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Lead Author: Joshua Purvis

Reviewer: Clara Wan


Editor: Lakshmi Subramani
Formation of Dibenzylacetone through an Aldol Condensation
Introduction
In this experiment, an aldol reaction will be performed using acetone, benzaldehyde,
sodium hydroxide, and ethanol to make dibenzylacetone. The word aldol is an abbreviation for
an alcohol and aldehyde. There are two types of aldol reactions: an acid catalyzed reaction and a
base catalyzed reaction; a base-catalyzed aldol reaction will be performed in this experiment. In
this reaction, the enolate of an aldehyde or ketone reacts at the alpha carbon with the carbonyl of
another aldehyde or ketone in basic conditions. This yields a molecule that contains a new
carbon-carbon bond, a carbonyl, and an alcohol group [1]. The mechanism for the base-catalyzed
aldol mechanism is shown in Figure 1. The starting molecules, acetone and benzaldehyde form a
crossed aldol reaction, which is only possible because acetone is the only molecule that contains
alpha hydrogens. The final product shown in Figure 1 has alpha hydrogens, so it can undergo a
second aldol condensation with itself, which will yield the desired product in this experiment,
dibenzylacetone.
Figure 1 Mechanism for Base-Catalyzed Aldol Condensation

Another product that could be made from these reagents is from the cannizzaro reaction.
This product results when the acetone in the experiment is not given enough time to react with
the base and ethanol to convert to form the enolate. The reaction follows the mechanism for a
nucleophilic acyl substitution. These reactions mostly follow the basic form of nucleophilic
attack, formation of the tetrahedral intermediate, and reformation of the carbonyl. However, the
Cannizzaro reaction differs in that when the carbonyl reforms, there is a hydride transfer to a
molecule of the original aldehyde to form two anions one carboxylate and one alkoxide. The
alkoxide is then protonated to form the alcohol product [2]. The Cannizzaro product for this
experiment will be benzyl alcohol. Its precipitate is often qualitatively described as white snot
and is starkly different from the yellow precipitate that the aldol reaction yields. The mechanism
for the formation of the Cannizzaro product is shown in Figure 2.
Figure 2-. Mechanism for Cannizzaro Reaction
O

O
OH

OH

OH

Table 1- Table of Reagents


Name

Molecular Weight
(g/mol)
Acetone
58.08
NaOH
39.99
Ethanol
46.07
Benzaldehyde 106.1

Melting Point
(oC)
-95.00
318.0
-114.0
-26.00

Boiling Point
(oC)
136.8
1388
78.37
178.1

Table 1 lists the reagents and their properties used in this experiment.

Density
(g/mL)
0.791
2.130
0.789
1.040

Experimental
In a 25mL Erlenmeyer flask, 0.1 mL of acetone and 3mL of a mixture of sodium
hydroxide and ethanol was combined along with a stir bar. This mixture was stirred together for
4 minutes at room temperature. Then, 0.3mL of benzaldehyde was added to the mixture, which
was capped and stirred for 30 minutes using the stir bar and a stir plate. After 30 minutes, the
solution was checked for a yellow precipitate, which did form. This precipitate was vacuum
filtered and washed with cold ethanol. The flask was also washed with cold ethanol to rinse all
the product out. The filtrate was tested for neutralization with pH paper- the neutralized solution
would turn the pH paper green. Filtrate in the flask was not tested for pH, but instead filtrate that
had just dripped down from the product. The product was dried until the solid did not clump
together. Finally, the melting point was found using a MelTemp and the mass was recorded.
Results
After isolating the aldol product with vacuum filtration, the mass and melting point were
recorded. The mass of the product was 0.457g, and the melting range was 104.7-108.5oC. The
qualitative observations of both the desired and undesired product are listed in Table 2.
Table 2- Qualitative Observations of the Aldol Reaction
Color
Yellow
White/Pink

Texture
Powdery
Snot-like

Formed from
Aldol condensation
Cannizzaro reaction

Table 2 illustrates the qualitative differences between the two products formed in the
experiment. One product was yellow with a powdery consistency. This was deduced to be from
the aldol condensation, based on research. The other product was a white, snot-like substance
that was presumably a result of the cannizzaro reaction.
Calculation of Theoretical and Percent Yield:
Cacluction 1- Finding Theoretical Yield and Limiting Reagant

