The Aldol Condensation Reactions :

Preparation of Benzalacetophenone (chalcone)

OBJECTIVES

1. The Aldol Condensation between 3-nitrobenzaldehyde and acetophenone in the

presence of base (ethanol) to produce α,β-unsaturated ketone.
2. To obtain the melting point of the pure product and NMR spectrum for the pure
product.

INTRODUCTION

Chalcone is an aromatic ketone that forms the central core for a variety of important
biological compounds. Other name for chalcone are benzalacetophenone. Chalcone can be
prepared by an aldol condensation between a benzaldehyde and an acetophenone in the
presence of a catalyst. From the aldol condensation it will forming carbon-carbon bond. In
this reaction, the conjugate base of an ketone or aldehyde was added to the carbonyl group
of another aldehyde or ketone to give a β-hydroxyaldehyde or β-hydroxylketone product.
This is the intermediate product of the crossed-aldol reaction. The crossed aldol happened
in this reaction because only one carbonyl compound can form anolate ion because it is only
compound that has α-carbon. Ketone can choose to form enolate ion because the presence
of α-carbon. The enolate ion will attacks the aldehyde compound or carbonyl compound to
form β-hydroxycarbonyl product. The β-hydroxycarbonyl product then eliminates a
molecule of water to form a conjugated system composed of a double bond and the
carbonyl group.
APPARATUS

 50mL Erlenmeyer flask

 Measuring cylinder
 Glass rod
 Beaker
 Vacuum Filtration
 Buchner Funnel

CHEMICAL

 0.75 g of 3-nitrobenzaldehyde
 0.60mL of acetophenone
 4.0mL of 95% ethanol
 0.5mL of sodium hydroxide, NaOH
 Ice water
 20mL of hot methanol

PROCEDURE

1. 0.75 g of 3-nitrobenzaldehyde was mixed with 0.6mL of acetophenone and 4mL of

95% ethanol in 50mL Erlenmeyer flasks. The mixture was stirred until the solid
dissolved.
2. 0.5mL of sodium hydroxide solution (6g NaOH solid in 10mL water) was added into
the mixture and the stirring process continued.
3. 10mL of ice water was added and scratching was performed to induce to
crystallization process.
4. The mixture then was transferred into a beaker containing 15mL of ice water.
5. The mixture was filtered to collect the solid by using Buchner funnel filtration set.
6. The solid collected was allowed to dry in oven with temperature of about 80oC for 30
minutes. The weight of the solid product was recorded.
7. The 0.5146 g of solid was crystallized with 20mL of hot methanol solution, and the
solid was filtered again. The solid was dried again in oven at temperature of about
75oC overnight to make sure complete drying process.
8. The dried solid product (3-nitrochalcone) was weighed and the percentage yield was
calculated.
9. The melting point and NMR test were done with the solid product (3-
nitrrochalcone).
CALCULATION

Mass of 3-nitrobenzaldehyde 0.7531 g

Mass of Filter paper (1) 0.6561 g
Mass of Filter paper (1) + crude 2.7175 g
Mass of crude 2.0614 g
Mass of crude after recrystallization 0.1395 g
Melting point 140 oC

Mass of acetophenone = volume of acetophenone x density of acetophenone

=0.6cm3 x 1.03g/cm3
=0.618 g
Mole of acetophenone 𝑚𝑎𝑠𝑠
=
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
0.618 𝑔
= 𝑔
120
𝑚𝑜𝑙

= 0.00515
Mole of 3- 𝑚𝑎𝑠𝑠
=
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
nitrobenzaldehyde
0.7531 𝑔
= 151𝑔
𝑚𝑜𝑙

=0.0050 mole
Theoretical yield = mole of 3 nitrobenzaldehyde x mole of 3 nitrochalcone (
(crude) crude)
= 0.0050 mole x 254 g/mol
=1.27 g
Percentage yield Actual yield
= 𝑥 100%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
(crude)
2.0614
= 𝑥 100%
1.27

=162%
Percentage yield Actual yield
= 𝑥 100%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑦𝑖𝑒𝑙𝑑
(purified product)
0.1395 g
= 𝑥 100%
1.27 𝑔

=10.98%
NMR result chalcone

Signal Chemical shift (ppm)

5H multiplet 7.59-7.45
1H doublet 2.09
DISCUSSION

In this experiment we are going to produce Benzalacetophenone (chalcone).The

chalcone formed from substituted aldehyde and acetophenone through the intermediate of
the reaction β-hydroxyketone via aldol condensation. The intermediate compound is 3-
hydroxy-3-(4-nitrophenyl)-1-phenylpropan-1-one. We used 3-nitrobenzaldehyde as the
acceptor while the acetophenone was added as the donor in this reaction. The
acetophenone was form enolate ion after we added 0.5mL sodium hydroxide and produce
water molecule.Before that the 95% of ethanol was added with the acetophenone. The use
of 95% of ethanol to give the equilibrium of the enolate formation to be shifted to the left.

From the result, we obtained the product seem to be pure enough by comparing the
actual melting point with the theoretical melting point. The actual melting point is 140 oC
while the theoretical melting point is 146oC. The percentage yield of crude product about
162% is more than we supposed to collect. There must be an error while handling the
experiment; it might be any contaminant from the glassware we used or the weight of the
sample not in correct method. This make the actual yield more than expected value of
sample. The weight of product also affect when the product are not dried completely. Thus,
to make sure there is no error in weighing the product, the solid must be dry at least
overnight to evaporate all the water moisture.

The NMR result we obtained is 1H, doublet signal was observed at 2.09 ppm. This
show that the C=C was observed in this NMR spectrum. Next the aromatic compound 5H,
multiplet was obtained at 7.59-7.45 ppm. In this spectrum there is many peak (noise) due to
interference that might present in the purified product.

CONCLUSION

The product yield from this experiment is 3-nitrobenzaldehyde that proven with the H1 NMR
spectrum. The percentage yield of the purified product obtained is 13.3% and the melting
point of the product is 140oC.

REFERENCES
  Kriz,Lapman, Graham solomons(2011) Introduction to organic laboratory techniques,
A small scale approach. 3rd edition (669).

 The royal society of chemistry (2017) Comprehensive organic chemistry experiment

for the laboratory. Retrieved from
http://www.rsc.org/suppdata/books/184973/9781849739634/bk9781849739634-
chapter%204.2.2.pdf

QUESTION

1. Give a mechanism for the preparation of the appropriate benzalacetophenone

using the aldehyde that you selected in this experiment.
2. Draw the structure of the cis and trans isomers of the compound that you
prepared. Why did you obtain the trans isomers ?

3. Using proton NMR, how would you experimentally determine that you have the
trans isomers rather than the cis one ?
4. Provide the starting materials needed to prepare the following compounds.