Chem 35.

1 TEG Group 5

Experiment 2: Aromatic Side Chain Oxidation

Espiritu, Walter Aljhon

Silong, Rafaelle
Tumimbang, Glenn Vincent

February 18, 2014

I. Abstract
Some conjugated compounds that are obtained from plants are known for their pleasant odor.
These compounds are then described as aromatic. The most common feature among these aromatic
compounds is their presence of a benzene ring, the most stable conjugated system. In this experiment, a
benzene ring derivative and an important aromatic ring reaction will be observed: 1,3 -dimethylbenzene
(meta-xylene) and oxidation, respectively.
II. Keywords: aromatic ring, oxidation, meta-xylene, meta-benzenedioic acid, alkyl benzene
III. Introduction
Benzoic acid is a widely used compound.
Its salts, such as sodium benzoate, are used as
food preservative, and it is also an important
precursor to plasticizers. In medicine, it is a major
constituent of commonly used antiseptics and
inhalant decongestants. With this, various
mechanisms for its production are observed in
organic chemistry. Aromatic side chain oxidation
is an important reaction in the production of
carboxylic acids. Aromatic hydrocarbons can
undergo this reaction as long as an alkyl group
has a hydrogen attached to it, requiring the use of
strong
oxidizing
agents such potassium
permanganate.

vacuum filtration and store the solid in the drying

oven.
Recrystallization and
chlorobenzoic acid

analysis

of

the

o-

IV. Methodology

Recrystallize the product using toluene as the

solvent. (Make sure that you add enough toluene
so that the solid dissolves at a higher temperature
but some of it stays undissolved in room
temperature.) Do not add too much toluene
because you will not be able to crystallize your
product. If you believe youve added too much
toluene you have to evaporate some of the
toluene in the hood. The crystals should be
suspended fully in toluene prior to filtration.
Finally, analyze the o-chlorobenzoic acid by
determining the melting point.

Preparation of o-chlorobenzoic acid

V. Results and Discussion

First, mix 1.5 g KmnO 4, 0.5 g 2chlorotoluene (use ~0.5 mL liquid and determine
its mass and moles) and 35 mL water. Then,
reflux the reaction mixture for about 1.5 hours,
after reflux, collect the filtrate via suction filtration.
(Note: Add sodium bisulfite to reduce the
permanganate ion present in the solution, there
should be no purple color present.) When the
purple color is no longer present filter the mixture
via vacuum filtration to produce a clear filtrate for
the isolation of the aromatic acid. Then, put the
clear and colorless solution in an ice bath and
acidify it by adding ~2.5 mL concentrated HCl.
Collect the precipitated organic product via

Any carbon atom attached directly to the benzene

ring is called a benzylic position.

Figure 1. Benzylic position.

Benzene ring has activating effect on the

reactions on the benzylic position, an example of

Chem 35.1 TEG Group 5

Experiment 2: Aromatic Side Chain Oxidation

which are reactions of alkyl benzenes with

oxidizing agents.

then it will always undergo oxidation by potassium

permanganate to produce benzoic acid.

Chromic acid (H2CrO4), for instance, is a

strong oxidizing agent and readily oxidizes
primary and secondary alcohols. However,
chromic acid does not react with either benzene
or alkanes.

2. Why did we use potassium permanganate

instead of sodium dichromate solution?

On the other hand, alkyl benzenes are

readily oxidized by chromic acid to form benzoic
acid, regardless of the identity of the alkyl group.

Sodium dichromate solution (Na 2Cr2O7) is

a strong oxidizing agent and highly corrosive.
Potassium permanganate is also corrosive but
fairly inexpensive. Also, it is believed that the
reaction with sodium dichromate is slower than
that of the reaction with potassium permanganate.
3. Show the correctly balanced oxidation
reduction equation for this reaction.
C6H5CH3 + 3[O] ==> C6H5COOH + H2O
C6H5CH3 + NaOH + 3[O] ==> C6H5COONa+ + 2H2O
C6H5COO(aq) + H+(l) ==> C6H5COOH

Figure 2: Oxidation of alkyl benzenes

Potassium permanganate (KMnO 4) is also

a strong oxidizing agent and reacts in the similar
way. However, the carboxylic acid product is
formed as its potassium salt, and then a
subsequent acidic workup converts the salt to the
desired product.

+ 6[O] ==>

+ 2H2O

C6H5CH3(g) + 3/2O2(g) ==> C6H5COOH(g) + H2O(g) (e.g.

air/150oC salt catalyst)

VII. Conclusion and Recommendation

Figure 3: O-chlorotoluene to o-chlorobenzoic acid

Regardless of chain length, alkyl groups are

converted to carboxylic acid groups ( -CO2H). An
exemption is the is the substituent ( -CR3)
because it lacks hydrogen, which is needed in
oxidation.
VI. Guide Questions
1. Do all aromatic hydrocarbons give rise to
benzoic acid upon oxidation by potassium
permanganate? If not, what type of alkyl chains
does not give carboxylic acids?
As long as the alkyl group attached to the
aromatic ring has at least one hydrogen atom,

In the experiment, it was observed that

aromatic hydrocarbons can produce a carboxylic
acid given that the alkyl group attached to the ring
has a hydrogen atom. Potassium permanganate
removes the hydrogen from the benzylic position,
forming a benzyl radical, with the oxygen
attacking the carbon to form the C-O bond. The
oxidizing agent used in the production of the
desired benzoic acid (in this case, ochlorobenzoic acid) proceeds faster than most
strong oxidizing agents.
It is recommended to perform the
experiment with another strong oxidizing agent
such sodium dichromate and compare the yield to
that of potassium permanganate.

Chem 35.1 TEG Group 5

VIII. References

Experiment 2: Aromatic Side Chain Oxidation

I hereby certify that I substantially contribute to this

report.

Carey, F. (2006). Organic Chemistry.

Klein, D. (2012). Organic Chemistry.

________________________
Walter Aljhon Espiritu

Oxidation of aromatic alkanes. Retrived from:

http://www.masterorganicchemistry.co
m/reaction-guide/oxidation-of-aromaticalkanes-with-kmno4-to-give-carboxylicacids/

________________________
Rafaelle Silong

________________________
Glenn Vincent Tumimbang