Oxidation of cyclohexanol to adipic Click to edit Master subtitle style acid

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 1-6hexanedioic 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

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This is minimized by the dropwise addition of cyclohexanol with gentle swirling after every drop. This is also minimized by controlling the reaction temperature.

Possible side reactions

2. Formation of cyclohexene

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This is minimized by the dropwise addition of cyclohexanol with gentle swirling after every drop. This is also minimized by controllingthe reaction temperature.

Experimental Procedure
1. 2 mL of nitric acid was placed in a micro-reflux setup.

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Experimental Procedure
2. 3.

The acid solution was heated to 55 60 C. 1.0 mL of cyclohexanol was added to the acid solution dropwise at a rate of 1 drop per 30 s.

Brown nitrog en oxides

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explosive and exothermic!

Experimental Procedure
4. Once the addition of cyclohexanol was completed, the temperature (55 60 C) was maintained for 30 minutes.
5.

The temperature was then elevated to 100 C 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 Cr2(SO4 )3 + 2CrO3 + H2SO4 3 + 6H2 O +

(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 ppt.)

+ MnO2 (brown

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

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Chemical tests
For adipic acid:
JONES TEST
Red-orange liquid mixture remained (-)
HOT, ACIDIC KMnO4 TEST Purple liquid mixture (-)

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Chemical tests
For adipic acid:
Reaction with 10 % NaHCO3 evolution of CO2 gas (+)

2CO2 + 2H2O

+ 2NaHCO3

COOCOONa+ 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 MELTING POINT

EXPERIMENTAL MELTING POINT RANGE

152 C

151- 152 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 Belts

Ropes Conveyor
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Hoses

Uses of adipic acid

2.

Used in lubricants, synthetic fibers, plastics , polyurethane resins and plastilizers. Small amounts are used as flavoring and gelling aid Used in medicine

3. 4.

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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

This industrial synthesis of adipic acid is detrimental to the environment. A by-product of the synthesis is nitrous oxide (N2O) causes global warming and ozone depletion as well as acid rain and smog. about 400,000 metric tons of nitrous oxide is emitted annually , which corresponds up to 8% of the worldwide anthropogenic emission of N2O

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Green synthesis of adipic acid

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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