CHM557 LABORATORY REPORT

EXPERIMENT 4

The Aldol Condensation Reaction:

Preparation of Dibenzalacetone

NAME: SYAFAWANI BINTI CAROL

STUDENT ID: 2019672332

GROUP: AS2533D

LECTURER NAME: MADAM NOORHIDAYAH BINTI PUNGOT

OBJECTIVE

 To synthesize Dibenzalacetone
 To carry out a mixed aldol condensation reaction
 To study the mechanism of aldol condensation reaction

APPARATUS

 Beaker
 Foil
 Thermometer
 Vacuum filter
 Buncher funnel
 Analytical balance
 Oven
 Meting point apparatus
 NMR spectrometer
 FTIR spectrometer

CHEMICAL

 5 g of NaOH
 40 mL 95% ethanol
 50 mL distilled water
 5.4 g of benzaldehyde
 1.5 g acetone
 20 mL of hot ethanol.
INTRODUCTION

The reaction of an aldehyde with a ketone employing sodium hydroxide as the base
is an example of a mixed aldol condensation reaction, the Claisen-Schmidt reaction.
The double mixed-aldol condensation reaction between acetone and benzaldehyde
was carried out. Acetone has α-hydrogens (on both sides) and thus can be
deprotonated to give a nucleophilic enolate anion. The alkoxide produced is
protonated by solvent, giving a β-hydroxyketone, which undergoes base-catalyzed
dehydration. The elimination process is particularly fast in this case because the
alkene is stabilized by conjugation to not only the carbonyl but also the benzene. In
this experiment, excess benzaldehyde such that the aldol condensation can occur on
both sides of the ketone.

Dibenzalacetone is readily prepared by condensation of acetone with two equivalent

of benzaldehyde. The aldehyde carbonyl is more reactive than that of the ketone and
therefore reacts rapidly with the anion of the the ketone to give a β-hydroxyketone,
which easily undergoes base catalyzed dehydration. Depending on the relative
quantities of the reactants, the reaction can give either mono- or dibenzalacetone.

Dibenzalacetone is a fairly innocuous substance in which its spectral properties

indicate why it is used in sun-protection preparations. In the present experiment,
sufficient ethanol is present as solvent to readily dissolve the starting material,
benzaldehyde and also the intermediate, benzalacetone. The benzalacetone once
formed, can then easily to react with another mole of benzaldehyde to give the desired
product in this experiment, dibenzalacetone.
EXPERIMENTAL PROCEDURE

1. 5 g of NaOH was dissolved in a mixture of 40 mL 95% ethanol and 50 mL

distilled water in a 200 mL beaker. The beaker was covered and the mixture
was allowed to cool to 20 °C.

2. In another beaker, 5.4 g of benzaldehyde was mixed with 1.5 g acetone. The
beaker was covered with foil, for later use.

3. Half of the mixture in (2) was added into (1) and been stirred for 15 minutes
until the solution turns to yellow and a precipitate is formed (the temperature
was keep in the range of 20 – 25 °C).

4. The rest of the mixture in (2) was added, and then continued stirring for 30
minutes (the temperature was keep below 24°C).

5. The residue was filtered off using vacuum filtration on a Buchner funnel. Rinse
with water, ethanol, and then was allowed it to air dry for 30 minutes.

6. The solid was weighed and the crude percent yield was determined.

7. The crude product was recrystallized with 20 mL of hot ethanol. Cooling and
scratching are necessary to initiate crystallization. The solid was collected by
vacuum filtration and been dry it in the oven.

8. The dry pure product was weighed and the percent yield was calculated.

9. The melting point was measured and the FTIR and NMR spectra of the product
was obtained.
RESULT

 IR spectrum of dibenzalacetone
 NMR spectrum of dibenzalacetone
DATA

Melting point of product dibenzalacetone 74°C

Weight of crude product 4.56 g
Weight of pure product 4.26 g
Percent yield of crude product 76.4%
Percent yield of pure product 71.4%

IR SPECTRUM

BOND ( Functional group ) Experimental wavenumber ( cm-1 )

CH (aromatic) 3060 – 3028
CO (carbonyl) 1651
C=C (aromatic) 1593, 1494

NMR SPECTRUM

Signal Chemical shift (ppm)

Protons a, Doublet 7.8
Protons b, Doublet 7.1
Protons c, d, e, Multiplet 7–8
CALCULATION

 Chemical equation of this reaction:

C3H6O + 2 C₇H₆O C17H14O

 Mole of benzaldehyde =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑏𝑒𝑛𝑧𝑎𝑙𝑑𝑒ℎ𝑦𝑑𝑒

5.4 𝑔
= 𝑔
106 𝑚𝑜𝑙

= 0.0509 mol

 Mole of dibenzalacetone:

1
= × 0.0509 mol
2
= 0.0255 mol
 Theoretical mass of dibenzalacetone:

𝑔
= 0.0255 mol × 234
𝑚𝑜𝑙
= 5.967 g

 Percentage yield of crude product:

𝒂𝒄𝒕𝒖𝒂𝒍 𝒚𝒊𝒆𝒍𝒅
= × 100%
𝒕𝒉𝒆𝒐𝒓𝒆𝒕𝒊𝒄𝒂𝒍 𝒚𝒊𝒆𝒍𝒅

4.56 𝑔
= × 100%
5.967 𝑔

= 76.4 %

 Percentage yield of pure product:

