Abstract

The aim of this experiment was to make benzilic acid by a multi-step synthesis that involved first
creating benzil from benzoin and nitric acid, then combining benzil with potassium hydroxide to
create the final benzilic acid product. In order to correctly synthesis, separate, and purify the
benzyl and benzilic acid within the corresponding synthesis, both processes were refluxed,
crystallized, and recrystallized. Melting point analysis and infrared spectroscopy were used to
verify the identification and purity of both products. The benzil’s infrared spectra revealed three
prominent peaks: 1646 cm-1, which indicated the ketone C=O bond, and 1582 cm -1 and 1432 cm-
1
, which indicated C=C phenyl links. The benzylic acid's infrared spectra revealed two prominent
peaks: 3399.07 cm-1, which indicates an OH alcohol bond, and 1718.96 cm -1 indicating a C=O
acid bond, and the broad peak from 3300 to 2600 cm -1 indicating the peak of an O H carboxylic
acid. It was discovered that benzilic acid has a melting point of 120–125°C. 64.4% of the
benzilic acid was produced.

Aim

The aim of the experiment is to synthesize benzilic acid from benzil and find its melting point
and yield
Introduction
Technically, the benzilic acid rearrangement is the 1, 2-rearrangement of 1, 2-diketones using a
base to generate α-hydroxy–carboxylic acids. The formation of benzilic acid by the reaction of
benzil with potassium hydroxide gives rise to the name of this reaction.

In a nucleophilic addition, a hydroxide anion targets one of the ketone groups to make the
alkoxide. In order to position the migrating group R for attack on the second carbonyl group, the
following step necessitates a bond rotation into the conformer. The migrating R group attacks the
α-carbonyl group in a coordinated step, making another alkoxide and simultaneously forming a
keto-group at the opposite carbon. This stage of migration determines the rate. This sequence is
similar to an acyl substitution that is nucleophilic (Wu et al., 2020).
Procedure

Three grams of potassium hydroxide was mixed in five ml of water in a small Erlenmeyer flask
while heating on a hot plate then the solution was cooled to room temperature. Two grams of
benzyl and 7 mill of methanol was added to a separate flask And she said until dissolved. The
two mixtures were added and mixed in the color change was noted. The solution was heated until
dissolved after heating it was cooled in an ice bath. Crystals were scraped with a stirring rod and
about 3 ml of methanol and cooled again. The careless crystals of potassium benzilate was
collected by suction filtration and re-crystallized with equal parts of ethanol and water. The
percentage yield was recorded and so as the melting point of the dried purified benzilic acid
Results analysis

Molar mass of benzil =210.23 g/mol

Mass of crude product=1.23g

Theoretical yield = (1.76g benzil)/ (210.23 g/mol) x 228.25g/mol benzylic acid= 1.91g

% yield = 1.23/1.91 × 100= 64.4%

Melting point 120°-125°C

Answers to the questions

1. The benzil’s infrared spectra revealed three prominent peaks: 1646 cm-1, which indicated the
ketone C=O bond, and 1582 cm-1 and 1432 cm-1, which indicated C=C phenyl links. In addition
to the broad peak from 3300 to 2600 cm-1 indicating an O H carboxylic acid peak, the benzylic
acid's infrared spectrum displayed notable peaks at 3399.07 cm-1 showing an OH alcohol link,
1718.96 cm-1 signifying a C=O acid bond, and 1490.34 cm-1 signifying C=C phenyl bonds.

3. A pinacol (1, 2-diol) is transformed into a ketone through the pinacol rearrangement, which
also entails the migration of a hydrogen atom and a carbocation rearrangement. In contrast, a
phenyl group migrates and a carbon-carbon bond rearranges during the conversion of benzene to
benzilic acid, resulting in the production of a carboxylic acid next to a benzene ring. Although
bond migration is a component of both rearrangements, the molecular environments in which
they occur and the chemical reactions they produce differ.
Discussion

The formation of carbanion is the first step in the benzilic acid rearrangement, which is the
conversion of benzil to benzilic acid. Deprotonation of an alpha carbon atom next to the carbonyl
groups in benzil (diphenylethane-1, 2-dione) starts the process. A base, such as an alkoxide ion
(OR⁻) or hydroxide ion (OH⁻), where R is an alkyl group, helps this deprotonation. One of the
alpha carbons is protonated by the base, making an intermediate carbanion. This step is preferred
because resonance delocalization of the negative charge between the two carbonyl groups
stabilizes the resulting carbanion. The carboanion migrates in the following stage, moving from
one carbon atom to the neighboring carbon atom through a 1, 2-migration. A new carbon-carbon
bond forms as a result of this migration, producing a new carbanion intermediate. A seven-
membered cyclic intermediate is formed as a result of the migration and is stabilized by
resonance. Then the end product, benzilic acid, is created when the cyclic intermediate is
protonated by a solvent molecule or a proton donor. Benzilic acid is formed when the
intermediate is protonated, which regenerates the carboxylic acid group and returns the
carbanion back into a neutral carboxylic acid group. (Hine and Haworth, 1958)

In a nucleophilic acyl substitution reaction, such as the rearrangement of benzil into benzilic
acid, the carbanion targets the nearby carbonyl carbon atom as a nucleophile. For the synthesis of
carboxylic acids from diketones, this rearrangement process is an important synthetic technique
in organic chemistry.

The melting point range was between 120-125°C and the crystals were colorless however the
solution that was formed was reddish brown and the percentage yield recovery was 64.4% that’s
making it

Conclusion

Reflex temperature is necessary for the full conversion of substituted benzil to benzilic acid,
which is carried out in the presence of potassium hydroxide as a base. However, these bases that
contain metallic ions produce waste that is metallic and wealthy, which can need more heat or
energy. The experiment was successful since the literature indicated that the melting point of the
second phase of the multi-step procedure to make benzilic acid was close, and the yield was
64.4%
References

Jack Hine and Howard W. Haworth (1958) The Mechanism of the Benzilic Acid Rearrangement
Journal of the American Chemical Society 80 (9), 2274-2275

Wu, H., Wang, Q., & Zhu, J. (2020). Catalytic enantioselective benzilic ester rearrangement.
Angewandte Chemie, 132(18), 7328–7332.