Experiment 2

CHEM 613
Experimental Organic Chemistry
2013
Anastazija Ristovska

Post-Lab
Claisen-Schmidt Condensation

The purpose of this reaction was to use acetone to merge two benzaldehyde molecules
into dibenzalacetone in basic environment and ethanol via a condensation reaction on both keto carbon atoms of acetone. 1284mg benzaldehyde was reacted with 338mg acetone in a 2:1
molar ratio. They were dissolved in 6ml 95% ethanol solvent and 2ml 10% sodium hydroxide
solution was added. Upon vigorous swirling a precipitate began forming. 20min later the solution
changed color from dark yellow after the addition of sodium hydroxide, to cappuccino color
after swirling and 20min into the reaction. The more we swirled the more blurred and opaque
the solution became, forming so much precipitate that soon virtually no liquid was left. The
product, dibenzalacetone, was collected and its mass was found to be 1024mg. The theoretical
yield was 1417mg, and thus the percent yield was 72.2%.
Reaction & Mechanism
A cross-aldol condensation is an advanced form of aldol concensation also known as
Claisen-Schmidt condensation in which the carbonyl compound, in our case benzaldehyde, does
not have an - hydrogen. The dibenzalacetone synthetic reaction is the most often mentioned
example of Claisen-Schmidt condensation. It is a reaction between a ketone and two aldehyde
molecules in which a condensation occurs between two aromatic aldehyde molecules and an
aliphatic ketone in basic environmentresulting in an ,-unsaturated ketone formation with high
chemical selectivity. Even though in our experiment we did not apply these techniques, the
reaction can be accelerated by applying magnesium oxide crystals as catalyst or using microwave
activation to accelerate the reaction. It is commonly known that reactants without substituents
on the benzene ring as benzaldehyde is have a faster reaction rate than reactants with substituent
groups on their benzene rings.
It is only possible that one product forms in Claisen-Schmidt condensation since the
aromatic aldehyde lacks -hydrogens. A reactant that does contain -hydrogens will allow for the
formation of four different compounds. The product obtained in a Claisen-Schmidt
condensation has the double bond produced during dehydration conjugated both to the benzene
ring as well as the carbonyl group.

Therefore 1,5-diphenyl-1,4-pentadien-3-one represents a system of 9 conjugated double

bonds and absorbs UV light. As any compound with the ability to absorb, reflect or scatter UV
rays, dibenzalacetone is a suitable ingredient for sunscreens because of its ability to protect the
skin from the harmful UV rays. The reaction mechanism is given in Figure 1.

Figure 1
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Figure 2
In this benzaldehyde IR spectrum the most important characteristic to notice is the carbonyl
peak at 1703cm-1. All the other peaks around 3000cm-1 are due to aromatic C-C in ring or C-H
bond vibrations.

Figure 3
The molecular ion peak is at m/z=106. The peak at m/z=77 comes from the benzene ring
without the aldehyde functional group attached to it.
3

Figure 4
The dibenzalacetone mass spectrum shows the molecular ion at m/z=234 as the peak
with greatest relative intensity, and there are other three dominant peaks at m/z=77 for a
benzene rings with no substituents, a peak at m/z=103 for a fragment of the molecule that has a
benzene ring with ethenyl group attached to it, and a peak at m/z=131 for a fragment that has
occurred after a benzene ring together with an ethenyl group has been severed molecule and
whats left is a fragment with a benzene ring and a carbon chain of three carbon atoms and
oxygen at the end of it.
In the H NMR spectrum of benzaldehyde shown in figure 5 we can see the aldehyde
proton at 10ppm not split by any other protons, whereas the benzene ring protons are all close
to each other in the 7.5 to 8.0 ppm region, with the ortho and para hydrogens peaks being more
downfield. The ortho hydrogens are around 7.9ppm, the para protons are at 7.6ppm, whereas
the meta protons are at 7.5ppm, being the least deshielded ones. The aldehyde group is
moderately deactivating and meta directing with respect to the benzene ring reactivity with
electrophiles.
In the dibenzalacetone H NMR spectrum shown in figure 6 we can see that the aldehyde
proton peak is no longer present, and all peaks are in the 7.0 to 7.7ppm range. The least
dishielded are the -protons to the carbonyl group at 7.0ppm, whereas the most dishielded
protons are the -carbonyl protons at 7.7ppm. The protons on the benzene ring that are closest
to the substituent are likewise disheilded and thus downfield.

Figure 5

Figure 6
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