Experiment 32: Multi-Step Synthesis

Morgan Lepley
(Lab partner: Lauren Mullinax Johnson)

Organic Chemistry Lab, CHEM 369

The University of Tennessee, Knoxville
TA: Bo Meng
Instructor: Dr. Laureta Smith
Date Performed: 4 August 2011
Due Date: 8 August 2011

Introduction:
The purpose of this experiment is to convert benzaldehyde to benzilic acid
with a three-step set of reactions. With the use of a thiamine-catalyzed reaction, two
equivalents of benzaldehyde react to form benzoin. Step two oxidizes benzoin to
form benzil by using nitric acid. Finally, benzil rearranges to form benzilic acid by
reactions with KOH and then H3O+. The full experiment can be found in
Introduction to Organic Laboratory Techniques: A Small Scale Approach as
Experiment 32.
Thiamine hydrochloride is used as a green reagent as opposed to thiamine
pyrophosphate (TPP) to catalyze the benzoin condensation. In the reaction, the
proton at carbon two is removed with a weak base to form the ylide, which acts as a
nucleophile and adds to the carbonyl group of benzaldehyde. Then another proton is
removed with a base to form a double bond, which then reacts with another
equivalent of benzaldehyde to form another intermediate. The base then removes
another proton to yield benzoin and the ylide, which can hen react with more
molecules of benzaldehyde. Next, the benzoin produced in the first step is oxidized
with nitric acid to prepare benzil in the final reaction, the benzil produces is
rearranged with potassium hydroxide and then an acid reaction, the benzil
produced is rearranged with potassium hydroxide and then an acid (hydrochloric
acid). The addition of potassium hydroxide to benzil yields a carboxylate salt,
potassium benzilate, which then reacts with an acid to produce the final product<
benzilic acid.

Equation 1: Thiamine Catalysis of Benzoin

Equation 2:Oxidation of Benzil

Equation 3: Rearrangement of Benzil to Benzilic Acid

Infrared Spectroscopy (IR) is performed after each step to determine if the

desired product is formed. The 1H and 13C Nuclear Magnetic Resonance
Spectroscopy (NMR) of the final product is also determined to ensure the correct
product is created. These spectra can be found in the attached appendix.
Procedures
On the first session of the experiment, 1.5 g of thiamine hydrochloride was
added to a 50-mL Erlenmeyer flask. The solid was then dissolved by swirling in 2mL of H2O. 15-mL of 95% ethanol was then added to the flask and the solution was
swirled until homogeneous. Next, 4.5-mL of aqueous NaOH solution was added and

swirled until the color changed from a bright yellow to a pale yellow. 4.5-mL of pure
benzaldehyde was added to the flask and swirled until homogenous. This flask
containing the solution was then closed with a stopper and placed in the lab drawer
to crystallize until the next lab period.
For the second lab session, the crystals were broken up with a metal spatula
and the solution was rapidly swirled and quickly transferred to a Buchner funnel to
be vacuum filtered. The benzoin crystals were washed with two 5-mL portions of
ice-cold and allowed to dry for 5 minutes in the funnel. After drying, the percent
yield and melting point of the crystals were determined. The crystals were then
recrystallized and vacuum filtered while washed with 95% ethanol. The percent
yield and melting point were then recalculated. The crystals then went into a drying
oven fro 20 minutes before being placed in the lab drawer to air-dry until the next
week.
The third session of the experiment began the synthesis of benzil. 2.50g of
benzoin were placed in a 25-mL round bottom flask and then 12-mL of concentrated
HNO3 was carefully added along with a magnetic stir bar. A condenser was attached
and the whole apparatus was placed under the hood where it was heated in a hot
water bath (~70C but not above) for one hr with stirring. The solution was then
poured into a 40-mL of cool H2O and stirred vigorously until the oil crystallized
completely as a yellow solid. The crystals were then vacuum filtered, washed with
cold water, and allowed to dry in the funnel. The crystals were then weighed and the
percent yield was calculated. They were then dissolved in hot 95% ethanol in an
Erlenmeyer flask on a hot plate with a 10mL/g ratio. Once dissolved it was allowed

to cool slowly until crystals formed and was then placed in an ice bath. The crystals
were vacuum filtered, rinsed with ice-cold ethanol, and allowed to sit until the next
lab period.
On the final week of the experiment the percent yield and melting point of
benzil were determined and then the synthesis of benzilic acid was started. 2.0 g of
benzil and 6-mL of 95% ethanol were added to a 25-mL round bottom flask with a
boiling stone and attached to a condenser. The apparatus was the heated with a
heating mantle until the solid dissolved. 5-mL of aq. KOH was added drop-wise and
the mixture was gently boiled and swirled for 15minutes. The condenser was
detached when the mixture cooled and was then transferred to a small beaker to
cool to room temperature. It was then placed in an ice bath for 15 minutes for
crystallization and then was vacuum filtered and rinsed with 4-mL portions of icecold ethanol and then transferred to a 100-mL Erlenmeyer flask containing 60-mL
of 70 C H2O. The solution was stirred until the solid dissolved. Unfortunately, the
solution did not undergo gravity filtration after the solid was most dissolved. 1.4-mL
of concentrated HCI was then carefully added drop-wise while swirling until a
precipitate formed and a pH of 2 was recorded. Once at room temperature, the
solution was placed in an ice bath for 26 minutes and then vacuum filtered, rinsed
with 30-mL portions of ice-cold water, and placed in a drying oven for 20 minutes.
The product was then weighed, the percent yield and melting point were
determined, and an IR was obtained.

