SEMESTER 20212

OCTOBER 2021 – FEBRUARY 2022

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

NAME : SITI NUR AFIQAH BINTI MAHAZAN

STUDENT ID : 2020897786
GROUP : AS2533A1
DATE : 09TH JANUARY 2022

Objective (1M)

Introduction (2M)

Procedure in flowchart (2M)

Calculation (5M)

Discussion (3M)

Conclusion (1M)

Questions (6M)

References

TOTAL (20M)
OBJECTIVES
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
Chalcone is an aromatic ketone that serves as the fundamental building block for several
important biological compounds. Benzalacetophenone and phenyl styryl ketone are some
other names for chalcone. Chalcones are antibacterial, antifungal, antitumor, and anti-
inflammatory in nature. Chalcone can be synthesised through aldol condensation of
benzaldehyde and acetophenone in the presence of a catalyst. The Claisen-Schmidt reaction
is another term for aldol condensation. An aldol condensation is an organic reaction in which
enol or enolate ions react with a carbonyl compound to form a β-hydroxyaldehyde or β-
hydroxyketone, which is then dehydrated to give conjugate enone.

The aldol reaction is one of the most effective ways to form a carbon-carbon bond. In the
presence of a base, benzaldehyde reacts with a ketone to produce α,β-unsaturated ketone.
This is an example of a crossed aldol condensation in which the intermediate dehydrates to
produce the resonance-stabilized unsaturated ketone. Ketone loses a proton from a α-carbon
to form an enolate ion, which attacks the carbonyl carbon of the aldehyde to yield, α,β-
hydroxy ketone after protonation. The intermediate, at least for aromatic aldehyde, is unstable
and undergoes base-catalysed dehydration to yield the unsaturated product.

The aldol condensation reaction between a substituted benzaldehyde and a ketone in the
presence of a base will be carried out in this experiment to produce an α,β-unsaturated
ketone. 3-nitrobenzaldehyde was chosen as the substituted benzaldehyde for this experiment.
The chemical equation for the aldol condensation reaction of 3-nitrobenzaldehyde with
acetophenone in aqueous base is shown below:
APPARATUS
Erlenmeyer flask (50 mL)
Beaker
Measuring cylinder (5 mL, 10 mL, 50 mL)
Bulb pipette (if any)
Glass pasteur pipette or plastic Pasteur pipette
Stainless steel spatula
Hirsch funnel
Hirsch flask
Rubber tubing
Rubber bung or rubber filter adapter
Bosshead for retort stand
Retort stand
Retort stand clamp
Filter paper
Glass rod
Aluminium foil
Conical flask (100 mL or 250 mL)
Thermometer
Sample bottle
Eppendorf tube
Hot plate
Aspirator vacuum pump
Oven
NMR Spectrometer
Melting point apparatus

CHEMICALS
3-Nitrobenzaldehyde
Acetophenone
95% Ethanol
Sodium hydroxide (NaOH) solution (6.0 g of NaOH in 10 mL of distilled water)
Ice
Methanol
PROCEDURE
RESULTS AND OBSERVATIONS
Results:

a. Weight of crude product : 1.0500 g

b. Weight of purified product : 0.4000 g

c. Melting point of the purified product : 146 ºC

d. Appearance of the purified product : Reddish yellow precipitate formed

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

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

y hydrogens
8.50 Singlet 1H

8.02 - 8.04 Doublet 4H

7.90 - 7.91 Doublet 1H

7.66 Singlet 5H

Structure of the purified product (trans-3-nitrochalcone):

 And/or IR spectroscopy:

Wave number (cm−1) Type of bond (group)

1,680−1,750 C=O (ketone)

1,600 C=C (alkene)

1,450−1,500 C=C (aromatic arene)

Observations:

Write the observations such as colour changes, colour of the precipitate etc during the period
of experiment.

Steps
After adding 0.5 mL NaOH solution, the
mixture was stirred with a glass rod until it
solidified.
The flask was filled with 10 mL of ice
water. To initiate crystallisation, cooled
and scratched the solid with a glass rod.
After the addition of sodium hydroxide,
NaOH.
Observations
The mixture becomes very cloudy.
A solid is present at this point, and the solid
is broken.
A colourless solution changes to a reddish
yellow solution with precipitate.

Calculations:

Volume of acetophenone=0.60 mL
−1
Density of acetophenone=1.03 g mL

Mass of acetophenone=Volume of acetophenone× Density of acetophenon e

−1
¿ 0.60 mL ×1.03 g mL

¿ 0.618 g
−1
Molar mass of acetophenone=120.15 g mol

Mass of acetophenone
No . of moles of acetophenone=
Molar mass of acetophenone

0.618 g
¿
120.15 g mol−1

¿ 0.00514357 mol (available)

Mass of 3−nitrobenzaldehyde =0.75 g

 −1
Molar mass of 3−nitrobenzaldehyde=151.12 g mol

Massof 3−nitrobenzaldehyde
No . of moles of 3−nitrobenzaldehyde =
Molar mass of 3−nitrobenzaldehyde

0.75 g
¿
151.12 g mol−1

¿ 0.004962943 mol(available)

From stoichiometry,

1 mol of acetophenone ≡1 mol of 3−nitrobelzaldehyde

0.00514357 mol of acetophenone≡ 0.00514357 mol of 3−nitrobelzaldehyde(required)
Since the no. of moles for available 3-nitrobenzaldehyde (0.004962943 mol) is less than
required (0.00514357 mol), thus the limiting reactant is 3-nitrobenzaldehyde.

a. Calculation of theoretical yield of product.

