DEPARTMENT OF PURE AND APPLIED CHEMISTRY

Visayas State University, Baybay, Leyte

CHEM 126 Organic Chemistry II
Laboratory Report
Name: Balagao, Sherey Mae U.
Course/ Yr: BS Chemistry 2
Group No.: 3

Date Performed: December 16, 2014

Date Submitted: January 13, 2014
Rating:
Experiment No. 4

I.

PREPARATION OF ADIPIC ACID FROM CYCLOHEXENE

Introduction
Dicarboxylic acids are organic compounds that contain two carboxyl functional
groups. These compounds are sometimes written as HO 2C-R-CO2H. Adipic acid,
a dicarboxylic acid

with

IUPAC

name

Hexanedioic

acid is

an organic

compound with the formula (CH2)4(COOH)2. From an industrial perspective, it is the

most important dicarboxylic acid: About 2.5 billion kilograms of this white crystalline
powder are produced annually, mainly as a precursor for the production of nylon. The
great majority of the 2.5 billion kg of adipic acid produced annually is used as monomer
for the production of nylon by a polycondensation reaction with hexamethylene
diamine forming 6,6-nylon. Other industrial uses of adipic acid are the production of
adhesives, plasticizers, gelatinizing agents, hydraulic fluids, lubricants, emollients,
polyurethane foams, leather tanning, urethane and also as an acidulant in foods. Adipic
acid is used after esterification with various groups such as dicapryl, di(ethylhexyl),
diisobutyl, and diisodecyl. Adipic acid otherwise rarely occurs in nature.

Nylon 6,6- a polymer of adipic acid and 1,6-diaminohexane

Adipic acid was commonly obtained by oxidation of castor oil with nitric acid
(splitting of the carbon chain close to the OH group), but it is also obtained by oxidation
of cyclohexanone or cyclohexene.
[O]

cyclohexene

Adipic acid

Just as the word reduction usually refers to the addition of hydrogen to a molecule,
the word oxidation usually means the addition of oxygen. The oxidation of an alkene is an
example of an addition reaction. Oxygen atoms in the oxidizing agent add to the carboncarbon double bond. As a result, the ring opens and the dicarboxylic acid is formed. The
purpose of this experiment is to synthesize adipic (hexanedioic) acid through the
permanganate oxidization of cyclohexene and also to gain familiarization of the laboratory
method for following the progress of permanganate oxidations.
II.

Results
Tabulated results obtained from the procedure, including any necessary
computations made with respect to the data is shown below. Accuracy of the overall
procedure is important to yield maximum amount of the product. At first, the original
procedure required chromic acid as the oxidizing agent but with chromic acid being
dangerous if not carefully handle, potassium permanganate was used as an oxidizing agent
instead.
Reaction Equation
+

cyclohexene
MW= 82g/mol

[O]

oxidizing agent
.(KMnO )
4

adipic acid
MW 146 g/mol

Volume of Cyclohexene used

2 mL

Moles of Cylohexene used

0.019 mol

Density of Cyclohexene

0.81 g/cm3

Moles of adipic acid produced

0.019 mol

Actual Yield

1.1 g

Theoretical Yield

2.77 g

Percent Yield

39.71%

Melting point of adipic acid

Calculations:
No. of moles of cyclohexene used:

149 oC -152oC

It was given that 2 mL of cyclohexene was used in the experiment obtained from the
previous experiment where it was produced from the dehydration of cyclohexanol. Using the
given volume of 2 mL, the molecular weight (82g/mol), and the density of cyclohexene
(0.81g/cm3), the theoretical number of moles of cyclohexene used can be calculated.
0.81gcyclohexene
1 mL cyclohexene
= 0.019 moles cyclohexene

No. of moles of cyclohexene = 2 mL cyclohexene

1 mol cyclohexene
82 g cyclohexene

0.019 moles of cyclohexene produces 0.019 moles of adipic acid because cyclohexene has a
ratio of 1:1 with adipic acid
Theoretical yield of adipic acid:
The theoretical amount of product obtainable in grams can be computed by multiplying
the moles of adipic acid produced to the molecular weight of adipic acid which is 146 g/mol.
This is by the knowledge that 0.019 moles adipic acid can be obtained and hence just by
converting it to grams, the theoretical yield is known.
Theoretical yield = 0.019 mol adipic acid x 146 g adipic acid
.
1 mol adipic acid
= 2.77 g adipic acid
Percentage yield of adipic acid:
To compute the percentage yield, actual yield which was the yield obtained from the
experiment is divided by the theoretical yield which was calculated above, multiplied the
whole to 100. The yield obtained from the experiment is 1.1 grams.
Percentage yield =
=

Actual yield
Theoretical yield
1.1 grams
2.77 grams

Percentage yield = 39.71%

III.