Data
Compound
Thiamine
Hydrochloride
Ethanol

Aqueous
Sodium
Hydroxide
Benzaldehyde

Benzoin

Nitric Acid

Benzil

Potassium
Hydroxide

Hydrochloric
Acid

Role in
Experiment
Used in Exp.
32A to make
the reaction
mixture
Used in all
three parts
of the
experiment;
used to
wash the
crystals in
the Buchner
funnel.
Used in Exp.
32A to make
the reaction
mixture
Used in Exp.
32A to make
the reaction
mixture
Used in the
preparation
of Benzil
Used in Exp.
32B to make
the reaction
mixture
Used in Exp.
32C for the
preparation
of Benzilic
Acid
Used in Exp.
32C to
prepare
Benzilic
Acid.
Used in Exp.
32C to
prepare

Mol wt
(g/mol)

Amount
used

m. p. (C)

b. p. (C)

Density
(g/cm3)

Hazard
Low toxicity,
may cause
burning
sensation

337.27

1.5g

248-260

46.07

21-mL

-114.3

78.4

.789

Volatile and
Flammable

39.997

4.5-mL

318

1388

2.13

Causes
burns

106.12

4.5-mL

-26

178.1

1.0415

Fire hazard

212.24

2.5 g

137

344

1.31

May cause
irritation to
skin and
eyes

63.012

12-mL

-42

83

1.5129

Corrosive

210.23

2.0 g

94.4395.08

346- 348

1.23

56.105
6

5-mL

360

1327

2.044

Reacts
violently
with acids.

36.46

1.3-mL

-27.32

110

118

Corrosive

Cause eye
and skin
irritation

Benzilic Acid

OH

Benzoin
IR refers to Figure 1.
IR
Cm -1
3416.34
2922.50
1678.52
1050-1150
1450, 1500, 1580, 1600

Stretch
R-OH
Ar-C-H
C=O
C-O alcohol
C=C within Aromatic

Benzil
IR refers to Figure 2.
IR
Cm -1
2921.6
1680
1591.70, 1452.21
1173.51

Stretch
H-C-C-H
C-C=O-R
C=C within an Aromatic
C=O

OH
1
6

3
2

5
4

OH

Benzilic Acid
IR refers to Figure 3.
IR
Cm -1
3399.06
2904.71
1247.95
1175.74

Chemical
shift
12.3
--7.5
7.4
7.3
2.84

Stretch
Ar-C-H
H-C-C-H
C=C within Aromatic
C=O

1H-NMR refers to Figure 4. 13C-NMR refers to Figure 5.

1H-NMR
13C-NMR
Integration
Splitting
Chemical
Splitting
Assigned
Shift
(if given)
1H
Singlet
-----176.12
Singlet
1
--141.06
Singlet
2
4H
Multiplet
128.48
Doublet
3
2H
Multiplet
128.33
Doublet
4
4H
Multiplet
127.30
Doublet
5
1H
Singlet
81.2
Singlet
6

Calculations
Benzoin: 3.18g crude was recovered and 4.68 was the theoretical.
3.18/4.68*100=67.9%
Melting point was 130-132 C
3.12g pure was recovered and 3.18 was the theoretical. 3.12/4.18*100=98%
Melting point was 134-135 C
Benzil: 2.33g crude was recovered and 2.49g was the theoretical. 2.33g/2.49g *
100= 93.6%

1.40g pure was recovered after crystallization and 2.33 was the theoretical.
1.40/2.33*100 = 60.1%
Melting Point: 90-92 C
Benzilic Acid: 1.72g was recovered and 2.17g was the theoretical. 1.72g/2.17g *
100= 79.3%
Melting Point: 147-149 C
Mechanisms
1. Benzaldehyde Benzoin through Thiamine Catalyzed Reaction

2. Benzoin (HNO3) Benzil

3. Benzil (1. KOH in Alcohol 2. H3O+) Benzilic Acid

Results and Discussion

The experiment began with benzaldehyde and thiamine hydrochloride,
which reacted to form a pale-yellow homogenous mix. After sitting and crystallizing

