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Aldol Condensation and Synthesis of Dibenzalacetone

Organic Chemistry II Lab (University of Alabama at Birmingham)

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Synthesis of Dibenzalacetone through Aldol Condensation

Lead Author: Olivia Rye

Reviewer: Kristen Rutledge
Editor: Christina Dabit

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Introduction
Aldol condensations play a vital role in organic synthesis due to their ability to form
carbon-carbon bonds. Aldol condensation begins by forming an enolate anion, which is produced
from either an aldehyde or a ketone. Due to resonance stability, enolate anions are able to act as a
nucleophile. The nucleophilic enolate anion attacks the electrophilic carbonyl carbon of an
aldehyde or ketone, forming a α,β-unsaturated carbonyl compound.1
Aldol reactions may be acid-catalyzed or base-catalyzed, although base catalysis occurs
more often. In base-catalyzed mechanisms, the enolate anion attaches to the carbonyl group
through nucleophilic addition, creating the tetrahedral carbonyl intermediate.2
The present experiment utilizes base-catalyzed aldol condensation to produce
dibenzalacetone, shown as figure 1. An acetone anion, acting as a nucleophile, attacks the
carbonyl carbon on benzaldehyde, acting as an electrophile, forming a β–hydroxyketone. After
hydroxide leaves, forming a double bond, the intermediate product acts as a nucleophile and
attacks another benzaldehyde, forming a second β–hydroxyketone. Hydroxide leaves a second
time, forming another double bond, resulting in the final product, dibenzalacetone.
Dibenzalacetone can form three different isomers: trans, trans (E,E), trans, cis (E,Z), and cis, cis
(Z,Z). Since trans, trans (E,E) minimizes steric hindrance, this is the product that is theoretically
formed at the greatest concentration.

Figure 1: Mechanism for aldol condensation and synthesis of dibenzalacetone.

One possibility from the aldol condensation reaction is the formation of two side
products, known as the Cannizzaro reaction, shown as figure 2. This mechanism involves a
simultaneous reduction and oxidation of the benzaldehyde-acetone tetrahedral intermediate.3
This mechanism occurs due to the hydride ion acting as a leaving group, making benzaldehyde
accept the hydride ion through a nucleophilic addition. Two unwanted side products, benzoic
acid and benzyl alcohol, are formed at the end of the Cannizzaro reaction.

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Figure 2: The Cannizzaro mechanism, which forms two side products: benzoic acid and benzyl
alcohol.

Table 1: Table of Reagents4-9

Reagent Molecular Boiling Melting Density
Weight (g/mol) Point (C) Point (C) (g/mL)
Acetone 58.08 56.0 -95.0 0.80
Benzaldehyde 106.12 179.0 -26.0 1.05
Benzoic Acid 122.12 249.0 122.4 1.32
Benzyl Alcohol 108.14 205.3 -15.2 1.04
Dibenzalacetone 234.30 130 110.0-111.0 N/A
Ethanol 46.07 78.2 -114.1 0.79
Sodium 39.99 1388.0 323.0 2.1
Hydroxide
Water 18.02 100.0 0.0 1.0
Sodium 68.05 N/A 260 0.868
Ethoxide

Procedure
Using a graduated pipette, 0.1 milliliters of acetone and 3.0 milliliters of aqueous
ethanolic sodium hydroxide solution was added to a small Erlenmeyer flask and swirled for four
minutes. After four minutes, 0.3 milliliters of benzaldehyde and a spin bar was added to the
Erlenmeyer flask, capped with a stopper, and stirred for thirty minutes. After thirty minutes had
passed, yellow precipitate was gathered and then filtered through vacuum filtration. The
precipitate was then washed with cold ethanol. Through the use of pH paper, the precipitate was
tested to ensure it was neutral. If the pH was not neutral, more water was added to wash the
compound. However, our compound did not need washing and was neutral. Once an orange
color appeared, verifying the compound to be neutral, the solid dried on the Hirsch funnel until
clumps were no longer visible. The mass of the solid was then weighed and melting point and IR
spectrum were obtained.

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Results
The reaction between acetone, sodium hydroxide, and benzaldehyde resulted in the
observable formation of a yellow precipitate. The present reaction resulted in 0.0614g
dibenzalacetone. Theoretical yield calculations result in 0.0702g dibenzalacetone as shown as
equation 1. The resulting percent yield of the present experiment is 87.46% as shown as equation
2.

