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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).
110-112.1
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
2.295g
16.8
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.
Solvent front
3.5cm
Baseline
*
R
*
C
1cm
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
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
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
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.