in the dark for one week, a mass of yellow-white crystals was produced and seeding
was not necessary. After drying in the Buchner funnel and being washed with icecold water, the mass of the benzoin crystals was calculated to be 3.18g (70% yield)
and the melting point was 130 C-132 C. the crystals were the recrystallized again
and dried in the Buchner funnel wile washed with 95% ethanol. The second
recrystalliztion of the first session yielded a mass of 3.12g (98% yield) of benzoin
and a melting point of 134 C-135 C. For the third session of the experiment, benzoin
was used to synthesize benzil. 2.5g of the previously synthesized benzoin was used.
When mixed with nitric acid and heated for a little over an hour, the mixture turned
yellow-orange and a rust colored gas was emitted. When poured into cool water the
mixture turned pale yellow and after scratching and seed, crystals formed. After
vacuum filtering, 2.33 g of benzil crystals were recovered, which was calculated to
be an 94% yield. Dissolving in 20-mL of hot 95% ethanol then purified these
crystals. After re-crystallizing, the crystals were again vacuum filtered, rinsed with
ice-cold ethanol. The benzil crystals were found to be 1.40 g for a 60.1% yield and
have a melting point of 90-92 C off of pure benzils melting point, 95 C.
Finally, in the fourth session, the synthesis of benzilic acid was started, 2.00g
of benzil was combined with 6-mL of 95% ethanol and reflux condenser was
attached. While heating on a heating mantle, 5.0-mL of aqueous potassium
hydroxide was added drop=wise with a Pasteur pipet through the condenser. As it
was added, a color change occurred and the mixture was dark brown. Once the
solution cooled, the condenser was detached and the liquid was transferred to a
small beaker and allowed to cool to room temperature. It was then placed into an ice

bath and took about 30 minutes to crystallize instead of 15 minutes, but once the
crystals started forming, the entire solution turned into sludgy, brown mass. These
crystals were the vacuum filtered and rinsed with 4-mL portions of ethanol, which
removed some of the brown tint and the crystals now had more of a tan appearance.
Once dried, the crystals were transferred to a 100-mL Erlenmeyer flask with 60-mL
of hot water and were stirred until the solid dissolved. Some solid particles
remained, but unfortunately, these particles were not filtered out by use of gravity
filtration. However, while the solution still warm, 1.3-mL of concentrated HCI was
added drop wise while swirling until a precipitant was consistent. The pH was then
monitored with litmus paper to determined if the pH value was 2, which produced a
dark red color on the litmus paper, the solution as allowed to cool as the benzilic
acid crystals formed and were again vacuum filtered and rinsed with 30-mL
portions of water and then allowed to dry in the funnel before they were placed in a
drying oven for 15 minutes. The final crystals were found to weigh 1.72 g, which
gave a high percent yield of 79.3%. The melting point was calculated as 147 C-149 C,
slightly off from the pure melting point of benzilic acid, 150 C.
After each product was made (benzoin, benzil, and benzilic acid), and IR
spectrum was conducted. For the benzoin, the major peaks appear at ~3416, 3060,
2922, ad 1678 cm-1. The large peak at 3416 represent the R-OH group, the peaks at
3060 and 2922 represent the Ar-H groups, and the tall peak at 1678 represents the
R2C=O group of benzoin. For the benzil, the major peaks present were at ~3063 and
1667 cm-1. The 3063 peak is the Ar-H stretch and the 1667 peak is the RcC=O stretch
of benzil. The peaks for the final product, benzilic acid were present at ~3399 (as a

broad mass) and 1719 cm-1, representing the COOH stretch and RcC=O stretch,
respectively. A peak around 3000 is also present on benzilic acid, which would
correspond to the Ar-H stretch. H-NMR and C-NMR wee also run for benzilic acid.
1H

and 13 C NRM spectra were also obtained from the final product, benzilic

acid. In the 1H-NMR, the broad singlet and 2.84 ppm corresponds to a O-H group,
and the extremely small peak around 13 ppm represent the O-H bond of the
carboxylic acid group. The 7.35 ppm and 7.48 ppm peaks correspond to the
aromatic Hs in the molecule in the 13C-NMR of benzilic acid the small peak and 81.2
ppm represents the R3C-OH bond, the peaks from 127.3 ppm to 141.1 ppm
correspond to the C bonds on the aromatic rings with different shifts due to meta,
para, or ortho positioning, and the peak at 176.1 corresponds to the C bond on the
carboxylic acid group.
Conclusion
The final product from the multistep reaction sequence conversion of
benzaldehyde to benzilic acid yielded 81% of the theoretical yield. However, this
product may not be entirely pure based on the percent yields of the other sections.
Mass could have been added by not fully washing the crystals, errors in weighing
the mass throughout the experiment, or most likely, not gravity filtering the
solutions before adding HCl during the last week. Regardless, the IR, H-NMR, and CNMR of the final product all correspond to the expected spectra of benzilic acid; all
major peaks are represented in each spectrum. Therefore, the processes of this
experiment proved to be effective in converting benzaldehyde to benzilic acid
through the steps and reactions discussed.

References
Pavia, Donald L., Gary M. Lampman, George S. Kriz, and Randall G. Engel. A SmallScale Approach to Organic Laboratory Techniques. 3rd ed. Belmont, CA: Brooks/Cole;
Cengage Learning, 2001. Print.
Appendices
Figure 1: IR spectrum of benzoin from session one and two.
Figure 2: IR spectrum of benzil from session three.
Figure 3: IR spectrum of benzilic acid from the final session. Final Product.
Figure 4: 1H-NMR of benzilic acid from the final session. Final Product.
Figure 5: 13C-NMR of benzilic acid from the final session. Final Product.