CHEM 210

Synthesis of n-Butyl Bromide (Exp 7)

Synthesis of tert-Butyl Chloride (Exp 8)

Tertiary ROH react with HCl and HBr in minutes;

secondary and primary require HBr and elevated
temperatures.
 Synthesis of n-Butyl Bromide (Exp 7)
Synthesis of tert-Butyl Chloride (Exp 8)
Lecture Outline
1. Purpose of the Experiment
2. Preparation of Alkyl Halides from Alcohols
3. Reactivity of Alcohols and Hydrogen
Halides
4. Nucleophilic Substitution Reactions
5. Mechanism of Nucleophilic Substitution
Reactions
6. Procedure
7. Percent yield
 Purpose
1. To review the synthesis of alkyl halides.

2. To synthesize two alkyl halides; n-butyl bromide

from n-butanol and tert-butyl chloride from tert-
butyl alcohol.

3. To apply the techniques of extraction, drying and

distillation in the purification of the alkyl halides.

4. To calculate the percent yield of the alkyl

halides.
 Overview
ROH + HX → RX + HOH (X =Cl; Br; I)
NaBr
H2SO4
CH3CH2CH2CH2OH CH3CH2CH2CH2Br
b.p = 118°C heat b.p= 101 °C
Soluble in water Insoluble in water

Reflux Assembly
 Preparation of Alkyl Halides
Alkyl halides can be prepared from Alcohols by the reaction
of alcohols with hydrogen halides.
n-Butyl bromide is prepared by the reaction of n-butanol and
hydrobromic acid.
A mixture of sodium bromide and sulfuric acid may be used
in place of HBr.
Use excess H2SO4 to
NaBr + H2SO4 HBr + NaHSO4 shift the reaction to the
right (HBr formation)

NaBr
H2SO4
CH3CH2CH2CH2OH CH3CH2CH2CH2Br
heat 70-83%
The reaction rate depends on the structure of the alcohol and
hydrogen halide
 Reaction of Alcohols with Hydrogen
Halides
ROH + HX → RX + HOH
Alcohol reactivity
CH3OH RCH2OH R2CHOH R3COH
Methanol Primary Secondary Tertiary

least reactive most reactive

Tertiary ROH react with HCl and HBr in minutes;
secondary and primary require HBr and elevated
temperatures.
 Reaction of Alcohols with Hydrogen
Halides

ROH + HX → RX + HOH

Hydrogen halide reactivity

HF HCl HBr HI

least reactive most reactive

 Preparation of Alkyl Halides

(CH3)3COH + HCl 25°C

(CH3)3CCl + H2O
3o 78-88%

80-100°C
OH + HBr Br + H2O
2o
73%
120°C
CH3(CH2)5CH2OH + HBr
CH3(CH2)5CH2Br + H2O
1o
87-90%
 Preparation of Alkyl Halides
The mechanism of the reaction depends on the structure of
the alcohol, the reaction can proceed via SN1 or SN2

Primary alcohols react by SN2 mechanism (substitution-

nucleophilic-bimolecular).

Tertiary & secondary alcohols react by a SN1 mechanism

(substitution-nucleophilic-unimolecular).

In both cases the first step is protonation of the alcohol

to form a better leaving group H2O
 The SN2 Mechanism
Reaction of Primary Alcohols with Hydrogen Halides.
The SN2 Mechanism

Two-step mechanism for conversion of primary alcohols

to alkyl halides:
Step 1 Protonation of the alcohol
proton transfer to alcohol to form
alkyloxonium ion
Step 2 bimolecular displacement of water
from alkyloxonium ion by halide
 SN2 Mechanism
Step 1: Proton transfer from HBr to 1-butanol
.. ..
CH3(CH2)2CH2 O: + H Br
..
:

fast, bimolecular
H
+ .. –
CH3(CH2)2CH2 O : + : Br:
..
H
butyloxonium ion
 SN2 Mechanism
Step 2: Reaction of alkyloxonium ion with bromide
ion.
H
.. – +
: Br: + CH3(CH2)2CH2 O :
..
H
slow, bimolecular

H
..
+
CH3(CH2)2CH2 .. :
Br :O:

1-Bromobutane H
 SN1 Mechanism
Reaction of secondary and tertiary Alcohols with
Hydrogen Halides. The SN1 Mechanism
25°C
(CH3)3COH + HCl (CH3)3CCl + H2O

tert-Butyl alcohol tert-Butyl chloride

Three-step mechanism for conversion of tertiary and

Secondary alcohols to alkyl halides

Step 1 Protonation of the alcohol

Step 2 Loss of water to form the Carbocation
Step 3 Carbocation capture by the halide ion
Step 1: Proton transfer

.. ..
(CH3)3C O: + H Cl :
..
H
fast, bimolecular
H
+ .. –
(CH3)3C O : + : Cl:
..
H
tert-Butyloxonium ion
Step 2: Carbocation formation

H
+
(CH3)3C O :

H
slow, unimolecular

H
+ + :O:
(CH3)3C

tert-Butyl cation H
Step 3: Carbocation capture

+ .. –
(CH3)3C + : Cl:
..

fast

..
(CH3)3C .. :
Cl

tert-Butyl chloride
 Reflux
Reflux is continuing boiling
of a solution in a flask
where the solvent is
continually returned to the
flask from a condenser
atop the flask.

