EXPERIMENT 4

THE ALDOL CONDENSATION REACTION: PREPARATION OF

BENZALACETOPHENONES (CHALCONES)

INTRODUCTION

An aldol condensation is an organic reaction in which an enol or an enolate ion reacts with
a carbonyl compound to form a β-hydroxyaldehyde or β-hydroxyketone, followed by a dehydration
to give a conjugate enone. Aldol condensations are important in organic synthesis, providing a
good way to form carbon–carbon bonds. For example, the Robinson annulation reaction sequence
features an aldol condensation; the Wieland-Miescher ketone product is an important starting
material for many organic syntheses.

Benzaldehyde reacts with a ketone in the presence of base to give α, β-unsaturated ketones.
This reaction is an example of a crossed aldol condensation where the intermediate dehydrates to
produce the resonance-stabilized unsaturated ketone. Ketone loses a proton from an α-carbon to
form an enolate ion, which attacks the carbonyl carbon of the aldehyde to yield, after protonation,
α, β-hydoxy ketone. The intermediate is, for aromatic aldehyde at least, instable and undergoes
base-catalysed dehydration to yield the unsaturated product. In its usual form, it involves the
nucleophilic addition of a ketone enolate to an aldehyde to form a β-hydroxy ketone, or "aldol"
(aldehyde + alcohol).

OBJECTIVE

1. To perform aldol condensation reaction between 3-nitrobenzaldehyde and acetophenone in

the presence of base to produce an α, β-unsaturated ketone (3-nitrohalcone)
2. To calculate the percentage yield of the crude and purified product.
3. To obtain the NMR spectrum for the pure product.

CHEMICALS

1. 3-nitrobenaldehyde
2. Acetophenone
3. 95% ethanol
4. Sodium hydroxide solution
5. Methanol
6. Ice water
APPARATUS

1. 100ml beaker
2. Glass rod
3. Filter funnel
4. Measuring cylinder
5. Conical flask
6. Spatula

PROCEDURE

1. 0.7515g of 3-nitrobenzaldehyde was mix with 0.6mL acetophenone and 4mL of 95%
ethanol in a conical flask. The mixture was stirred until the entire solid is 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 could dry in oven with temperature of about 80°C for 30 minutes. The
weight of the solid product was recorded.
7. The entire solid (1.0633g) was recrystallized with 42.5mL hot methanol solution, and the
solid was filtered again. The solid was dried again in oven at temperature of about 80°C
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-nitrochalcone).

RESULT AND OBSERVATION

Weight (g)
Weight of 3-nitrobenzaldehyde 0.7555
Weight of crude solid 1.9171
Weight of crude solid to recrystallize 0.500
Weight of dry pure product 0.2513

Observation
  Colourless solution turns to reddish yellow and the precipitate form after the addition of
sodium hydroxide solution.

CALCULATION
Molar mass of acetophenone = 120g/mol

Molar mass of 3-nitrobelzaldehyde =151g/mol

Molar mass of 3-nitrochalcone = 253g/mol

Density of acetophenone = 1.03g/cm3

Mol of 3-nitrobenzaldehyde = 0.75 g

151 g/ mol
= 0.004967mol

0.6mL of acetophenone = 0.6cm3 of

acetophenone

Mass of acetophenone = 0.6cm3 × 1.03g/cm3

= 0.618g
Mol of acetophenone = 0.618 g
120 g/ mol

= 0.00515mol

Mass of product (3-nitrochalcone) = 0.2513g

Melting point of product (3-nitrochalcone) =57 °C

Percentage yield = mass of product molar mass of product mass of

 starting
material
molar mass of x 100%
starting material

FTIR
Result
DISCUSSION
In this experiment, we performed the aldol condensation reaction between a
substituted benzaldehyde and a ketone in the presence of base to produce an α, β-unsaturated
ketone.
In this experiment, the percentage yield of the crude is 19.88 % while the melting
point that we observed is 57 ºC. This is different from the melting point of the theoretical
result which is 146 ºC. There might be some errors occur during the experiment which cause
the varying of the temperature. Those error maybe come from filtration process by using the
Buchner funnel vacuum filtration. The pressure used to collect the sample is a bit high from
the recommendation level due to the limitation of time. Apart from that, the high pressure
also causes the sample to pass through the filter paper which then enter the liquid in the
conical flask. This directly make the actual yield mass to decrease.
The chemical equation between 3-nitrobenzaldehyde
and

acetophenone
shown below.

Limitations of equipment especially the Nuclear Magnetic Resonance (NMR) and

FTIR require us to share with other groups as well. We have to wait approximately a week
before we can obtain the NMR results due to the limitations of equipment that we have in the
campus. The initially formed β-hydroxyketone rapidly dehydrates to generate an α, β-
unsaturated ketone, even under the basic conditions usually employed for the acyl addition
reaction. Elimination is favoured because of resonance stabilization of the fully conjugated
product. The partially saturated β-hydroxyketone intermediate initially formed can be isolated
in moderate to good yield. The frequency of signal for trans compound is between 12-18Hz
and a cis-compound is between 6-12Hz. The mechanism of this reaction is show on below:
CONCLUSION
At the end of the experiment, we can perform the condensation reaction between 3-
nitrobenzaldehyde and acetophenone in the presence of a base that is ethanol successfully.
The presence of a base is to produce an α, β-unsaturated ketone. The percentage yield of the
crude that we got is 19.88 % and we able purify the product in order to obtain the NMR
spectrum of the pure product.

REFERENCES
1. Aldol condensation. (2019, May 28). Retrieved May 30, 2019, from
http://en.wikipedia.org/wiki/Aldol_condensation
2. Aldol Condensation Reaction. (n.d.). Retrieved May 25, 2019, from

https://brainmass.com/chemistry/organic-reaction-intermediates-and-

mechanisms/aldol-condensation-reaction-104832
3. Wachter, N. M. (2013). Using NMR To Investigate Products of Aldol Reactions:

Identifying Aldol Addition versus Condensation Products or Conjugate Addition

Products from Crossed Aldol Reactions of Aromatic Aldehydes and Ketones. ACS

Symposium Series NMR Spectroscopy in the Undergraduate Curriculum,91-102.

doi:10.1021/bk-2013-1128.ch007