Oxidation of

cyclohexanol to adipic
acid
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A special synthesis in Chemistry

44.1

by

David Joram Mendoza

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 Recall Exer 2: Oxidation
of a secondary alcohol
( cyclohexanone
• from
cyclohexanol is oxidized to cyclohexanone
with household bleach ( sodium hypochlorite)
cyclohexanol)

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 In this case,
cyclohexanol was
oxidized to a
dicarboxylic acid  1-6-
hexanedioic acid or
adipic acid.

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 Proposed Mechanism*

* by Mayo, et al. , 2011

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 Possible side reactions
1. Formation of dicyclohexyl ether

This is minimized by the dropwise addition of

cyclohexanol with gentle swirling after every
drop. This is also minimized by controlling
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 Possible side reactions
2. Formation of cyclohexene

This is minimized by the dropwise addition of

cyclohexanol with gentle swirling after every
drop. This is also minimized by
controllingthe reaction temperature.
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 Experimental Procedure
1. 2 mL of nitric acid was placed in a micro-reflux set-
up.

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 Experimental Procedure
2. The acid solution was
Brown
heated to 55 – 60 ºC. nitrog
3. 1.0 mL of en
oxides
cyclohexanol was
added to the acid
solution dropwise at a
rate of 1 drop per 30
s.

explosive and
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exothermic!
 Experimental Procedure
4. Once the addition of
cyclohexanol was
completed, the temperature
(55 – 60 ºC) was maintained
for 30 minutes.
5. The temperature was
then elevated to 100 ºC
over ( for about 10
minutes) and was further
maintained for another 5
minutes.
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 Experimental Procedure

6. It was cooled to room

temperature and was
then placed in an iced
bath for crystallization of
adipic acid.

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 Experimental Procedure
7. The light yellow
crystals were then
collected through
suction filtration with
frequent washings
with ice-cold water.

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 Experimental Procedure
8. The white crystals were then dried
and weighed. A percent yield of 87.1 %
was incurred.

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 Percent Yield
A percent yield of 87.1 % was incurred.

The possible sources of error include:

1. Incomplete transfer/ spillage of
cyclohexanol during the addition to the
acid solution
2. Incomplete isolation of crystals during
suction filtration
3. Dissolution of some crystals to water
( since adipic acid is partially soluble to
water)
4. Possible presence of side products
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 Chemical tests

For cyclohexanol:
JONES TEST
Red-orange liquid
mixture to green
(+)

2 + 2CrO3 + H2SO4  3 + 6H2 O +

Cr2(SO4 )3 (green)

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 Chemical tests

For cyclohexanol:
HOT, ACIDIC KMnO4
TEST
Disappearance of
purple color and
formation of brown
precipitate (+)

+ hot, acidic KMnO4  + MnO2

(brown
ppt.)

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 Chemical tests

For cyclohexanol:
Reaction with 10 % Litmus test
NaHCO3
Blue to blue
No evolution of gas
Red to red
(-)
( neutral)

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 Chemical tests

For adipic acid:

JONES TEST HOT, ACIDIC KMnO4
Red-orange liquid TEST
mixture remained Purple liquid mixture
(-)
(-)

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 Chemical tests

For adipic acid:

Reaction with 10 %
NaHCO3
evolution of CO2
gas (+)

+ 2NaHCO3  +
2CO2 + 2H2O
COO-
COO-
Na+
Na+
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 Chemical tests

For adipic acid:

Litmus test

Blue to red
Red to red
( acidic)

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 Melting point
determination

THEORETICAL EXPERIMENTAL
MELTING POINT MELTING POINT
RANGE
152 º C 151- 152 º C

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 Uses of adipic acid
1. It is the monomer used in the
manufacture of nylon -6,6:

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 Uses of adipic acid
USES OF NYLON 6-6
 Carpet fiber
 Apparel
 Airbags
 Tires
 Zip Ties
 Ropes
 Conveyor Belts
11/25/12  Hoses
 Uses of adipic acid

2. Used in lubricants, synthetic fibers,

plastics , polyurethane resins and
plastilizers.
3. Small amounts are used as flavoring
and gelling aid
4. Used in medicine

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 Disadvantage of the
synthesis
The synthesis is similar to the industrial
production of adipic acid wherein a
mixture of cyclohexanol
and cyclohexanone (called "KA oil“) is
oxidized with nitric acid to give adipic acid,
via a multistep pathway.

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 Disadvantage of the
synthesis
ü This industrial synthesis of adipic acid is
detrimental to the environment.
ü A by-product of the synthesis is nitrous
oxide (N2O)  causes global warming
and ozone depletion as well as acid rain
and smog.
ü about 400,000 metric tons of nitrous
oxide is emitted annually , which
corresponds up to 8% of the worldwide
11/25/12 anthropogenic emission of N2O
 Green synthesis of
adipic acid
ü catalytic oxidation of cyclohexene in
the presence of a phase-transfer
catalyst (Aliquat 336).

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 The End
Thank you for
listening!

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