ABSTRACT

Benzil, prepared by oxidation of benzoin with nitric acid, is rearranged with the presence of a
strong base to a benzylic acid. The initially obtained potassium benzilate were crude and was
further purified by recrystallization. The tendency of melting point (98 ◦C-99◦C) towards the
theoretical melting point (115◦C) verified the qualitative indication of its purity of the product. A
percentage yield of 39% was obtained which is very low.

AIM

The goal of this experiment was to synthesize benzilic acid from benzyl by molecular
rearrangement in the presence of a base.

INTRODUCTION

Benzilic acid is an organic, white crystalline aromatic acid compound which is soluble in many
primary alcohols and it is used in preparation of quite a few pharmaceuticals such as glycollate
pharmaceuticals, and it is mostly known as the acid used in the esterification to make the
incapacitating hallucinogen (BZ) (Selman, 1959). In general, synthesis is a laboratory technique
in which through reactions, a new product can be created. This allows scientists to synthesize
more complex and useful chemicals. The synthesis done in this experiment includes the steps of
the reaction being done, isolation, purification, and finally characterization. In this specific lab,
potassium hydroxide, and heat are used to reduce the benzil. The first technique for the
reaction is reflux. In reflux, a condenser is used so the reaction solution can be heated without
losing any product from evaporation as condensation happens consistently. The reason that the
reaction is heated in the first place is to increase the energy of the system. As the heat
increases, the thermal energy of the particles increases, which increases the energy to the
activation energy level At this point, the bonds are able to break and the collisions form the
reactions. Once the reaction has taken place, the technique of filtration is used to isolate the
product. After filtration, the moles of the final product will be used over the moles of the
starting reactant to calculate the percent yield. Once this is calculated, the product is
characterized using the lab technique of IR spectrum analysis and melting point analysis. These
both may be compared to established samples to determine the accuracy of the product. The
synthesis of benzilic can also be performed by the oxidation of benzoin by sodium bromate in
the presence of sodium hydroxide and this reaction occurs via an intermediate formation of
benzil and also the reaction occurs in the presence of heat at around 85 degrees Celsius for
about 3hours.
Figure 1.1: Reaction Scheme

PROCEDURE

3.00g of potassium hydroxide was dissolved in 5ml of distilled water in a 50ml conical by
heating on a hot plate. The solution was the allowed to cool while dissolving 2.00g of benzil in
7ml of methanol in a 50ml round bottomed flask, it was heated until it is dissolved. The solution
was cooled in an ice bath before being mixed with potassium hydroxide solution. The mixture
was swirled and the colour change was noted. It was the heated in a hot plate until it goes into
a solution before being cooled in an ice bath until the crystal was formed. The crystals was then
collected by suction filtration before being recrystallized from ethanol and water. After suction
filtration the yield and the melting point of the product were recorded.

RESULTS

Table.1: Preparation of benzilic acid

Mass of KOH 3.03g

Mass of Benzil 1.84g
Mass of petri dish + filter paper 48.96g
Mass of petri dish + filter paper + product 49.74g
Mass of product 0.78g
Colour change Yellow to orange
Melting point of the product 98◦C-99◦C
Weight of the Starting Benzil= 1.84g
Molecular mass of benzil= 210.2g\mol

mass
Moles of Benzil =
molar mass

1.84 g
=
210.2 g ¿

= 0.008754 moles

Weight of the Benzilic Acid Product= 0.78g

Molecular weight of benzilic acid= 228.3g\mol

mass
Moles of benzilic acid =
molar mass

0.78 g
=
228.3 g ¿

= 0.003417 moles

Percent Yield of Benzilic Acid

0.003417 moles of benzili acid

%yield = x 100
0.008754 moles of benzil

= 39%

Table.2 :shows the peak values for benzil’s IR spectrum

Peak Frequencies (cm-1) Functional Group

1531 C=C in an aromatic
1582 C=C in an aromatic
1646 C=O in a ketone
3050 C-H in an sp2
Table.3: shows the peak values for benzilic acid’s IR spectrum

Peak Frequencies (cm-1) Functional Group

1718 C=O in an aldehyde
2916 O-H in an alcohol
3399 C-H in an sp2

DISCUSSION

In the benzilic acid rearrangement, the process for the formation of benzilic acid from benzil is
through base catalysis. The reaction occurred by attacking from a hydroxide ion to the ketone
group of benzil. Based on Kwart and Sarasohn (1961), the formation of alkoxide required a
strong base as potassium hydroxide, since the alternative base as phenoxide which was not
basic enough to attack to the ketone group. After the attack from hydroxide ion, the phenyl
group migrated to second carbonyl group for obtaining another alkoxide group, while the first
alkoxide was changed into carboxylic acid group. The alkoxide group is more basic than the
carboxylic acid group; therefore, the proton from its hydroxide tends to transfer to the alkoxide
to form benzilate potassium. Finally, the proton, which came from hydrochlodric acid, acidifies
the benzilate salt to benzilic acid. Once the benzil is synthesized, the melting point range was
found to be 98°C-99°C which is lower than 115°C, the literature value and this can be due to the
errors happened in the experiment. From the IR spectrum for starting agent, benzil, a peak at
1646 cm-1 is indicated for the ketone group, which was replaced to form benzilic acid. For the
benzilic acid IR spectrum, the sharp peak at 1718 cm-1 presented for carbonyl group in an
aldehyde. The peak at 2916 cm-1 corresponds to the O-H stretching of the carboxylic group. The
absorbance for O-H group of alcohols is at a higher wavenumber than the O-H group in the
carboxylic group since the hydrogen bonding for the carboxylic group.

CONCLUSION
This experiment synthesized benzilic acid from benzIL, the lower melting point and the lower
percentage yield shows that the experiment had which can be close to gross errors and given
another chance there can be a lots of improvements.
REDERENCES

Kwart, H., & Sarasohn, I. M. (1961). Studies on the Mechanism of the Benzilic Acid
Rearrangement; the Rearrangement of Alloxan (I). Journal of the American Chemical Society,
83(4), 909–919. https://doi.org/10.1021/ja01465a039

Selman, S., & Eastham, J. F. (1960). Benzilic acid and related rearrangements. Quarterly
Reviews, Chemical Society, 14(3), 221. https://doi.org/10.1039/qr9601400221

Benzilic+acid | Sigma-Aldrich." Benzilic+acid | Sigma-Aldrich. Sigma-Aldrich, n.d. Web. 17 Feb.

2016.

Multi-Step Synthesis Lab- Week 1. (2016). Arizona State University: CHM 238: Organic
Chemistry Lab II, 1-6.Retrieved February 4, 2016.
EXERCISE

1) From the IR spectrum for starting agent, benzil, a peak at 1646 cm -1 is indicated for the
ketone group, which was replaced to form benzilic acid. For the benzilic acid IR spectrum, the
sharp peak at 1718 cm-1 presented for carbonyl group in an aldehyde. The peak at 2916 cm -1
corresponds to the O-H stretching of the carboxylic group. The absorbance for O-H group of
alcohols is at a higher wavenumber than the O-H group in the carboxylic group since the
hydrogen bonding for the carboxylic group.

2)

3) the intermediate in the benzil rearrangement is a benzylic carbocation, while the

intermediate in the pinacole rearrangement is an allylic carbocation. This difference leads to
different reactivity and selectivity for each reaction.
EXPERIMENT TITLE: SYNTHESIS OF BENZILIC ACID FROM
BENZIL REARRANGEMENT
SURNAME: TAPOLOGO
INITIAL: M
ID: 201602480
LAB DAY: THURSDAY @10AM
EMAIL: 201602480@UB.AC.BW