Date performed: April 22, 2019

8L Date finished: May 6, 2019

Group No. 5
EXERCISE 9B
Synthesis of Dibenzalacetone by Aldol Condensation

V. Results and Discussion

A mixed-double aldol condensation was employed in the synthesizing of

dibenzalacetone using 1 mole of acetone and 2 moles of benzaldehyde. The first procedure
would involve the deprotonation of the α-hydrogens of the acetone to produce a nucleophilic
enolate anion using sodium hydroxide as the base. This step involves an acid-base reaction
between a strong base such as the hydroxide ion given by the sodium hydroxide and a
hydrogen located α to a carbonyl group of the aldehyde or ketone, which is relatively acidic due
to the stabilization of the conjugate base. When half of the mixture of benzaldehyde and
acetone was mixed with the ethanolic sodium hydroxide, the hydroxide ion removed the α-
hydrogen of the acetone causing the bond breakage between the carbon-hydrogen bond. Since
carbon is more electronegative than hydrogen it obtained the two electrons from that bond,
producing an enolate ion. The enolate ion produced would now attack the first mole of
benzaldehyde to form a benzalacetone. The product was made to be neutral by protonating it
with ethanol to give neutral hydroxy-ketone. The process goes on again when the other half of
the benzaldehyde-acetone mixture was added after ten minutes and swirled for 20 minutes for
faster reaction (Figure 6).
 Figure 6. Mechanism of synthesis of dibenzalacetone

Dibenzalacetone was synthesized because there were 2 moles of benzaldehyde that was
attacked by the enolate ion on each side of the acetone. This would prove the significance of
the 2:1 proportion of benzaldehyde and acetone as the goal was to produce a dibenzalacetone
which can only be obtained if there were 2 moles of benzaldehyde attached on either side of
the acetone. To easily determine if dibenzalacetone was successfully synthesized a yellow solid
precipitate should form from the reaction mixture.

After synthesizing the dibenzalacetone the next step would be to determine the yield by
collecting it using suction filtration. It was then washed with cold ethanol to dissolve the
impurities for a higher yield this is because dibenzalacetone is soluble in hot ethanol that’s why
it is important to wash using cold acetone to avoid dissolving the product and only dissolving
the impurities. After collecting the product, it was weighed but only after pressing it between
two sheets of filter paper to remove as much as water as possible and to dry the product. Table
2 shows the yield of the product collected.

To compute for the percent yield, the theoretical mass was first calculated as follows:
1.04𝑔 𝑚𝑜𝑙 1 𝑚𝑜𝑙 𝑑𝑏𝑎
1.25 𝑚𝐿 𝐵𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒 ( )( )( ) = 1.435𝑔 𝐷𝑖𝑏𝑒𝑛𝑧𝑎𝑙𝑎𝑐𝑒𝑡𝑜𝑛𝑒
1𝑚𝐿 106.118𝑔 2 𝑚𝑜𝑙 𝑏𝑒𝑛𝑧

0.748𝑔 𝑚𝑜𝑙 1 𝑚𝑜𝑙 𝑑𝑏𝑎

0.46 𝑚𝐿 𝐴𝑐𝑒𝑡𝑜𝑛𝑒 ( )( )( ) = 1.450 𝑔 𝐷𝑖𝑏𝑒𝑛𝑧𝑎𝑙𝑎𝑐𝑒𝑡𝑜𝑛𝑒
1𝑚𝐿 58.078𝑔 1 𝑚𝑜𝑙 𝑎𝑐𝑒𝑡

Benzaldehyde was identified as the limiting reagent while acetone as the excess
reagent. The theoretical mass of the product is 1.435 g of Dibenzalacetone.

After calculating for the theoretical mass, percent yield was calculated by dividing the
yield obtained during the experiment to the calculated theoretical yield then multiplied by
100%.

𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝑦𝑖𝑒𝑙𝑑 = 𝑥 100%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑

1.39𝑔
𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝑦𝑖𝑒𝑙𝑑 = 𝑥 100% = 96.86%
1.435𝑔

The percent yield calculated was 96.86% which means that 96.86% of the reactants was
synthesized to form dibenzalacetone. The percent yield indicates the success of synthesis of
dibenzalacetone. Therefore, most of the reactants was synthesized to dibenzalacetone and only
small amounts produced the side products and the others may be because of impurities. This
maybe because the product was not washed with enough ice-cold ethanol or it was not cold
enough and not all the impurities was washed. Also, there might be minute amounts of the
crystals that was lost during the processes of transferring them from one container to another.

After collecting the synthesized crude dibenzalacetone, a small amount was set aside for
the melting point determination and comparison with the recrystallized dibenzalacetone. The
remaining crude dibenzalacetone was used for the recrystallization process. It was transferred
in a 100 ml beaker and dissolved with minimal amount of hot ethyl acetate, using too much hot
ethyl acetate would make the solution unsaturated which can cause for the recrystallization
difficult to effect therefore resulting to lower recovery and can also cause absence of crystals.
Filtration using hot-gravity filtration set-up was done to remove the totally insoluble impurities
and to avoid premature recrystallization. The filtrate was cooled to room temperature before
subjecting it to cold water bath to avoid rapid cooling which causes random inclusion of soluble
impurities causing for the crystals to not form well. The crystals was then collected using
suction filtration and was washed by cold acetate to further purify the product. Table 4 shows
the data for the percent recovery after recrystallization.

