Silesian University of Technology

Faculty of Chemistry - Macro group

Year II; 4th semester

Organic Chemistry – Laboratory

Exercise topic:

2-Chloro-2-methylpropane from 0.30

mole of t-Butanol
Preparation recipe: Organic Synthesis J.F. Norris, A.W. Olmsted, 1961, Coll. Vol. 1, 144

CH3 CH3
H3C OH + HCl H3C Cl + H2O
CH3 CH3

74.12 [g/mol] 36.46[g/mol] 92.57[g/mol]

C3H9OH HClconc C3H9Cl

Student’s Name: Szymon Targosz

Supervisor: dr inż. Wojciech Szczepankiewicz

Marks grade:
Recipe, lab techniques and safety rules competence: ………… /3 marks
Exercise performance: ………… /5 marks
Report: ………… /2 marks
End mark: ………… /10 marks
 A) PREPARATION RECIPE: [recalculated amounts per 0.3 mol]

Place the t-Butanol (25g) [22.236g, 28.508ml, 0.3mol] in two-neck round bottom flask equipped
with Allihn condenser. Add concentrated (36%) hydrochloric acid (85ml) [75.6024ml, 0.8808mol],
anhydrous calcium chloride (10g) [8.8944g] and stir bar. Second neck is used in order to introduce
reagents and after it is closed tight with stopper. Place the flask on magnetic stirrer and stir vigorously
for 30 min then left until separation of layers. Introduce the reaction mixture into separation funnel.
Wash the organic layer with freezing water (20ml) [17.79ml] till slightly acidic solution is obtained.
Then wash organic layer with 5% sodium bicarbonate (20ml) [17.79ml, 1.9569g (5%)] and again with
freezing water (10ml) [8.8944ml]. Dry the organic layer over anhydrous calcium chloride, filter with
fluted filter paper directly to the distillation flask and distil under normal pressure. Collect fraction
boiling at 49-51°C. Obtaining 28g [24.904g, 29.648ml, 0.269mol] of crude product with 90% yield.

Note 1: Laboratory coat must be worn at all time in the laboratory. Safety glasses must be put on face
before entering the laboratory. Work in protecting gloves. Work under the fume cupboard.
Note 2: Remember about leveling the pressure in separation funnel.

Waste Disposal: Acidic aqueous layer neutralize carefully with solid sodium carbonate until
precipitate will appear then pour into the savage system. Forerun and after-run(tail fraction) pour out
into container for liquid halogenated organic waste (F).

B) MATERIAL SAFETY DATA SHEET AND RISK ASSESSMENT

Reagents:

 2-methyl-2-propanol (t-Butanol) : R11, R20, R36/37, (S2), S9, S16, S46,

 Concentrated hydrochloric acid: R34, R37, (S1/2), S26, S45,
 anhydrous calcium chloride: R36, (S2), S22, S24,
 aqueous sodium bicarbonate: causes serious eye irritation

Unit Operations:

 Stirring: risk of spilling off the reaction mixture around. Risk of electrocution
 Separation: risk of exploding if pressure is not leveled
 Distillation: Electric shock and thermal burn probability
C) EQUIPMENT DRAWINGS
Reaction with magnetic stirring and Allihn condenser:

5 6 5 6
4 7 4 7

3 8 3 8

2 9 2 9
1 1 1 1 10

Separation process: Distillation:

5 6 5 6
4 7 4 7

3 8 3 8

2 9 2 9
1 1 01 1 10
D) PHYSICOCHEMICAL PROPERTIES OF PRODUCTS AND REACTANTS
OF REACTION

Molar
Density Boiling temperature Melting temperature
Substance mass
[g∙cm-3] [◦C] [◦C]
[g∙mol-1]
t-Butanol 74.12 0.78 82 25
Conc. hydrochloric acid 36.46 1.18 48 -27
2-chloro-2-methylopropane 92.57 0.84 51 -26
Water 18.02 1 99.97 0
Sodium bicarbonate 84.01 2.2 - 50
Anhydrous calcium chloride 110.99 2.15 1935 772