Acetone :

0.1mL acetone 0.791 grams acetone 1 mol acetone 1 mol dibenzalacetone 234.29 grams dibenz

1
1 mL
58.08 grams
1 mol acetone
1mol
0.31908 grams dibenzalacetone

Benzaldehyde :

0.3 mL Benz . 1.04 g Benz . 1 mol Benz . 1 mol dibenzalacetone 234.29 g dibenzalacetone

1
1 mL
106.121 g
1 mol Benz .
1 mol
0.344411 grams dibenzalacetone

From the calculation, it is proven that acetone was the limiting reagent in this reaction, and that the
theoretical yield was 0.31908 grams of dibenzalacetone.
Calculation 2- Finding Percent Yield

Percent Yield=

Experimental Yield
100
Theoretical Yield

0.457 g
100
0.31908 g

143.22 yield

Discussion
In this experiment, dibenzylacetone was formed through the crossed aldol condensation
between acetone and benzaldehyde. This was confirmed through the measured melting point of
104.7-108.5oC. This range is slightly lower than the expected range of 110-111oC, but it is likely
that the second product in the reaction vessel contaminated the final sample. When taking a
sample to find the melting point, the cannizzaro product was avoided, but there must still have
been a little bit in the smaple.This second product was deduced to be the product of the
Cannizzaro reaction, phenylmethanol, due to its snot-like texture and white color. The yield for
the experiment was 0.457g. This gave us a 143.22% yield, meaning that there was more product
than theoretically possible. This means that there were impurities present in the sample- making
the percent yield over 100%. This may have been improved by allowing the ethanol and sodium
hydroxide stir for a minute longer in order to ensure the formation of the enolate, so that the
Cannizzaro product would not have formed.
Conclusion
The condensation produced 0.457g of product, making the percent yield 143.22%. The
product was not completely yellow powder, there were small pink clumps scattered through the
product indicating that the product was not pure. This was confirmed by a melting point of
104.7-108.5oC, which was lower than the expected melting point, indicating that the product
contained some impurity. The impurity, Cannizzaro, in the product could have been due to the
benzaldehyde and the acetone not mixing well enough before adding the base to the flask. It is
also possible that the flask used was not cleaned well and one of the reactants reacted with
something present in the flask. The percent yield could be improved by turning the vacuum
filtration suction on slower so product does not leak through to the filtrate. In addition, some
solution was spilled out of the funnel connected to the vacuum filtration device that led to some
loss of product.

References
1.

Farmer, Steven. Aldol Reaction. UCDavis


Chemwiki. http://chemwiki.ucdavis.edu/Core/Organic_Chemistry/Reactivity_of_Alpha_
Hydrogens/Aldol_Reaction (accessed 09 March 2016)
2. Reusch, William. Hydrogen Transfer Redox
Reactions. https://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/suppmnt3.htm (ac
cessed 09 March 2016)
Questions
1. A. Write a Detailed Mechanism for the formation of benzalacetone
O
O

HO

CH2

H3C

H3C

H3C

O
H

O
H3C

OH

HO

HO

H
H

O
O
-

H2C

O
H

O
OH
H

HO

B. Give the IUPAC name for dibenzalacetone


1,5-Diphenyl-1,4-pentadien-3-one
C. Do you expect the configuration of the double bonds in this compound to be E,Z, or a mixture
of both.
E is expected because it is the more energetically favorable configuration, because it
keeps the benzyl rings the farthest apart.
2. It is important that the molar ratio of reactants in this reaction be 2:1. What would happen if
the ratio was closer to 1:1?
a. There would be very little dibenzalacetone because there would not be
enough benzaldehyde to react at both ends of the acetone.
3. A chemist carries out this reaction using 10 moles of acetone and 16 moles of benzaldehyde
and obtains 6 moles of dibenzalacetone. What is the percent yield for this reaction?
a.

75% yield

4. Give the structures of the aldol products that form when each of the following compounds
or mixtures is treated with NaOH.
a.

Butanal
O

H
H3C

H3C

b.

Cyclopentanone

c.

Acetophenone
CH 3

d. p-Chlorobenzaldehyde and 2,2-dimethylcyclohexanone


O
CH3
CH3