EXPERIMENT 5 : PREPARATION OF AN ,  UNSATURATED

KETONE VIA MICHAEL ADDITION AND ALDOL

CONDENSATION REACTIONS

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. 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.

O O H O H
O
║ ║ │ ║ │
║
–H2O
C6H5 – C – H + CH3 – C – R -OH C6H5 – C – CH2 – C – R C6H5 – C ═ C –
C–R
│
│
OH
H
Intermediate
As illustrated for the reaction of benzaldehyde with a general ketone, the
ketone looses a proton from an α-carbon to form an enolate ion, which attacks the
carbonyl carbon of the aldehyde to yield, after protonation, a β-hydroxy ketone. This
intermediate is, for aromatic aldehydes at least, instable and undergoes base-catalyzed
dehydration to yield the unsaturated product.
Objective

 To synthesis benzalacetophenones (chalcones) by aldol condensation reaction.

 To determine the percentage yield of the crude product.
 To identify the melting point of the purified product.
 To obtain the NMR spectrum of benzalacetophenones (chalcones) .

Procedure

0.75 g of 3-nitrobelzaldehyde is placed in a 50 mL Erlenmeyer flask. Then, 0.60

mL of acetophenone and 4.0 mL of 95% ethanol are added to the flask. The flask is
swirled to mix the reagent and dissolved any solids present. The flask is warmed on
the hot plate to dissolve the solids. Then, it is cooled at room temperature. 0.5mL of
sodium hydroxide is added into the mixture and swirled until it solidified or the
mixture become very cloudy.
For isolation of the crude product, 10mL of ice water is added into the flask.
The mixture is stirred if solids or oil is present to break up the solid mass. The mixture
is transferred to a beaker with 15mL ice water. The precipitate is stirred to break it up
and the solid is collected on Bȕchner funnel. The product is washed with cold water.
The solid is allowed to dry for 30minutes. The solid is weighed and the percentage
yield is determined.
 For the crystallization, 0.50g of sample is crystallized from 20mL of hot
methanol. The flask is gently scratched to induce crystallization while cooling. The
literature melting point is 146oC.

Data

Mass of 3-nitrobenzaldehyde 0.7583 g

Mass of crude product 2.8759 g
Melting point 140oC

Calculation

Mass of 3-nitrobenzaldehyde = 0.7583g

No. mol of 3-nitrobenzaldehyde = Mass of 3-nitrobenzaldehyde
MW
= 0.7583 g
151 g/mol
= 0.005022 mol

H O H H O
│ ║ │ │ ║
- C = O + CH3- C - -C=C–C-
+ H2O

NO NO
3-nitrobenzaldehyde 3-nitrochalcone

0.6mL of acetophenone = 0.6cm3 of acetophenone

Mass of acetophenone = 0.6cm3 × 1.03g/cm3

= 0.618g

0.618𝑔
Mol of acetophenone =
120𝑔/𝑚𝑜𝑙

= 0.00515mol

Limiting reagent: 3-nitrobenzaldehyde

From the above reaction equation,

1 mol 3-nitrobenzaldehyde ≡ 1 mol 3-nitrochalcone

Therefore, no.mol of 3-nitrochalcone is 0.005022 mol.

Mass of 3-nitrochalcone (theoretical) = No.mol of 3-nitrochalcone x MW

= 0.005022 mol x 253 g/mol
= 1.271 g (theoretical)
Mass of 3-nitrochalcone (actual) = 0.6621 g

Percentage yield = Actual yield x 100%

Theoretical yield
= 2,8759 x 100%
1.271
= 226.27%

Discussion

In this experiment, benzalacetophenones (chalcones) are prepared by the reaction of a

substituted benzaldehyde with acetophenone in aqueous base. Based on the chemical
equation, the limiting reactant for the reaction is 3-nitrobenzaldehyde. By comparing
the number of mol of both compound, the theoretical mass of 3-nitrochalcone can be
calculated. From the result, quite big percent of crude product have been obtained.
The product seems to be not pure enough since the percentage yield obtained is only
226.27%. The melting point of the purified product is 140oC that is quite close to the
literature melting point which is 146oC. The mechanism of this reaction is show on
below:

1
O OH- O

-
CH3 CH 2

2
O O O

- -
CH 2 O +
- + N
O N
-
O O O

O
3 NaOH O
-
O +
-
N O +
N
-
O O
O OH

O
+ -
O N O
4

- -H2O
O + O
N
O OH

We did not get result closes to the theoretical, due to several errors that occur
while doing this experiment. Firstly, error while collecting the solids by using
Buchner funnels. The pressure that we use to collect the solids is too high and causes
the filter paper full of holes. That will cause the amount of crude product give effect
to their weight. The temperature of the oven should be below 50oC to avoid the bond
between molecule break and give bad effect for our result. We have to make sure that
the crude product is dry enough before being weighed to avoid error while weighing.

Conclusion
 From this experiment, 3-nitrochalcone is prepared by aldol condensation reaction
between substituted benzaldehyde (3-nitrobenzaldehyde) and acetophenone in
aqueous base. The percentage yield of the crude product obtained is 226.21% and the
melting point of the purified product is 140oC. The 3-nitrochalcone has been
successfully obtained from the NMR spectrum.

Questions

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

the aldehyde that you selected in this experiment.

1
O OH- O

-
CH3 CH 2

2
O O O

- -
CH 2 O +
- + N
O N
-
O O O

O
3 NaOH O
-
O +
-
N O +
N
-
O O
O OH

O
+ -
O N O
4

- -H2O
O + O
N
O OH
2. Draw the structure of the cis and trans isomers of the compound that you prepared.
Why did you obtain the trans isomer?

The trans isomer is obtained due to the low melting point which is shows 146oC
rather. It is also due to the NMR spectrum its shows that the product is in structure
trans isomer.

3. Using proton NMR, how could you experimentally determine that you have the
trans isomer rather than cis one?

Using proton NMR, the trans-isomer has frequency between 12 – 18 Hz while the cis-
isomers have frequency between 6 – 12Hz.

4. Provide the starting material needed to prepare the following compounds.

5. Prepare the following compounds starting from benzaldehyde and the appropriate
ketone. Provide reactions for preparing the ketones starting from aromatic
hydrocarbon compounds.

References

1. (2017, 12). The Aldol Condensation Reaction: Preparation of

Benzalacetophenones. AllBestEssays.com. Retrieved from
https://www.allbestessays.com/essay/The-Aldol-Condensation-Reaction-Preparation-
of-Benzalacetophenones/68383.html
2. T.W. Graham Solomons, Craig B. Fryhle, Organic Chemistry, Asia, John Wiley
and Sons, 2011.

3. Donald L. Pavia, Gary M. Lampman, George S. Kriz, & Randall G. Engel

Introduction of Organic Laboratory Techniques, 2nd Edition (2005)