−1
Molar mass of product (trans−3−nitrochalcone)=253.25 g mol
Theoretical yield=No . of moles of limiting reactant × Molar mass of product
−1
¿ 0.004962943 mol ×253.25 g mol
¿ 1.2569 g
b. Percentage yield of the crude and purified products.
Actual yield
Percentage yield of crude product= × 100 %
Theoretical yield
1.0500 g
¿ x 100 %
1.2569 g
¿ 83.54 %
Actual yield
Percentage yield of purified product = × 100 %
Theoretical yield
0.4000 g
¿ x 100 %
1.2569 g
¿ 31.82 %
DISCUSSION
The three main goals of this experiment are to synthesise trans-3-nitrochalcone from an aldol
condensation reaction of 3-nitrobenzaldehyde with acetophenone in aqueous base, to
determine the melting point of trans-3-nitrochalcone, and to characterize trans-3-
nitrochalcone using 1H NMR and/or IR spectroscopy.

To prepare the crude product, 3-nitrobenzaldehyde was weighed and acetophenone was
added to the flask along with 95 percent ethanol. The reagents were combined, and any solids
were dissolved by heating the solution on a hot plate. Before moving on to the next step, the
solution should be cooled to room temperature. The mixture was then treated with a sodium
hydroxide solution prepared by the lab assistant. The mixture was stirred until it became very
cloudy. Cooling the flask with ice water and scratching with a glass rod are required to
initiate crystallisation. The solid was collected using vacuum filtration on a Buchner funnel.
The solid was washed with cold water and allowed to air dry for 30 minutes before being
weighed. The preparation is then followed by recrystallization to obtain pure trans-3-
nitrochalcone.

The formation of unsaturated ketones products is the result of this experiment because
ketones are less reactive than aldehyde in aldol condensation because the carbonyl of ketones
is hysterically hindered and is not as susceptible to nucleophilic attack. In this experiment, the
limiting reagent is 3-nitrobenzaldeyde. The theoretical yield is determined by referring to the
3-nitrochalcone mole obtained from stoichiometry, which is 1.2569 g. The actual yield
obtained for crude product is 1.0500 g and for purified product is 0.4000 g. The substance
appears to be sufficiently pure based on the comparison of the actual melting point with the
theoretical melting point, approximately 146 °C. According to the literature review, the
frequency of signal for trans-compound is between 12-18 Hz, proving that the compound
yield is that trans-compound. This frequency is compared to a lower cis-compound
frequency, 6-12 Hz.

This experiment's crude and pure product yield percentages were 83.54% and 31.82%,
respectively. The percentage yield for purified product decreases due to recrystallization of
the crude product. Errors may occur during the filtration process of a product using Buchner
funnel vacuum filtration. The pressure used to collect the solid might be too high for the filter
paper to form holes that will allow the liquid to pass through the solid and into the conical
flask. As a result, the product passed through the filtration paper, affecting the percentage
yield of the product. When the crude product was weighed, it was not properly dried, which
increased the actual yield. To evaporate all the moisture from the solid, it must be left
overnight.

CONCLUSION

In conclusion, the product yield from this experiment is trans-3-nitrochalcone, as

demonstrated by the 1H NMR spectrum. The crude product yield obtained was 83.54%, and
the pure product yield was 31.82%. Finally, the melting point of the product obtained was
around 146 °C.
QUESTIONS
1. Draw the structure of the cis and trans isomers of the compound that you have
prepared.

2. Using proton NMR, how could you experimentally determine that you have the trans
isomer rather than cis isomer? (Consider the use of coupling constants for the vinyl
hydrogen)
trans-isomer has less steric hindrance because the hydrogen and phenyl groups are on
opposite sides of the double bond, whereas cis-isomer has both phenyl groups on the
same side. As a result, the cis-isomer has a high steric hindrance. trans-isomer is
obtained as the product because it has less steric hindrance, which causes the cis
isomer to become more stable.

3. Draw the full mechanism for the aldol condensation of benzaldehyde and acetone (in
the presence of NaOH/H2O).
 a. What type of elimination occur for an aldol condensation reaction?
Elimination of water (dehydration)

b. What product must form before the elimination reaction can occur?
Enolate anion

REFERENCE

Pavia, Lampman, Kriz and Engel, Introduction to Organic Laboratory Techniques 3 rd Edition
(2011). page 669-673.

3-nitro-trans-chalcone (24721-24-2) 1H NMR. (n.d.). Retrieved January 09, 2022, from

https://www.chemicalbook.com/SpectrumEN_24721-24-2_1HNMR.htm

IR Spectrum Table & Chart. IR Spectrum Table. (n.d.). Retrieved January 09, 2022, from
https://www.sigmaaldrich.com/MY/en/technical-documents/technical-article/analytical-
chemistry/photometry-and-reflectometry/ir-spectrum-table

Libretexts. (2021, September 12). 5.5: The basis for differences in chemical shift. Chemistry
LibreTexts. Retrieved January 09, 2022, from
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Book
%3A_Organic_Chemistry_with_a_Biological_Emphasis_v2.0_(Soderberg)/
05%3A_Structure_Determination_Part_II_-
_Nuclear_Magnetic_Resonance_Spectroscopy/
5.05%3A_The_Basis_for_Differences_in_Chemical_Shift
APPENDIX 1
1
H spectrum trans-3-nitrochalcone:

IR spectrum trans-3-nitrochalcone: