SEMESTER 20234

OCTOBER 2023 - FEBRUARY 2024

EXPERIMENT 4
THE ALDOL CONDENSATION REACTION:
PREPARATION OF BENZALACETOPHENONES
(CHALCONES)

NAME :FARHAN DHANIAL BIN MD ZAID

STUDENT ID :2022818846
NAME :MUHAMMAD HAZIQ BIN ZULKFILI
STUDENT ID :2022828062
NAME :MUHAMMAD HAIKAL BIN ISMAIL
STUDENT ID :2022836196
GROUP :AS2223A
DATE :3/1/2023

Objective (1M)

Introduction (2M)

Procedure in flowchart (2M)

Calculation (5M)

Discussion (3M)

Conclusion (1M)

Questions (6M)

TOTAL
Title: The Aldol Condensation Reaction: Preparation of Benzalacetophenones

Objective:
1. To synthesize trans-3-nitrochalcone from aldol condensation reaction of
3-nitrobenzaldehyde with acetophenone in aqueous base.
2. To determine the melting point of trans-3-nitrochalcone.
3. To characterize trans-3-nitrochalcone using 1H NMR spectroscopy and/or IR spectroscopy.

Introduction:
The reaction of an aldehyde with a ketone employing sodium hydroxide as the base
is an example of a mixed aldol condensation reaction, the Claisen-Schmidt reaction.
The double mixed-aldol condensation reaction between acetone and benzaldehyde
was carried out. Acetone has α-hydrogens (on both sides) and thus can be
deprotonated to give a nucleophilic enolate anion. The alkoxide produced is
protonated by solvent, giving a β-hydroxyketone, which undergoes base-catalyzed
dehydration. The elimination process is particularly fast in this case because the
alkene is stabilized by conjugation to not only the carbonyl but also the benzene. In
this experiment, excess benzaldehyde such that the aldol condensation can occur on
both sides of the ketone. Dibenzalacetone is readily prepared by condensation of acetone with
two equivalent of benzaldehyde. The aldehyde carbonyl is more reactive than that of the
ketone and therefore reacts rapidly with the anion of the ketone to give a β-hydroxyketone,
which easily undergoes base catalyzed dehydration. Depending on the relative
quantities of the reactants, the reaction can give either mono-or dibenzalacetone.
Dibenzalacetone is a fairly innocuous substance in which its spectral properties indicate why
it is used in sun-protection preparations. In the present experiment,
sufficient ethanol is present as solvent to readily dissolve the starting material,
benzaldehyde and also the intermediate, benzalacetone. The benzalacetone once
formed, can then easily to react with another mole of benzaldehyde to give the desired
product in this experiment, dibenzalacetone.

Procedure:
a. Preparation of crude product

1. 3-nitrobenzaldehyde (0.75 g) was weight and place into a 50 mL Erlenmeyer

flask.
2. Acetophenone (0.60 mL) and 95% ethanol (4.0 mL) was added to the flask
containing the 3-nitrobenzaldehyde.
3. The flask was swirled to mix the reagents and dissolve any solids. It may be
necessary to warm the mixture gently to dissolve the solids (heat the solution
onto a hot plate). The solution should be cooled to room temperature before
proceeding to the next step.
4. NaOH solution (0.5 mL) was added (prepared by the lab assistant using 6.0 g
of NaOH in 10 mL of water).
5. The mixture was stirred with glass rod until it solidifies or until the entire
mixture becomes very cloudy.
6. Ice water (10 mL) was added to the flask. If a solid is present at this point,
break up the solid mass by stirring with a spatula. Cooling and scratching with
glass rod is necessary to initiate crystallization.
7. The mixture was transferred to a beaker with ice water (15 mL).
 8. The solid was collected by vacuum filtration on a Buchner funnel. The solid
was washed with cold water and allow it to air dry for 30 minutes.
9. The solid was weighed (crude product) and calculate the weight of solid.
Determine the percent yield of the solid (crude product).

b. Recrystallization of crude product

1. The solid was crystallized (0.5 g) which was obtained from the above step
from hot methanol.
2. 20 mL of methanol was measured and place it into 50 mL beaker. The
methanol was heated on the hot plate until the temperature reach boiling point
of methanol which is 64.5ºC. Transfer the hot methanol into the solid.
3. The solution was cooled at room temperature and continue cooling in an ice
bath. Scratching with a glass rod is necessary to initiate crystallization.
4. Collect the solids/crystals by vacuum filtration. Wash the solids/crystals with a
small amount of cold methanol. Allow the solids/crystals to dry by sucking air
through them. Dry it in the oven
5. Weigh the dry pure product (solids/crystals) and determine the percent yield of
the pure product.
6. Measure the melting point of the pure product (literature melting point is
146ºC) and obtain a 1H NMR and/or IR spectra of the pure product.

