Meilen, 16.12.2007
Organic chemistry practical course (OCPI)
HS 07
529-0229-00
Fabienne Vukotic
06-910-541
D-BIOL
Assistant: Guo Xiaoqiang
Synthesis of
Adipic acid
1. Method
The method for the synthesis of Adipic acid is an oxidation of cyclohexanone
with potassium permanganate as the oxidizing agent and sodium hydroxide
as a basic catalyst.
2. Reaction Equation
O
O
KMnO4
OH
HO
NaOH
H2 O
O
3. Mechanism
O
O
O
O
O
H
OH
O
- H2 O
Mn
O
O
Mn
O
O
O
H
O
O
O
+ MnO4
O
O
OH
HO
O
O
O
O
4. Physical and Chemical Properties of Substances
Potassium
permanganate
CAS: 7722-64-7
M: 158.03 g/mol
mp: 50 °C
CH-toxicity class: 3
Risk Phrases
-R8: Contact with combustible material may
cause fire
-R22: Harmful if swallowed
-R50/53: Very Toxic to aquatic organisms, may
cause long-term adverse effects in the aquatic
environment
Safety Phrases
-S60: This material and/or its container must be
disposed of as hazardous waste
-S61: Avoid release to the environment.
Cyclohexanone
CAS: 108-94-1
M: 98.14 g/mol
d: 0.947 g/mL at 25 °C
bp: 155 °C
mp: -47 °C
n20D: 1.450
MAK: 200 mg/m3, 50 mL/m3
CH-toxicity class: 4
Risk Phrases
-R10: Flammable
-R20: Harmful by inhalation
Safety Phrases
-S25: Avoid contact with eyes
Sodium hydroxide
CAS: 1310-73-2
M: 40.00 g/mol
mp: 318 °C
CH-toxicity class: 2
Risk Phrases
-R35: Causes severe burnsIrritating to eyes,
respiratory system and skin
Safety Phrases
-S26: In case of contact with eyes, rinse
immediately with plenty of water and seek
medical advice
-S37/39: Wear suitable gloves and eye/face
protection
-S45: In case of accident or if you feel unwell,
seek medical advice immediately (show label
where possible)
Hydrochloric acid
(conc.)
CAS: 7647-01-0
M: 36.46 g/mol
d: 1.19 g/mL at 25 °C
bp: 85 °C
mp: -25 °C
MAK: 7 mg/m3, 5 mL/m3
CH-toxicity class: 2
Risk Phrases
-R34: Causes burns
-R37: Irritating to the respiratory system
HCl
Acetic acid
CAS : 64-19-7
Safety Phrases
-S26: In case of contact with eyes, rinse
immediately with plenty of water and seek
medical advice
-S36/37/39: Wear suitable protective clothing,
gloves and eye/face protection
-S45: In case of accident or if you feel unwell,
seek medical advice immediately (show label
where possible)
M: 60.05 g/mol
d: 1.049 g/mL at 25 °C
bp: 117-118 °C
mp: 16.2 °C
n20D: 1.3716
MAK: 25 mg/m3, 10 mL/m3
CH-toxicity class: 4
Risk Phrases
-R10: Flammable
-R35: Causes severe burns
Safety Phrases
-S23: Do not breathe gas/fumes/vapor/spray
(appropriate wording to be specified by the
manufacturer)
-S26: In case of contact with eyes, rinse
immediately with plenty of water and seek
medical advice
-S45: In case of accident or if you feel unwell,
seek medical advice immediately (show label
where possible)
Adipic acid
CAS: 124-04-9
M: 146.14 g/mol
D: 0.88 g/mL
CH-toxicity class: 4
Risk Phrases
-R36: Irritating to the eyes
bp: 265 °C
mp: 151-154
5. Experimental Setup
reflux:
vacuum filtration:
20o
20o
safety bottle
vacuum
500 mL
NS 14
20o
250 mL
LaboBib©
300
50
AN
AN
AUS
AUS
1500
500
100
o
0 U/min
250
C
200
150
1000
750
6. Amounts of Substance used
Substance
measured
amount [ml]
3.1
[g]
[mmol]
eq
Cyclohexanone
2.95
30.1
1.04
KMnO4
9.15
57.9
2.0
Water
75
NaOH (10%)
10 drops
Potassium permanganate is the limiting reactant since it requires two
equivalent for one equivalent cyclohexanone.
7. Experimental Section (Procedure)
In a 250 mL round bottom flask, 9.15 g (2.0 eq.) of KMnO4 are dissolved in 75
mL of water and, while stirring, 2.95 g (1.04 eq.) of cyclohexanone are added.
The resulting mixture is heated to 30 °C and 10 drops of a 10 % NaOH solution
are added. The Temperature is then raised to 50 °C for 20 min and then to 100
°C for 1 min. After the mixture has cooled down to RT, it is acidified to pH 0
using concentrated HCl. It is put in an ice bath for 15 min for crystallization.
The crystals are vacuum filtered, washed with cold water, and characterized.
8. Yield
The theoretical yield is 28.95 mmol. The experimental yield is 1.29 g = 8.83
mmol.
The yield percentage therefore is 30.5%
9. Characterization
Melting point
A melting point range of 151 -154 °C was measured. The literature value for
adipic acid is 104 -107 °C.
IR-Spectrum (see attachement)
bands [cm-1]
3200 – 2400
2951
1685
interpretation
COOH
sat. C-H
C=O
Literature spectrum
http://riodb01.ibase.aist.go.jp/sdbs/cgi-bin/direct_frame_top.cgi
10. Remarks and Discussion
The yield is relatively low but the product can be identified as the desired
substance by its IR spectrum and the measured melting point.
11. Literature
Coblentz Society, Inc., "Evaluated Infrared Reference Spectra" in NIST
Chemistry WebBook, NIST Standard Reference Database Number 69,
Eds. P.J. Linstrom and W.G. Mallard, June 2005, National Institute of
Standards and Technology, Gaithersburg MD, 20899. NIST Chemistry
Webbook. 4 Dec. 2007 <http://webbook.nist.gov>.
EMolecules - Searching the World's Chemistry. 2007. EMolecules, Inc. 4 Dec.
2007 <http://www.emolecules.com>.
IGS Giftliste. 31 July 2007. BAG. 4 Dec. 2007
<http://igs.naz.ch/igs/igsServer/de.kisters.igs.igs40.servlets.igs40Servlet>.
Kirste, Burkhard. "Chemikalien: Sicherheitsdaten." Institut für Chemie und
Biochemie an der FU Berlin. 28 July 1994. FU Berlin. 4 Dec. 2007
<http://www.chemie.fu-berlin.de/chemistry/safety/chemsafety.html>.
"Risk & Safety." Sigma-Aldrich. 2007. Sigma-Aldrich Co. 4 Dec. 2007
<http://www.sigmaaldrich.com/Help_Pages/Help_Welcome/Product_
Search/Risk___Safety_Statements.html#Safety%20Phrases>.
Sigma-Aldrich. 2007. Sigma-Aldrich Co. 4 Dec. 2007
<http://www.sigmaaldrich.com/Area_of_Interest/Europe_Home/
Switzerland__Schweiz_.html>.