By using this technique, it

is possible to heat a
reaction mixture at the
boiling point of the solvent
without losing the solvent
through evaporation

Set-up for reflux

 Synthesis of n-butyl bromide procedure
 In a 250 mL round bottom flask place
18.0 g of sodium bromide, 20 mL of water
and add 12.5 mL of n-butanol (density =
0.81 g/m/L).
 Cool the mixture in an ice bath and
carefully add 15 mL of concentrated*
sulfuric acid H2SO4 (18 M) in small
portions (~ 2 mL each) swirl the solution
after each addition and cool in ice.
 Add two boiling chips. Mount the flask
on a heating mantle, attach a condenser
quickly, and assemble a reflux set-up.
 Reflux gently for 30 minutes. While
refluxing swirl the reaction mixture to
ensure complete reaction.

* Attention concentrated H2SO4 is corrosive handle with gloves

Allow the reaction mixture to cool down for 3 minutes.
 At the end of the refluxing period. Two layers will be formed
 Remove the condenser and carefully transform the set up for
distillation. Heat the flask strongly so that the liquid distils steadily,
collect the distillate in a 50 mL Erlenmeyer flask containing 5 mL
of water. Cool the receiving flask in an ice bath.
The n-butyl bromide will codistill with water (steam distillation)
 Oily drops should appear in the bottom of the receiver. Continue
the distillation until no more oil drops distil into the water, or
when one layer is left in the distillation flask and foaming starts.
 In order to determine when to stop, make the following test.
Remove the Erlenmeyer flask and place a test tube containing 1-2
mL of water. If no oily drops collect at the bottom of the test tube
within a few minutes, the distillation is complete.
 Purification of the crude n-butyl bromide:
Transfer the cooled distillate into a separatory funnel. Observe
two layers.
 Draw off the organic layer (lower layer) into a clean flask.
 Pour the aqueous layer (upper layer) through the mouth of the
funnel into another flask.
 Return the organic layer to the separatory funnel and shake well
with an equal volume of 10 % aqueous solution of Na2CO3 ( to
neutralize traces of the acid).
 Draw off the lower organic layer into a small, clean, dry 50 mL
Erlenmeyer flask.
 Add anhydrous CaCl2, cover and allow the flask to stand with
occasional swirling until the alkyl halide is dry (absence of
turbidity).
 Decant into a dry 50 or 150 mL Erlenmeyer flask.
 Weigh the product.
Notes. 1. Check for the organic layer if in doubt.
2. Never discard any of the layers until the end of the experiment
 Synthesis of tert-Butyl Chloride
25°C
(CH3)3COH + HCl (CH3)3CCl + H2O
tert-Butyl alcohol tert-Butyl chloride

• Tertiary alcohols can be easily converted to their

corresponding alkyl chlorides by the addition of
concentrated hydrochloric acid to the alcohol.
• In this experiment, concentrated hydrochloric acid
is used to prepare tert-butyl chloride from tert-butyl
alcohol via SN1 reaction.
• Optimal SN1 conditions require the reaction to take
place at cold temperatures and under acidic
conditions.
 Synthesis of tert-butyl chloride procedure
Important!! Work UNDER THE HOOD and wear gloves during the
experiment
 Measure, using the 10 mL graduated cylinder, 7.5 mL of tert-
butanol.
 Measure, using the 100 mL graduated cylinder (VERY
CAREFULLY), 25 mL of conc. HCl*
 Transfer the two solutions to a100 mL separatory funnel. Swirl the
funnel (keep it opened) carefully for two minutes to mix the
contents.
 Place the stopper on the separatory funnel and invert it while
holding the stopper firmly and then open the stopcock immediately
to release excess pressure pointing the funnel towards the back of
the fume hood. Repeat one more time.
*NOTE: Conc. HCl is extremely corrosive, use ONLY in the fumehood.
Wash any spills immediately with cold water and neutralize with dilute
sodium bicarbonate.
 Shake gently and vent frequently for 2-3 minutes.
 Drain the lower HCl (aqueous) layer very carefully into a 250 mL
Erlenmeyer flask.

Purification of the crude tert-butyl chloride:

 Measure, using the 100 mL graduated cylinder, 40 mL of
saturated sodium bicarbonate, and transfer it in portions to the
separatory funnel. Swirl several times until the bubbling ceases.
 Shake gently several times and vent the funnel at frequent
intervals.
 Drain the lower aqueous layer in portions into the 250 mL
Erlenmeyer flask where the HCl was previously collected .
 Wash the organic layer with 30 mL of water.
 Drain the lower aqueous layer into the 250 mL Erlenmeyer flask
where the HCl and the sodium bicarbonate were collected.
 Transfer the organic layer (the crude tert-butyl chloride) into a
clean and dry 50 mL Erlenmeyer flask and dry it using a few
granules of anhydrous calcium chloride (drying is complete when
the solution turns from cloudy to clear).
 Decant the colorless crude product to a clean, pre-weighed 50
mL Erlenmeyer flask
 Weigh the Erlenmeyer flask with the product and calculate the
mass of your synthesized tert-butyl chloride.

Note: Discard the aqueous layer in the sink while the organic layer
in a waste bottle.
Calculate percent yield

Actual yield
% yield =  100
Theoretica l yield

Theoretical yield is calculated from the stoichiometry

of the reaction and the number of moles of limiting
reactant used.

Which is the limiting reactant?

In this experiment the mole ratio is 1:1

⇨ Theoretical yield of alkyl halide
= # of moles x molar mass