Eq. 1

Percent yield =
Eq. 2
The melting point apparatus showed condensation of formed product at 97.3C with the
product completely melted by 106.8C. Additionally, the IR spectrum obtained of the product
with key peaks labeled are shown as figure 3 and table 2.

Figure 3: IR Spectrum of Dibenzalacetone

Table 2: IR Table for Dibenzalacetone

Frequency/cm-1 Functional Group
3025.88-3053.11 sp2 C-H stretching
1649.48 C=O stretching
1589.70-1447.09 Aromatic C=C stretching and
alkene C=C stretching
693.42-981.20 Alkene =C-H bending

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Discussion
A reaction between acetone and benzaldehyde resulted in the nucleophile utilized in aldol
condensation. Benzaldehyde, containing no α carbons, acts as the electrophile. Observable data
suggests that dibenzalacetone was formed, apparent via the formation of the yellow precipitate.
Had the Cannizzaro reaction occurred, the precipitate would have turned white. After vacuum
filtration was performed, the product immediately tested neutral and therefore, did not have to be
washed with water, which acts as a neutralizer during this part of the experiment.
The three isomers of dibenzalacetone have different melting points. They are as follows:
cis, cis <25C, cis, trans 60C, and trans, trans 100C. The product obtained in the present
experiment resulted in a melting point range of 97.3C-106.8C. This indicates that the more
stable trans, trans (E,E) isomer of dibenzalacetone was formed.
The IR spectrum confirmed that the possible Cannizzaro reaction did not occur. This
reaction results in an alcohol group, which would show a large, broad peak between 3200 and
3600 cm-1. Instead, the IR spectrum confirms that dibenzalacetone was formed. Additionally,
results indicate that almost all of the reactants were converted into products. Acetone contains
sp3 hybridized carbon-hydrogen bonds. The obtained frequency values show a peak between
3025.88 and 3052.11 cm-1. This indicates sp2 hybridized carbon-hydrogen bonds which are
present in dibenzalacetone. Additionally, only one peak is present at the carbonyl frequency,
~1700 cm-1. Two peaks would indicate unreacted acetone and/or benzaldehyde in the obtained
product as both contain carbonyl groups along with the product. Additionally, the last reactant,
sodium hydroxide, was not found unreacted in the product. Sodium hydroxide contains an
alcohol group which are observed on IR spectrums as a large, broad peak between 3200 and
3600 cm-1. Water via hydrogen bonding would result in similar peaks. As it did not, the resulting
IR spectrum indicates adequate drying while also confirming that dibenzalacetone with minimal
unreacted reactants were produced.

Conclusion
The present experiment utilizes the mechanism of aldol condensation in order to form the
trans, trans (E,E) dibenzalacetone isomer. This was initially confirmed by the observable yellow
precipitant that formed at the end of the reaction. Additionally, melting point measures as well as
IR spectroscopy indicated the formation of (E,E) dibenzalacetone. The obtained IR also
confirmed that no unreacted reagents remained and the product was adequately dried. The
percent yield of the product was calculated and found to be 87.46% recovery from the original
reactants. Errors such as transferring the precipitate from the flask to the Hirsch funnel could
have resulted in loss of product, as well as over-drying.

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Answers to Handout
1. The dibenzalacetone in the E, E conformation would be the major product. In the E, E
conformation it is seen that it is the most stable form of dibenzalacetone due to the least
amount of steric hindrance compared to the other two isomers.

2. Acetone anion, the nucleophile in the reaction of acetone and benzaldehyde, attacks the
carbonyl carbon on the benzaldehyde. This reaction occurs due to the electrophilic nature
of the carbonyl carbon on benzaldehyde. The electrophilic character is produced, since
there is a strong presence of electron withdrawing from the benzene, which is also less
sterically hindered. Therefore, the reaction will continue and react with benzaldehyde
instead of another acetone molecule.
3. If 2 moles of benzaldehyde react with 1 mole of acetone give 1 mole of dibenzalacetone.
If only 1 mole of benzaldehyde is used, the resulting product is dibenzalacetone.

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References
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