Discussion

x 100%

This experiment is in connection with the last experiment because it uses

cyclohexene as one of its starting material. This experiment carried out the oxidative
cleavage of cyclohexene to produce adipic acid.

Cyclohexene, an alkene, is susceptible to oxidation because it has a carbon-carbon

double bond which is a site of relatively high electron density. Oxidative cleavage of
alkenes is a well-known reaction. Several reagents are known to react with alkenes which
result in complete breaking of both bonds to the carbon atoms. With relatively mild
oxidation, only the pi bond of the alkene is cleaved, producing epoxides and 1,2-diols.
More vigorous oxidation can result in the complete cleavage of the carbon-carbon double
bond, leading to the formation of various carbonyl compounds, with the specific product
dependent on the substitution pattern of the alkene and on the nature of the oxidant used.
Reaction of cyclohexene with potassium permanganate under basic conditions results in
oxidation. The cyclohexene is oxidized by the permanganate which leads to a ring opening
reaction producing adipic acid as the final product.

The mechanism of this type of reaction is shown below

MnO2 Brown
precipitate

The first step of the reaction is the interaction of the oxidizing agent which is the
potassium permanganate with the cyclohexene, which occurs at the double bond of
cyclohexene. MnO4 ion attaches to the carbons in the double bond creating two separate
Carbon-Oxygen bonds. Then, the resulting molecule undergoes a reaction with water in a
series of several steps which are quite complex, to produce a diol molecule (1,2cyclohexanediol)

and the compound Manganese Oxide (MnO 2) which is a brown

precipitate.
But before the 1,2-cyclohexanediol is further oxidized (which is the mechanism
shown above), the manganese product actually loses water to form MnO 3 ion which is
unstable. The unstable MnO3 ion undergoes a reaction with water to regenerate the
permanganate ion. The permanganate ion that was regenerated is the one that oxidized the
diol further. To better understand the said reaction, it is illustrated below:

2 OH

The permanganate ions in the solution further oxidize the 1,2-cyclohexanediol as

being a strong oxidizing agent thus forcing a ring opening reaction and converting the cyclic
structure into an alkyl chain with two terminal aldehyde groups, a di-carbonyl compound.
Possible mechanism:

The di-carbonyl compound produced from previous step is still oxidized by the
permanganate ions in solution, forming a product that is figuratively close to being a dicarboxylic acid but without hydrogen. The negatively charged oxygen from the produced
molecule attracted the free potassium ions in the solution from potassium permanganate
(KMnO4). The reaction is illustrated below:

[O]

The di-carboxylic salt product is then converted into adipic acid through the
addition of concentrated Hydrochloric acid (HCl) to the solution and then cooling it in a
waterbath. The solution is then acidified in order to induce protonation and break the bond
it formed with potassium ions. This is the final step of the reaction mechanism and it is
shown below:

2KCl

As the mechanism of the reaction is discussed already, parts of the procedure

that was done is also to be discussed. At the start of the procedure where cyclohexene was
added by potassium permanganate, an excess permanganate ions were form at the solution
and this excess permanganate ions need to be removed because it could possibly affect or
interfere the reactions. Methanol was added to the mixture which is being heated in a water
bath in order to remove the excess permanganate ions in the solution.

