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Aldol condensation reaction

Chemistry (Trinity College Dublin University of Dublin)

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Experiment 1

Aldol Condensation reactions

Introduction

(a) Objectives
 To synthesize Dibenzalacetone.
 To synthesize Benzalacetophenone.
 To measure the melting point of the sample.
 To understand the mechanism of an Aldol Reaction.

(b) Theory

An Aldol condensation reaction is one in which an enol or an enolate ion reacts

with a Carbonyl compound to form β-hydroxyaldehyde or a β-hydroxyketone,
hence a dehydration gives a conjugate enone. In both parts of this practical
experiment Benzaldehyde reacts with a ketone in the presence of a base to
produce β-unsaturated ketones. The reaction that the experiments follow is an
example of a crossed aldol condensation reaction where the intermediate in the
reaction becomes dehydrated to produce the resonance- stabilised unsaturated
ketone. The ketone loses a proton from an alpha-carbon to then form an enolate
ion, which attacks the carbonyl carbon of the aldehyde to yield, after protonation
alpha, beta-hydroxyketone. The intermediate formed for the aromatic aldehyde is
unstable and is subjected to base-catalysed dehydration, until the unsaturated
product is yielded. An important point to note is that a crossed-aldol condensation
leads to a number of different products, unless one of the carbonyl compounds
that is involved in the reaction cannot form an enolate ion (meaning compound
has no alpha-hydrogens). An aromatic aldehyde, such as Benzaldehyde is
sufficient for the reaction as only one enolate ion will form, which is from the other
carbonyl compound. Hence formation, the nucleophilic enolate ion attacks the
carbonyl carbon to form a 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. The elimination process with
regards to part one of the experiment was particularly fast as the alkene is
stabilised by conjugation to not only the carbonyl but also benzene. The
theoretical melting point of Dibenzalacetone is 110-111 °C. In theory, the melting
point of Dibenzalacetone is 55-57°C.

Reaction Mechanisms:

See post practical part (i) for reaction mechanisms

Experiment procedure

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Part One – Synthesis of Dibenzalacetone.

Benzaldehyde (2.88g; 2.77mL) was added to a conical flask with acetone (0.79g;
1mL). The solution was shaken to ensure a homogeneous solution. Hence, 2M
sodium hydroxide (40mL) and ethanol (30mL) was added to a beaker. Half of the
solution from the conical flask was added to the beaker and mixed several times.
After 15 minutes, the remainder of the solution was added to the beaker. Ethanol
was used to ensure that all of the material had been transferred to the reaction
vessel. The reaction was timed for 30 minutes and hence the product was collected
by suction filtration. The solid that was collected was washed with water (3 x 60mL)
and then sucked as dry as possible. The product was then weighed using a scales
and the percentage yield before Recrystallisation was calculated. The
Dibenzalacetone was then recrystallized from ethanol (2.5mL/g). The product was
then dried in air and the percentage yield and melting point of the sample was
determined.

Part Two- Synthesis of Benzalacetophenone.

Benzaldehyde (2.88g; 2.77mL) was added to a conical flask with acetophenone

(3.26g; 3.17mL). The solution was mixed to ensure a homogeneous solution. Half of
the mixture was added to a beaker containing 2M sodium hydroxide (40mL) and
ethanol (30mL). The solution was swirled well and after 15 minutes the remainder of
the benzaldehyde/acetone mixture was added. Ethanol was used to transfer all the
solution to the reaction vessel. The solution was placed in ice. The reaction was
timed for 30 minutes, swirled occasionally. The solid was recrystallized. The product
was hence collected by suction filtration. Percentage yield and melting point was
determined.

Results

Part One:

Mr of acetone: 3(12.011)+ 6(1.0079) + 15.9994= 58.0798g.

Theoretical yield: 0.79g/ 58.0798g= 0.01360197521 moles.

Mr of Dibenzalacetone: 17(12.011)+ 14(1.0079) + 15.9994= 234.297g.

Amount of Dibenzalacetone Crystals obtained: 2.69g.

Actual yield: 2.69g/234.297g= 0.01148115426 moles.

Percentage yield before Recrystallization: Act/Theoretical:

0.01148115426/0.01360197521 x 100/1= 84.40799284%.

Recrystallization:

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Crystals attained after Recrystallization: 2.69g- 1.47g= 1.22g.

Actual yield: 1.47g/234.297g=0.006274088016moles.

Theoretical Yield: 0.006274088016/0.01148115426 x 100/1= 54.64684015 is approx

equal to a 55% yield.

Melting point of Dibenzalacetone: 95 °C.

Part Two:

Mr of Benzaldehyde: 6(12.011) + 5(1.0079) + 12.011+ 1.0079+

15.9994=106.1238g.

Mr of Acetophenone: 8(12.011) + 8(1.0079) + 15.9994= 120.1506g.

1 x 2.88g/ 106.1238g= 0.02713811605 moles.

120.1506g x 0.02713811605= 3.260660926g

X= amount of Acetophenone required= 3.260660926g.

Density of Acetophenone= 1.03g/cm^3.

Amount required = 3.165690219 approx 3.17mL.

Discussion

In part one of the experiment the yield dramatically dropped after recrystallization. It
can be thought that this occurred for a number of reasons. One of which could
perhaps be that not all of the crystals were washed with ethanol and then transferred
into the filtration apparatus. Another could be that there was a number of impurities
present before recrystallization and hence some of these impurities were removed
after recrystallization. In addition, some of the product may have been lost due to
evaporation. Finally, some of the product could also have been lost during the
filtration process. The melting point was lower (95 °C) than the expected (110-111°C).
The lower melting point resulted as there was impurities present and impurities tend
to lower the melting point of compounds. In Part two of the experiment the limiting

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reagent was found and its molar value and hence its molar value was multiplied by
the molecular mass of Acetophenone in order to calculate the value of x. The X
value was the amount of Acetophenone that was required to synthesis
Benzalacetophenone. The value of X was divided by the density of the ketone in
order to calculate the value in mL. The percentage yield and melting point for Part
Two was not calculated, due to the fact the experiment was not successful. The
experiment was not successful, due to not following procedures efficiently enough.
The mixture of Benzaldehyde and Acetophenone was added entirely to the NaOH
and ethanol, instead of in two aliquots (the second being after 15 minutes). Due to
not following the correct procedure Crystals did not form in the conical flask.
Perhaps, heating would have helped the solution to speed up the formation of
Crystals too.

Conclusions

Condensation reactions are reactions which join two or more molecules together,

usually with the loss of a small molecule such as water or an alcohol. Precaution

needs to be taken when following lab procedures, to ensure one obtains coherent

results. An enolate ion acts effectively as a nucleophile, which can be used to

synthesize Dibenzalacetone. Chalcone (Benzalacetophenone) is an important

aromatic ketone and enone that forms the central core in many biological

compounds.

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