E) CALCULATIONS

Conc. hydrochloric 2-chloro-2-

Scale t-Butanol Water
acid methylopropane
[mol] 1 1 1 1
Stoichiometrically
[g] 74.122 36.461 92.567 18.015
per 1 mole
[ml] 95.028 30.899 110.2 18.015
[mol] 0.3 0.3 0.3 0.3
Stoichiometrically
[g] 22.236 10.938 27.77 5.4046
per 0.30 mole
[ml] 28.508 9.2697 33.06 5.4046
According to [mol] 0.3373 0.9903 (36%) 0.3025 0.3025
recipe [g] 25 100.3 28 5.4496
per 25 g [ml] 32.051 85 33.333 5.4496
According to [mol] 0.3 0.8808 (100%) 0.269 0.269
recipe [g] 22.236 32.115 24.904 4.8461
per 0.30 mole [ml] 28.508 27.216 29.648 4.8461
According to [mol] 0.3 0.8808 (36%) 0.269 0.269
recipe [g] 22.236 89.211 24.904 4.8461
per 0.30 mole [ml] 28.508 75.6024 29.648 4.8461
Excess and yield - 193.6% 90% [calculated 89.667%] -

F) Materials for synthesis:

Reagents:

 t-Butanol 35 [ml]
 conc. Hydrochloric acid 80 [ml]
 Water 50 [ml]
 Sodium bicarbonate: 5 [g]
 anhy. Calcium chloride 10 [g]
Equipment:

1. Stirring:

 Round-bottomed, two-necked flask (V = 250 [ml])

 Magnetic stirrer with dipole
 Stopper
 Allihn condenser
 Support stand
 Rubber hoses
 Clamps
 Clamp holders
 Beakers and funnels for introduction of reagents

2. Separation of layers:

 Separatory funnel
 Support ring
 Support stand
 Clamp holder
 Glass rod, indicator paper

3. Distillation:

 Heating mantle + cables + regulator

 Support stand
 Rubber hoses
 Clamps
 Clamp holders
 Distillation flask, receiving flasks
 Thermometer
 Distillation head
 Labjacks
 G) Description of the performed synthesis:

9.03.2011

 10:30 – I’ve set apparatus, turned on water in reflux condenser and warm up the bottle with t-
butanol (because it’s frozen)
 10:50 – I’ve introduced into two-necked round bottom flask about 28.5ml of t-Butanol then 75.5ml
of concentrated(36%) hydrochloric acid and about 8.9g of anhydrous calcium chloride
 11:00 – Started stirring (should be vigorously but it was rather medium stirring)
 11:30 – End of the stirring. I’ve closed thoroughly the flask with the crude product and left for a
week until next laboratory classes.

16.03.2011

 8:55 – I’ve take out flask with crude product and put it into the cooling water bath(water, ice, NaCl,
T≈-5°C). I’ve set the apparatus separation.
 9:10 – I’ve prepared 5% sodium bicarbonate solution
 9:30 – I’ve introduced crude product into the separation funnel then washed it with 10ml of freezing
water, checked pH – strong acidic
 9:40 – added 8ml of water, checked pH – slightly acidic
 9:45 – I’ve poured out lower aqueous layer washed crude product with 18ml of 5% sodium
bicarbonate (careful on pressure leveling)
 9:50 – I’ve washed crude product with two portions of freezing water, 10ml+10ml
 10:00 – I’ve poured out lower aqueous layer, neutralized it with sodium bicarbonate, diluted and
poured out into the sewage system; upper organic layer I’ve poured into flask with a stopper and
introduce into it the anhydrous calcium chloride until precipitate has been changed from jelly to
powdery, the flask put into water bath and wait until crude product dries over anhydrous calcium
chloride
 11:15 – I’ve set distillation apparatus. I’ve weighted the receiver flask(for product), receiver
flask(for forerun and after-run) and stopper
mflask for product =52.87 [ g ] mforerun, after−run flask =61.80 [ g ]m stopper =13.50[ g]
 11:30 – I’ve filtered dried crude product with fluted filter paper directly into the distillation flask.
I’ve introduced five porous pots into distillation flask and started distillation.
 11:35 – I’ve collected no forerun; I’ve started the pure product collecting at 49°C, temperature was
increasing until 51°C then I’ve changed receiver to after-run flask and collected after-run between
51°-53°C.
 11:40 – I’ve finished distillation. I’ve weighted the flask with pure product and after-run.

m pure ∏ . flask =88.50 [g]mafter−run flask =65.10[ g]

m pure product =88.50−66.37=22.13 [g]
mafter −run=65.10−61.80=3.30[ g]
22.13
Yield theoretical= ∙ 100 %=88.86 %
24.90
88.86
Yield practical = ∙ 100 %=98.7 %
90
 12:30 – I’ve poured out the after-run into container for liquid halogenated organic wastes, I’ve given
back the pure product, closed and signed, to the storage. I’ve cleaned apparatus and labware glass

H) Summary:
I’ve obtained 22.13 grams of pure 2-chloro-2methylpropane with theoretical yield 88.86% and
practical yield 98.7%.