Synthesis and Characterization of Dibenzalacetone

Tan Yong Jie (m15604)

Synthesis and Characterization of Dibenzalacetone
Aim: The aim of this experiment is to prepare a sample of dibenzalacetone (via a
reaction of acetone with benzaldehyde) and determine its yield. The purity of the
product will be determined using a melting point apparatus and TLC will also be
conducted to determine if there is contamination from reactants.
Introduction Benzaldehyde, a primary component of bitter almond oil, has a
characteristic pleasant almond-like odor. Benzaldehyde can also be obtained from
other natural sources such as from almonds, apricots, apples and cherry kernels,
which contain significant amounts of amygdalin, a glycoside that breaks down under
enzyme catalysis into benzaldehyde (1). Notably on oxidation, benzaldehyde is
converted into an odourless benzoic acid, which is a common impurity in laboratory
samples (1).
Acetone is a colourless, volatile, flammable liquid that is the simplest ketone. It is
miscible with water and serves as an important solvent for cleaning purposes in the
laboratory. It is also an important component of nail polish removers as well as paint
thinners (2). Dibenzylideneacetone is used as a sunscreen component and as a
ligand in organometallic chemistry. It is a bright-yellow solid insoluble in water, but
soluble in ethanol. Sunlight causes the compound to be converted to a cyclobutane
mixture in a [2+2] cycloaddition (3).
Suction filtration is a method used to remove solvent from solid crystals by the
application of reduced pressure in the Bchner flask (3). This method offers more
control over the rate of filtration compared to gravity filtration. In this experiment
suction filtration was used to remove the solvent from the crude product as well as
the final product (3).
Recrystallization is a purification technique that exploits the differential solubility of
compounds in solvents of different temperatures. A near minimum of hot solvent is
added to the crude product to dissolve it and then the mixture is allowed to cool
slowly to room temperature (4). As the temperature decreases, the compound
becomes less soluble and as the solution becomes saturated with the compound it
crystallizes out of the solution. Since crystallization is a very thermodynamically
selective process that excludes foreign particles, the compound obtained will be
pure. A minimum of ice cold solvent is then applied to remove any impurities on the
surface (4).
Thin-layer chromatography (TLC) is a chromatography technique used to separate
non-volatile mixtures. In a lab setting, TLC can be used to determine the number of
components in a mixture, verify a substances identity or monitor the progress of a
reaction (5). TLC has wide applications including analysis of ceramides and fatty
acids, detection of pesticides or insecticides in food and water, analysing the dye
composition of fibers in forensics, assaying the radiochemical purity of
radiopharmaceuticals, or identification of medicinal plants and their constituents (5).
The stationary phase used in this experiment is silica gel coated on aluminium, a
polar absorbent. On a molecular level, molecules are continuously moving back and
forth between the free and absorbed states in a dynamic equilibrium that depends on
three factors, namely the polarity and size of the molecule, the polarity of the
stationary phase and the polarity of the solvent. Since silica is polar, more polar
molecules will be more strongly attracted to the stationary phase. The two solvents

Synthesis and Characterization of Dibenzalacetone

Tan Yong Jie (m15604)
used in this experiment, hexane and ethyl acetate, are non-polar and weakly polar
respectively.
Mechanism:

Procedure:
Benzaldehyde (0.0196mol, 2.0 ml) and acetone (0.0109 mol, 0.8ml) was added to a
100ml conical flask. NaOH (0.0500mol, 2.0g) pellets were placed in ethanol
(0.343mol, 20 ml) and DI water (20 ml) and mixed well in a 100ml conical flask. This
solution was then added to the mixture of benzaldehyde and acetone and swirled
continuously for 15 minutes. The product was then collected from the filter paper by
suction filtration using DI water as poor solvent. The crude product was recrystallized using hot ethyl acetate as the solvent heated to 150C before the solvent
was removed using suction filtration. The crystals were spread on a piece of filter
paper on a watch glass and dried under IR lamp for 5 minutes. The yield and the
melting point of the product was determined using melting point apparatus and
weighing balance, respectively. A small amount of the product was removed using a
capillary tube and dissolved in 1 mL of ethanol to be used for TLC analysis. For TLC
analysis, a stock sample of benzaldehyde was used for the reactant control. A 20ml
solvent system of 10 %Ethyl acetate and 90% hexane was used for TLC analysis.
Results:
Table 1 Observed melting point range of product as determined by melting point determination apparatus
compared with theoretical melting point as determined by (6).

