Adipic Acid
Adipic Acid
Adipic Acid
R2
H
R3
+/or
R1
mild
oxidation R1
OHOH
H
R2 R3
R2
vigorous
oxidation
H
R3
R1
OH
O + O
R2
R3
O
R3
In this experiment, we will carry out the oxidative cleavage of cyclohexene yielding 1,6hexanedioc acid (adipic acid).
O
OH
HO
cyclohexene
adipic acid
Adipic acid is used in the production of Nylon 6,6 which is made by alternate units of adipic
acid and 1,6-diaminohexane by amide linkage. Nylons are among one of the most important
commercial polymers (large molecules) made up of many covalently-linked smaller molecules
(monomers). A monomer is a molecular building block that can be used to make up a polymer
chain when bond together with other monomers. Since Nylon 6,6 is made up from two
different monomer of adipic acid and 1,6-diaminohexane, is called a copolymer.
O
n
OH
HO
+ n H2N
NH2
O
adipic acid
H
N
H
N
O
Nylon 6,6
1,6-diaminohexane
H
N
O
-caprolactam
Nylon 6 (perlon)
The laboratory-scale oxidation cleavage of alkene is accomplished with hot, basic KMnO 4
solution. Industrial method uses nitric acid. The hazardous of each method are:
N
H
Hot, basic KMnO4: harsh oxidizer; produce large quantities of MnO 2 waste.
HNO3: many chemical and safety hazards and environmental risks; produce nitrous oxide
(N2O) which is a suspected green house gas; adipic acid production is believed to be the
source of 10% of all non-natural nitrogen oxides (NO x).
In this experiment sodium tungstate (Na2WO4) is used as an alternative oxidation procedure.
Na2WO4 is a catalyst for oxidation of cyclohexene to adipic acid by hydrogen peroxide.
Hydrogen peroxide procedure is appreciably greener than other two methods. It doesnt need
strongly basic solution and the only byproduct of the reaction is water rather than MnO 2.
Another green feature of this reaction is, the tungstate functions catalytically, with intermediate
reduced tungstate products being oxidized back to the tungstate oxidation state by hydrogen
peroxide.
Na2WO4 is soluble in water, while cyclohexene is not. Therefore the cyclohexene and aqueous
solution of Na2WO4 and H2O2 will be immiscible. To keep this reaction as green as possible, we
want to avoid the use of any other solvent. In order to effect the reaction between cyclohexene
and WO42-, then, we need to enhance the solubility of WO42- in cyclohexene. This can be
effected by the technique phase transfer catalysis. Ammonium salts bearing hydrophobic
groups, while still ionic, are soluble in less-polar media such as organic solvents. Through ion
pairing, such salts can bring anions from aqueous media to these less-polar media, thereby
making them available for reaction. This phenomenon is referred to as phase transfer. Since
ammonium salt can play its role many times, it may be used in catalytic quantities, hence the
name phase transfer catalysis.
cyclohexene
2 R4N+X-
adipic acid
(R4N)[reduced W]
(R4N)2WO4
2 R4N+Xorganic phase
aqueous phase
Na2WO4
2 NaX
2 NaX
Na2[reduced W]
H2O2
In this experiment, we will use a commercial phase transfer catalyst known as Aliquat 336,
[CH3(CH2)7]3NCH3+Cl-. Since both aliquat 336 and Na2WO4 function catalytically, only hydrogen
peroxide is needed as a stoichiometric reagent. In addition, although we dont do so in this
experiment, it is possible to reuse the aqueous layer containing the tungstate catalyst, further
enhancing the green nature of this procedure.