Through spot tests on filter paper, the removal of excess permanganate ions
were being observed. Presence of puple color ring around a brown color spot (MnO 2)
indicates that excess permanganate ions were still present. Addition of methanol to the
mixture was gradually done until the purple color ring disappeared. Potassium
permanganate (KMnO4) as a very strong oxidant able to react with many functional groups,
such as secondary alcohols, 1,2-diols, aldehydes, alkenes, oximes, sulfides and thiols.
Under controlled conditions, KMnO4 oxidizes very efficiently primary alcohols to
carboxylic acids. Methanol as a primary alcohol was partially oxidized first into aldehyde
before being fully oxidized to formic acid, the carboxylic acid product. Illustration of
oxidation stages of methanol is shown below:

[O]

[O]

Methanol

Methanal

Formic acid

When a primary alcohol is converted to a carboxylic acid, the terminal carbon

atom increases its oxidation state by four. It was observed in the experiment that the flask
used was completely covered with the brown color Manganese dioxide (MnO 2). Sodium
hydroxide (NaOH) was added to the flask. Sodium hydroxide did two important reaction to
flask. First was the rinsing measure where it is intended to maximize the yield of adipic
acid. There is a partial oxidation of MnO2 by NaOH that is why MnO2 was removed from
the sides of the flask. The other possible use of NaOH is the neutralization of formic acid
which was formed during the oxidation of methanol. The reaction of NaOH and formic acid
is an acid-base reaction forming the salt sodium formate. The oxidation reaction and acidbase reaction of NaOH with MnO2 and formic acid respectively are shown below:
Oxidation reaction
2MnO2

4NaOH

O2

2Na2MnO4

2H2O

Neutralization of formic acid

HCOOH (aq) + NaOH (aq)

NaCOOH (aq) + H2O ( l )

After the acidification of the dicarboxylate salt which it forms the adipic acid,
boiling procedure was done to remove any excess water present in the mixture as well as
any formic acid left behind with a boiling point close to water at 100.8oC. It also remove
any unreacted methanol from the previous step having a boiling point at 64.7 oC. Then next
after the boiling procedure was the step common in obtaining the purest possible final
product, recrystallization, was done where 1.1 g pure white adipic acid was obtained
(39.7% yield). Amount of solvent used was calculated in advance because using too much
solvent leads to a loss of product.
Discussion on Yield
The group obtained 39.77% of the final product. This percentage yield is higher
that the yield obtained by the group from the previous experiment. Still human error is a
factor in obtaining this yield. The yield may be higher if the group did not broke the beaker
containing the mixture during the boiling procedure. Other reason of the loss of product
could be the addition of the initial reactants and the start of the experiment, proper swirling
of the mixtures affect the yield of the product. Despite those some circumstances, its still a
success as the group obtained pure, white crystals of adipic acid.
IV.

Conclusion
Therefore, gaining familiarization of the procedure on how to synthesize adipic
acid was achieved by this experiment. It also gave insights into one of the important
reaction of organic chemistry, oxidation reaction, which define as the addition of oxygen
or the removal of hydrogen where in the experiment, cyclohexene was oxidized to produce
adipic acid. As of today the mechanism is not yet fully specified because some pathways
take several steps that are not yet fully understood. Though the students might not also
understand it fully but at least there is a better understanding on how the reaction
mechanism undergoes.

V.

Answer to questions
1.

What reaction is effected by the addition of methanol to unreacted

permanganate?
-Addition of methanol affects the further oxidation of the diol intermediate to
remove any excess permanganate in the solution.
2.

Does this reaction affect your product?

-Addition of methanol to unreacted permanganate dont have much effect on the

product or even with the yield because at that point, the excess permanganate oxidized
those needed to be oxidized.
VI.

References

http://wwwchem.uwimona.edu.jm/lab_manuals/c10expt12.html

http://www.uvm.edu/~mcase/courses/chem143/adipic_acid.pdf

http://www.researchgate.net/publication/229106098_Clean_synthesis_of_adipic
_acid_from_cyclohexene

http://en.wikipedia.org/wiki/Adipic_acid

https://www.thechemco.com/chemical/adipic-acid/

http://pages.towson.edu/jdiscord/www/332_lab_info/332labsirpmr/expt2oxidati
on.pdf

http://bowluss.faculty.yosemite.edu/uploads/11_Preparation%20of%20adipic
%20acid%20from%20cyclohexene.pdf

http://oatao.univ-toulouse.fr/9999/