𝒂𝒄𝒕𝒖𝒂𝒍 𝒚𝒊𝒆𝒍𝒅
= × 100%
𝒕𝒉𝒆𝒐𝒓𝒆𝒕𝒊𝒄𝒂𝒍 𝒚𝒊𝒆𝒍𝒅

4.26 𝑔
= × 100%
5.967 𝑔

= 71.4 %
DISCUSSION

Condensation is a process which joins two or more molecules usually with the loss of
a small molecule such as water or an alcohol. Aldol condensation (Claisen-Schmidt
reaction) definitely is a process which join two carbonyl groups with a loss of water
molecule in order to form β-hydroxyketone. The product is also known as adol because
it containing two functional groups which includes aldehyde (or ketone) group and
alcohol group. The product dibenzalacetone was formed from the reaction between
an acetone molecule and two benzaldehyde molecules. Generally, the aldol
condensation is carried out under a base condition.

Sodium hydroxide was mixed with distilled water then was used to react with sufficient
ethanol as the first step. The particular reaction is an exothermic reaction which
released the heat energy to the surrounding from the reaction. The sodium hydroxide
was functioned as a catalyst in the reaction. The ethanol acts as a solvent which allows
the acetone and benzaldehyde to dissolve and react with each other. After that,
acetone and benzaldehyde were mixed in the solvent which turns to yellow colour
quickly. Eventually, the product was formed with a yellow precipitate appear in the
reaction after a few seconds. However, there are some impurities and side products
were formed in the yellow precipitate. So, recrystallization was carried out by using
ethyl acetate as solvent in order to purify the product and hence a pure product could
be obtained for the FTIR and IR spectra analysis. In the recrystallization process, the
yellow precipitate in ethyl acetate was immersed into an ice-bath in order to obtain a
higher yield of product. This is because the heat energy in the precipitate easily to be
released since the precipitation formation is an exothermic reaction and hence it
maximizes the formation rate of the product.
Acetone is considered as a stable and unreactive compound, so it should be converted
into anionic form to increase its nucleophile properties to initiate the reaction. The
sodium hydroxide dissolves in water to produce hydroxide ion and it tends to attack
the α-hydrogen in acetone and to form water molecule. The deprotonation of acetone
caused the enolate ion was produced as nucleophile which will be used in the
synthesis of dibenzalacetone. An enolate ion was formed which it exists as resonance-
stabilized structure which shown in the following diagram:

The acetaldehyde enolate ion attack to the benzylic carbon of benzaldehyde via
nucleophilic addition to form the intermediate as shown in below:

The oxygen attached to the benzylic position of carbon tends to attract one proton
from water molecule to form hydroxide group in the intermediate. This is the formation
of an aldol since the molecule consists of a carbonyl group and an alcohol group. In
the basic condition, the hydroxide ion tends to remove one proton from the α-carbon
resulting the formation of C=C double bond at the α and β carbon. At the same time,
the hydroxide group attached to the β carbon forms a leaving group. After the
condensation, benzalacetone was formed after two water molecules leaved as shown:
The benzalacetone tends to form benzalacetone enolate ion after the hydroxide group
from the surrounding attack the proton which attached to the carbon at benzylic
position.

The same process has been take place as in the Diagram 2 but with the more bulky
benzalacetone enolate ion as the material. The benzalacetone enolate ion acts as a
nucleophile which attacks another benzaldehyde. The protonation of the aldol took
place followed by the hydroxide groups have been eliminated as leaving groups. As a
result, the nucleophilic addition and base-catalyzed dehydration lead to the formation
of the desired product which is dibenzalacetone. The mechanism of dibenzalacetone
formation was shown below:
The overall mechanism of the dibenzalacetone was summarized:
The percentage yield of dibenzalacetone in this experiment is 71.4%. Some of the
product has been lost during the process of recrystallization. In recrystallization, some
of the product dissolved in the ethyl acetate. The melting point of the product is 74°C
which is lower than the actual melting point (110 °C ~ 111 °C). This is because there
is some impurities exist in the particular compound which will tend to lower the melting
point of the dibenzalacetone.

CONCLUSION

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.
QUESTION

1) Give the mechanism for the preparation of the appropriate

benzalacetophenone using the aldehyde that you selected in this experiment

Mechanism:
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.

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

Coupling constants of nearby NMR-active nuclei can also give information on

their relative position and bonding orientation. For instance the two vinylic
protons in disubstituted alkenes often have characteristic coupling constants (<
5 Hz for geminal, 5–12 Hz for cis and >10 Hz for trans). These are not rigorous
proof of geometry, especially for values between 10 and 12 Hz, but if you have
a mixture of two isomers, the one with the greater coupling constant can be
confidently assigned as trans.
LABORATORY TECHNIQUE

The techniques involves in this experiment is separation, distillation, liquid-liquid

extraction and drying.

REFERENCES

 Donald L.Pavia et al (2011), Introduction to Organic Laboratory

Techniques,Cengage Learning

 Aldol condensation reaction retrieved from https://www.studocu.com/en-

gb/document/trinity-college-dublin-university-of-dublin/chemistry/coursework/aldol-
condensation-reaction/1741486/view

 Synthesis of Dibenzalacetone by Aldol Condensation retrieved from

http://1chemistry.blogspot.com/2011/11/objective-1.html