Observed melting point range(C)

110-112.1

Theoretical melting point(C)

110-111

Table 2 Yield of product as determined using molar mass calculations assuming product is 100% pure
(calculations shown below table).

Mass of watch
Mass of watch
glass and filter glass, filter paper
paper
and product
34.315g
34.701g
Molar ratio
Benzaldehyde : Acetone
2: 1

Mass of Theoretical Mass % Yield

product of product
0.386g

2.295g

16.8

Mass of Benzaldehyde 1.04* 2 = 2.08g

No of moles of Benzaldehyde 2.08/106.121 = 0.0196mol mol (3 s.f.)
2

Synthesis and Characterization of Dibenzalacetone

Tan Yong Jie (m15604)
Mass of Acetone 0.791* 0.80 = 0.6328g
No of moles of Acetone 0.6328/ 58.08 = 0.0109mol (3s.f.)
Compound
Acetone
Benzaldehyde
Number of moles
0.0109
0.0196
Theoretical Mol Ratio(Reaction 1
2
stoichiometry)
Molar ratio
0.0109
0.0098
Simplified Molar ratio
1.1
1
Benzaldehyde is the limiting reagent.
Therefore molar ratio of product (Dibenzalacetone) : Benzaldehyde is 1:1.
Theoretical number of moles of product = 0.00980 mol
Theoretical Mass of product: 0.0098* 234.29 = 2.296g
Table 3 Observations recorded for reaction steps
Step
Mixture of reactants in 100 ml conical
flask
Collection of crude product by suction
filtration

Observation
Heat was produced and a yellow
precipitate was formed in a clear solution.
A small amount of yellow crystal was
collected on the filter paper. The filtrate
was cloudy and yellow with lost product.
A minute amount of yellow solid was
recovered from the filter paper.

Collection of pure product after

recrystallization and suction filtration
0.5cm

Solvent front

3.5cm

Baseline
*
R

*
C

1cm

Figure 1 Drawing of TLC plate. R= Reactant (Benzaldehyde), C=co-spot, P= Product (Dibenzalacetone).

Solvent system: 10% ethyl acetate and 90% hexane.

Table 4 Rf values for the reactant and product in 10% ethyl acetate and 90% hexane.
Analyte
Rf
Reactant- Benzaldehyde
1.7/3.5 = 0.486
Co-spot- Spot further from baseline
1.8/3.5=0.514
(Benzaldehyde)
Product- Dibenzalacetone
1.4/3.5=0.4
3

Synthesis and Characterization of Dibenzalacetone

Tan Yong Jie (m15604)
Co-spot- Spot closer to baseline
(Product )

1.4/3.5=0.4

Discussion:
This experiment is a mixed aldol condensation reaction. It is also known as a ClaisenSchmidt reaction, which involves a reaction between an aldehyde (benzaldehyde) and
a ketone (acetone) catalysed by a base (NaOH). This reaction is exothermic and thus
releases the heat observed due to the two dehydration reactions and formation of new
bonds in a stable product Dibenzalacetone which has higher melting and boiling
points than the reactants. The extensive conjugation of dibenzalacetone causes it to
absorb light in the visible spectrum at ~400 nm, resulting in a yellow colour. This is
due to the delocalisation of electrons in the cloud that results in a lowering of the
promotional energy required for an electron to jump into a higher energy orbital.
Based on the beer equation the energy is low enough such that visible light has
enough energy to allow the electrons to be promoted to the next orbital, and
absorbance of purple light near 400nm results in a yellow colour. Dibenzalacetone
precipitates out of the solution because it is not soluble in water.
A 2:1 molar ratio of acetone to benzaldehyde is used so that the aldol condensation
will occur on both sides of acetone and yield the most product. However, it might still
be possible that mono-substituted acetone (benzylideneacetone) might be
contaminating in the product. Benzylideneacetone has a much lower boiling point at
near 39-42 C compared to dibenzaleacetone. It is of a paler yellow compared to
dibenzaleacetone. In addition, it is also UV active due to the presence of the benzene
ring. Thus TLC analysis will be able to identify if it is a contaminating factor in the
product obtained. Benzylideneacetone is less polar than dibenzaleacetone and thus
might absorb less onto the stationary phase and thus travel further in the solvent.
However, the possibility of benzylideneacetone should be as the 2:1 molar ratio
should be able to discourage the formation benzylideneacetone (Excess benzaldehyde
is not used since this leads to a sticky product due to side reacctions).
Other possible side products include mesityl oxide resulting from the selfcondensation of acetone. However, mesityl oxide has a high boiling point and low
melting pont of only -41.5C, it is in a liquid state and thus will likely be filtered of
during suction filtration.
The product, benzylideneacetone, is insoluble in water and thus large amounts can be
used to wash away impurities without affecting yield. The main impurities should be
sodium compounds which can be washed of in water such as sodium carbonate which
results from the failure to remove sodium hydroxide completely during suction
filtration. Lowering the concentration of sodium hydroxide can reduce the formation
of sodium by products but can also increase the chance of benzylideneacetone
contamination. Anhydrous sodium carbonate has a high melting point of 851 C, but
monohydrates and heptahydrates have much lower melting points of 100 C and 33.5
C respectively. Thus melting point analysis will be more likely to detect this
impurity.
For TLC, the results show that the product dibenzalacetone is slightly more polar
compared to the benzaldehyde as it travels less far in the largely non polar solvent
(90% hexane 10% EA) compared to benzaldehyde (Rf=0.4 compared to average of
0.5). This might be due to more favourable interaction between benzaldehyde and the
hexane/EA mixture. However since the Rf value is about the same this might be due
to the similar polarity of the two compounds which occurs mainly due to the O
4

