam bath. Collect the pure t-butyl
chloride in a receiver cooled in ice.
Collect the material that boils
between 49
and 52 .
Weigh the product and calculate
the percentage yield.

DISSCUSSION
Synthesis of t-butyl chloride
In
this
experiment,
n-butyl
alcohol, a primary alkyl halide, is
prepared by reacting the alkyl
halide with sodium bromide and
sulfuric acid. From the chemical
reaction presented below, the
reaction produces hydrogen halides
during the reflux when sodium
bromide reacted with sulfuric acid.
2 NaBr + H2SO4
Na2SO4

2 HBr +

The produced hydrogen halide is

used to convert the alkyl halide
into
n-butyl
bromide
via
nucleophilic
substitution.
Meanwhile, the excess sulfuric acid
serves as a reagent that speeds up
the reaction by shifting the
equilibrium and thus produces
more hydrobromic acid. Sulfuric
acid will also be protonated as
hydroxyl group of the alkyl halide in
order to remove water from the
equation rather than the hydroxide
ion OH-. Sulfuric acid will also be
protonated to produce water and
be deactivated to become a
nucleophile to avoid the n-butyl
bromide from being converted back
into its alcohol form because water
can do a nucleophilic attack on the
n-butyl bromide.
The synthesis of this alkyl halide
is SN2 reaction. The hydrogen
bromide reacts with the alkyl halide
attacking it from the opposite side,
thereby inverting stereochemical
configuration, of the leaving group.
The mechanism is shown in the
figure 2 as below.

Figure 2

Sodium bicarbonate is added to

serve as neutralizer to the acidic

solution.
The
drying
agent
anhydrous calcium chloride is
added in order to absorb water
droplets in and to purify the
organic layer. To ensure that all
water droplets are eliminated, an
excess anhydrous calcium chloride
should be added because if there is
any water droplets that remains in
the materials collected, it would
interfere with the analysis. After
the drying agent is filtered out, the
boiling stones are added to prevent
over boiling during distillation. The
distillation is done to purify the nbutyl bromide in the temperature
range of 98 and 102 .
Synthesis of n-butyl chloride
In this experiment, t-butyl alcohol
is converted to t-butyl chloride. In
order to synthesize t-butyl chloride
from t-butyl alcohol, hydrochloric
acid is used to react with t-butyl
alcohol. During the reaction, t-butyl
alcohol will undergo SN1 reaction.
The SN1 reaction is where the rate
of formation of t-butyl chloride is
dependent
only
on
the
concentration of the alcohol and is
independent to the amount of acid
used. A strong concentrated HCl is
added to t-butyl alcohol to provide
an acidic medium and to protonate
the electron rich hydroxyl group
allowing it to leave as a molecule
of H2O.

The t-butyl alcohol will act as a

nucleophile which will attack the
proton from the hyrdonium ion in
the solution. Considering BronstedLowry theory, t-butyl alcohol is
considered as a base in this
reaction. It is because t-butyl
alcohol accepts proton from the
hydronium ion and hence forming
t-butyl oxonium ion. In order to
synthesize the molecule, the bond
between carbon and oxygen of the
molecule must be broken. This
breaking of the bond will result to
the formation of a carbocation and
H2O. This carbocation will act as an
electrophile. Due to the lack of
electron, a nucleophile, Cl-, will
attack
the
carbocation
and
therefore stabilizing the molecule.
The carbocation will accept the
electron given by Cl- forming tbutyl chloride.
In adding HCl to t-butyl chloride a
simple reaction will be observed. A
visible 2 layers will be form of
which (with the aid of a sepatatory
funnel) the two layers will be the tbutyl chloride (upper) and the
aqueouas solution (lower). After
draining,
anhydrous
calcium
chloride will be added and will act
as a drying agent where it will
remove any amount of water from
the organic solution. It also helps in
decreasing the solubility of the
solution to aqueous solvents. The
steam bath will be performed to
purify the crude product.

In addition, to neutralize the

acidic medium that was caused by
HCl, a sodium bicarbonate will be
added. This can be shown as:
NaCHO3 + HCl ---- > NaCl + H 2O
+ CO2
A salt sodium chloride, water and
carbon dioxide will be formed
during the neutralization process.
Due to the neutralization, water will
be produce giving a visible, yet,
another two layers, as being highly
soluble; sodium chloride will be
discarded
together
with
the
aqueous layer. To isolate and
reduce the solubility of the organic
layer from water, distilled water
will be used to wash the organic
layer. To produce the crude product
of the t-butyl alcohol, a drying
agent, anhydrous calcium chloride
is added.
REFERENCES
Books:

Bruice, Paula Y. Organic Chemistry.

4th ed. Pearson Prentice Hall. 2004
Boyd,
R. N. & Morrison,
R.T.
Organic Chemistry. 6th Ed. Prentice
Hall. 1992
Carey,
Francis
A.
Organic
th
Chemistry. 4
ed. McGraw-Hill.
2000
Chang, Reymond. Chemistry. 10th
ed. McGraw-Hill. 2010
McMury,
John.Organic.
th
Chemistry.8
ed.
Brooks/Cole,
Cengage Learning. 2012
Web:
(2013,
02).
Nucleophilic
Substitution: Synthesis of N-Butyl
Bromide and T-Pentyl Chloride.
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