Percent Recovery was calculated by dividing the mass of the recrystallized sample by the
mass of the crude sample and then multiplied by 100%
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑟𝑒𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑧𝑒𝑑 𝑠𝑎𝑚𝑝𝑙𝑒
𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = 𝑥 100%
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐𝑟𝑢𝑑𝑒 𝑠𝑎𝑚𝑝𝑙𝑒
0.06𝑔
𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝑟𝑒𝑐𝑜𝑣𝑒𝑟𝑦 = 𝑥 100% = 4.32%
1.39𝑔
The percent recovery calculated was 4.32% which means that the mass of the
recrystallized sample was low compared to the mass of the crude sample. Percent recovery
accounts for the amount of purified sample collected by recrystallization. The low percent
recovery maybe caused by many factors. First, maybe because too much hot ethyl acetate was
used when dissolving the crude sample, this may result to the difficulty of formation of crystals.
Second, it may have not been properly cooled to room temperature first before cooling in a
cool water bath which can cause for impurities to form.

After the collection of the crude and recrystallized dibenzalacetone, their melting point
was determined and compared to the theoretical value of 110–111 °C. This is to determine the
purity of the products.
 As seen in table 1, the theoretical melting point is closer to the melting point of the
recrystallized dibenzalacetone than that of the crude dibenzalacetone. We can conclude that
the recrystallized dibenzalacetone is purer than the crude because it has a closer value to the
theoretical. Impurities can cause for a wide range of melting point values; it can also increase or
decrease the melting point which is why the melting point of the crude dibenzalacetone is
much lower than the theoretical value.
The last procedure that was employed was the characterization of the product from the
reagents. This was done using three different test: Baeyer’s test, Iodoform Test and
Bromination. Baeyer’s test uses a cold dilute neutral KMnO4 as a reagent and is used to identify
unsaturation (alkenes and alkynes); the loss of the purple color of the reagent and formation of
brown precipitate shows a positive result for the test. During the experiment, only the
synthesized product (dibenzalacetone) poses a positive result to the test while the reagents
(acetone and benzaldehyde) did not react with the regent. The second test, Iodoform test, is
used to identify methyl ketones and secondary methyl ketones. Formation of yellow precipitate
when subjected to a I2/KI and NaOH reagent indicates the positive result for this test in which
only the acetone produced during the experiment. The last test which was bromination is used
to test for saturation and identify alkane and alkyl benzenes. It uses a Br2/CH2CL2 reagent and
a discoloration shows a positive result. Only the dibenzalacetone pose a positive result to the
test (Table 6).

VI. Summary and Conclusion

The reaction of an aldehyde with a ketone employing sodium hydroxide as the base is
an example of a mixed aldol condensation reaction. Dibenzalacetone is readily prepared by
condensation of acetone with two equivalent of benzaldehyde. The molar ratio of the reagents
was found to be important in order to produce dibenzalacetone. It is crucial that the number of
moles of the reagents is enough in order to synthesize the desired product. The benzalacetone
once formed, can easily react with another mole of benzaldehyde to give the desired product in
this experiment, dibenzalacetone. Sufficient amount ethanol is also found to be important in
this experiment because it is used as a solvent to readily dissolve the starting material,
benzaldehyde and also the intermediate, benzalacetone. Another important compound in this
experiment is the presence of a base to act s a catalyst for the reaction to move forward by the
process of deprotonation, in this experiment sodium hydroxide was used.
During the experiment 1.39g of crude dibenzalacetone was synthesized using 1.25 ml of
benzaldehyde and 0.46 ml acetone. The percent yield calculated was 96.86% which means the
product was successfully produced however when recrystallization was performed only 0.06g
recrystallized dibenzalacetone was collected resulting to a low percent recovery of 4.32%. After
calculating for the percent yield and percent recovery, melting point was determined to know
the purity of the samples collected and compared to the theoretical melting point of pure
dibenzalacetone. It was concluded that the recrystallized dibenzalacetone was purer because
its melting point is closer to the theoretical value. Characterization of the dibenzalacetone was
done to make sure that the synthesized product is really dibenzalacetone and to differentiate
the product from the reagents used. Three chemical test was performed in which it was
confirmed that the synthesized product was dibenzalacetone.

VII. References
JASPERSE C.P. 2018. Dibenzalacetone by Aldol Condensation. Minnesota State University
Moorhead Chem 365 Lab Manual. pp 45-47. Retrieved from:
[Link]

MAHRWALD, R. (2004). Modern Aldol Reactions. 1, 2. Weinheim, Germany: Wiley-VCH. pp.

1218–1223. Retrieved from:
[Link]
ndensation

WADE, L. G. (2005). Organic Chemistry (6th ed.). Upper Saddle River, NJ: Prentice Hall. pp. 1056
– 1066. Retrieved from: [Link]

MORENZONI-LEWIS R. nd. Aldol Condensation Synthesis of Dibenzalacetone using the Claisen-

Schmidt Reaction. Retrieved from: [Link]
Condensation-Synthesis-of-Dibenzalacetone-using-the-Claisen-Schmidt-Reaction-copy-
doc

NUFFNANG. 2011. Synthesis of Dibenzalacetone by Aldol Condensation. Retrieved from:

[Link]

ROBERTSON, D.L. 2009. Elimination Reactions: Acid-Catalyzed Dehydration of 2-Pentanol.

Retrieved from: [Link]

VIII. Remarks and Recommendation

1. When no crystals were formed during recrystallization, scratching the sides of
the test tubes can induce the formation of crystals.
2. Optimum amount of solution should be strictly followed to avoid errors during
the experiment which can affect the results.