Synthesis and Characterization of Dibenzalacetone

Tan Yong Jie (m15604)
containing ketone/aldehyde group. From the TLC, it was found that the product did
not contain any benzaldehyde as not spot was observed at a Rf value of 0.4. This
suggests that the reactant was consumed completely or successfully removed during
filtration/recrystallization.
Experimental flaw
The compound was not pure and had a
large melting point variation that was far
from the theoretical value.

Improvements
Wash product crystals with DI water
thoroughly to remove any sodium
compound impurities before drying
under IR lamp. Use a lower
concentration of NaOH. (Take note that
lower concentrations of base may slow
formation of product and thus lead to
side reactions)
Recrystallization using a less steep
cooling curve. A controlled cooling
curve that has a less steep temperature
gradient can be used for recrystallization
by placing the product in a water bath
on a hot plate and reducing the
temperature gradually over a long period
of time to 0 C.
Crystallization was slow and crystals Use a seed crystal; A sample of pure
failed to appear after 15 minutes.
Dibenzalacetone prepared before the
solution can be used as a nucleation
factor to allow the Dibenzalacetone to
form around the crystal. Ideally a super
saturated solution should be prepared by
using a minimal amount of ethyl acetate
during recrystallization step.
The seed crystal is carefully suspended
in the solution and the container is
covered in aluminium foil in order to
keep out dust and reduce temperature
fluctuations.
The product is impure due to the Add a trace amount of activated carbon
presence
observed
of
coloured to the hot solution followed by hot
impurities.
filtration to remove the charcoal. The
activated carbon absorbs organic
compounds to the surface but also leads
to the loss of yield. Thus a small amount
should only be used if coloured
impurities such as polar or polymeric
compounds are determined to be
present.
The yield is low at only 16.8%.
Human error: Some of the product
mixture was split onto the table. Cold
solvent was not added to filter paper
before suction filtration; product
5

Synthesis and Characterization of Dibenzalacetone

Tan Yong Jie (m15604)
escaped into the filtrate. Solution:
Remember to perform steps according to
logbook and be more careful.

Conclusions:
Dibenzalacetone was successfully synthesised with a yield of 16.8% and a melting
point range of 110-112.1C.
Questions:
1) As mentioned before, benzylideneacetone will be product formed.

Benzylideneacetone
2)

References:
(1) Holleman, A. F.; Wiberg, E. Inorganic Chemistry; San Diego: Academic Press,
2001; pp 1732.
(2) Lyday, P. A. Iodine and Iodine Compounds. In Ullmann's Encyclopedia of
Industrial Chemistry; Wiley-VCH, Weinheim, 2005; pp 382390.
(3) Greenwood, Norman N.; Earnshaw, Alan. Chemistry of the Elements (2nd
ed.); Butterworth-Heinemann, 1997; pp 137-145.
(4) Haynes, William M. CRC Handbook of Chemistry and Physics (92nd ed.);
Boca Raton, FL: CRC Press, 2011; pp 164.

Synthesis and Characterization of Dibenzalacetone

Tan Yong Jie (m15604)
(5) Chang R. Chemistry 10th edition; McGraw-Hill: 2010; pp 5962.

(6) Conard, C. R.; Dolliver, M. A. Dibenzalacetone; Org. Synth. 1943, 2, 167.