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Chem143 Lab 7

Martin Case/Corinne Sadlowski

Synthesis of Adipic Acid


http://en.wikipedia.org/wiki/Adipic_acid
http://en.wikipedia.org/wiki/Potassium_permanganate
Write-up for this lab to be completed on 11/02 and 11/04
Reagents and Equipment
Cyclohexene from Lab 6
Potassium permanganate (6.0 g per gram of cyclohexene)
Concentrated H2SO4 (~1 mL)
Sodium bisulfite
Erlenmeyer flasks
Water bath
Separatory funnel
Disposable pipettes

Purpose
This is the second of two labs that will conduct a two-step synthesis of adipic acid. In the first lab
you preparep cyclohexene by the dehydration of cyclohexanol, and in this lab you will oxidize
cyclohexene to adipic acid (Scheme 1).
Scheme 1. Synthesis of adipic acid
OH
-H2O

cyclohexanol

[O]

cyclohexene

HO2C

CO2H

adipic acid

The oxidation of an alkene is an example of an addition reaction. Oxygen atoms in the oxidizing
agent add to the carbon-carbon double bond. As a result, the ring opens and the dicarboxylic
acid is formed. Several oxidants have been shown to accomplish this transformation efficiently,
and the reagent of choice for this lab is potassium permanganate, KMnO4. The mechanism for
the reaction is shown in Scheme 2. Notice that this reaction produces the syn-1,2-diol and that
three equivalents of cyclohexene consume 4 equivalents of KMnO4. Under the conditions that
we will use, another two equivalents of KMnO4 are consumed in the oxidation of the diol to the
dialdehyde, and another two in the oxidation to the diacid. Overall, the conversion of 3 moles of
cyclohexene to 3 moles of adipic acid consumes 8 moles of KMnO4

Chem143 Lab 7

Martin Case/Corinne Sadlowski

Scheme 2. Oxidation of cyclohexene using KMnO4


O
MnO4

O
Mn
O

3 MnO3

H2O

MnO4

OH
H2O

MnO3
OH

2 MnO2
O

OH
MnO4
OH

MnO4

HO2C

CO2H

The acid is actually produced as a water-soluble potassium salt. The first step of the work-up is
to wash the aqueous reaction mixture with an organic solvent to remove any non-acidic byproducts or intermediates. We then acidify the aqueous layer to protonate the acid. Adipic acid
should precipitate at this stage. Keeping your aqueous volume to a minimum is critical because
the solubility of adipic acid in water is 1.8 % by weight at room temperature.
Experimental Procedure
1. Prepare a water bath at 50 - 60 C by heating a beaker of water with a burner.
2. For each gram of cyclohexene, mix 6 g of potassium permanganate with 40 mL water in an
Erlenmeyer flask. Add the cyclohexene and mix by swirling. The flask should get warm.
Keep mixing until the warmth subsides.
3. Place the flask in the water bath and maintain the temperature at 50 - 60 C by occasional
heating. Let the reaction go for 45 min, noting any changes.
4. Check for the presence of excess permanganate by withdrawing a drop from the reaction
mixture and touching it on a paper towel. If you see a purple ring around a brown center
(manganese dioxide), permanganate is still present. If permanganate is still present, add
approximately 1 mL of methanol and heat and stir for several minutes. Repeat until
permanganate is no longer present.
5. Filter the hot mixture using a Buchner funnel into a clean filter flask, and rinse the solids with
a few mL hot water (dont use too much water!).
6. Transfer the filtrate to a separatory funnel and extract the aqueous phase with two 25 mL
ethyl acetate washes (ethyl acetate is the top layer). After the washes, transfer the aqueous
layer to an Erlenmeyer flask.
7. Carefully acidify the aqueous mixture with concentrated H2SO4. The solution should be
acidified to pH ~2 according to pH paper.
8. Cool the flask in an ice-bath to initiate crystallization of the product.
9. When crystallization is complete, collect the crystals by vacuum filtration.
10. Weigh your product and calculate a yield.

Chem143 Lab 7

Martin Case/Corinne Sadlowski

Write-up
Calculate a maximum theoretical yield and comment on your yield. There is no analysis of the
product from this lab: we know from the workup that any product has to be an acid. However,
this would not be acceptable in a research lab. What analytical methods would you suggest for
confirming the identity of the product? Why do we use concentrated H2SO4.for the acidification
and not (for example) concentrated HCl? Why is methanol added to the excess permanganate,
what is the product of this reaction, and why does it not interfere with the isolation of the adipic
acid?
Waste disposal
The first organic washes are flammable, and should be disposed of in the appropriate labeled
waste container. The aqueous waste is acidic and therefore corrosive. After it has been
neutralized with excess sodium hydrogen carbonate it is harmless and can go down the sink.
Manganese dioxide should be disposed of as solid chemical waste, and contaminated
glassware can be cleaned with a dilute solution of sodium bisulfite.
Safety
Your pre-lab should include a comprehensive safety assessment of all the solvents and
chemicals used in this lab. Potassium permanganate and concentrated H2SO4 are extremely
corrosive and any splashes of either of these materials should be washed down immediately
with copious amounts of water.