Results:
a. Weight of crude product: 4.56g

b. Weight of purified product: 4.26g

c. Melting point of the purified product : 74 ºC

d. Appearance of the purified product : Yellow precipitate

1
e. H NMR data (in Table) of the purified product:

Chemical shift, δ (ppm) Multiplicity Number of Type of proton

hydrogens
7.8 Douplet 2 C-H
7.1 Douplet 2 CO
7-8 Multiplet 6 C=C

Calculation:

Mole of benzaldehyde= 5.4 𝑔 106 𝑔 𝑚𝑜𝑙 = 0.0509 mol

Chemical equation of this reaction: C3H6O + 2 C₇H₆O

Theoretical mass of dibenzalacetone: = 0.0255 mol × 234 𝑔 𝑚𝑜𝑙 = 5.967 g

Mole of dibenzalacetone: = 1 2 × 0.0509 mol = 0.0255 mol

Percentage yield of crude product: = 4.56 𝑔 5.967 𝑔 × 100% = 76.4 %

Percentage yield of pure product: = 4.26 𝑔 5.967 𝑔 × 100% = 71.4 %
Discussion:
Condensation is a process which joins two or more molecules usually with the loss of a small
molecule such as water or an alcohol. Aldol condensation (Claisen-Schmidt reaction)
definitely is a process which join two carbonyl groups with a loss of water molecule in order
to form β-hydroxyketone. The product is also known as adol because it containing two
functional groups which includes aldehyde (or ketone) group and alcohol group. The product
dibenzalacetone was formed from the reaction between an acetone molecule and two
benzaldehyde molecules. Generally, the aldol condensation is carried out under a base
condition. Sodium hydroxide was mixed with distilled water then was used to react with
sufficient ethanol as the first step. The particular reaction is an exothermic reaction which
released the heat energy to the surrounding from the reaction.

The sodium hydroxide was functioned as a catalyst in the reaction. The ethanol acts as a
solvent which allows the acetone and benzaldehyde to dissolve and react with each other.
After that, acetone and benzaldehyde were mixed in the solvent which turns to yellow colour
quickly. Eventually, the product was formed with a yellow precipitate appear in the reaction
after a few seconds. However, there are some impurities and side products were formed in the
yellow precipitate. So, recrystallization was carried out by using ethyl acetate as solvent in
order to purify the product and hence a pure product could be obtained for the FTIR and IR
spectra analysis. In the recrystallization process, the yellow precipitate in ethyl acetate was
immersed into an ice-bath in order to obtain a higher yield of product. This is because the
heat energy in the precipitate easily to be released since the precipitation formation is an
exothermic reaction and hence it maximizes the formation rate of the product.

The percentage yield of dibenzalacetone in this experiment is 71.4%. Some of the product has
been lost during the process of recrystallization. In recrystallization, some of the product
dissolved in the ethyl acetate. The melting point of the product is 74°C which is lower than
the actual melting point (110 °C ~ 111 °C). This is because there is some impurities exist in
the particular compound which will tend to lower the melting point of the dibenzalacetone.

Conclusion
The product yield from this experiment is 3-nitrobenzaldehyde that proven with the H1NMR
spectrum. The percentage yield of the crude product obtained is 76.4% and the melting point
of the product is 74 °C.

Questions
1.
2. Coupling constants of nearby NMR-active nuclei can also give information on their
relative position and bonding orientation. For instance the two vinylic protons in
disubstituted alkenes often have characteristic coupling constants (< 5 Hz for geminal, 5–12
Hz for cis and >10 Hz for trans). These are not rigorous proof of geometry, especially for
values between 10 and 12 Hz, but if you have a mixture of two isomers, the one with the
greater coupling constant can be confidently assigned as trans.

3.

a. E1elimination
b. Form enolate

References

1. L. (2023, January 23). Aldol Reaction. Chemistry LibreTexts.

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_
(Organic_Chemistry)/Reactions/Reactivity_of_Alpha_Hydrogens/Aldol_Reaction
2. Pavia, Lampman, Kriz and Engel, Introduction to Organic Laboratory Techniques 3 rd
Edition (2011). page 669-673.