Experiment 1:

Aldol
Condensation
Reactions
Name: Avril Watson
Student number: 14302674
Objectives:
The objectives were split into two for this experiment. Firstly, to synthesize
dibenzalacetone using the reactants benzaldehyde and acetone. Secondly, to
calculate the amount of acetophenone required to react with 2.88g of
benzaldehyde to synthesize benzalacetophenone (1,3-diphenylprop-2-en-1one) and in both cases to recrystallise from ethanol. Another objective of this
practical was to refamilarise ourselves with some lab techniques and
calculations we learned in Junior Freshman Chemistry.
Theory:
This practical was all about aldol condensation reactions. An aldol
condensation reaction is very important in organic chemistry as it is a perfect
way to create carbon-carbon bonds. Firstly an aldol reaction occurs with the
use of the hydrogen atom on an alpha carbon. At least one of the reactants
must have an alpha hydrogen or the reaction does not work. It involves a
reaction with an enol or enolate ion to form an aldehyde or a ketone. It is
then dehydrated, resulting in a conjugated enone, i.e. a double or triple bond
separated by a single sigma bond. Generally it forms an alkene.
In the first steps of both of these reactions, when there is aldol addition, the
product undergoes a loss of water made from the alpha hydrogen and the
hydroxyl group from sodium hydroxide. The water lost is then used in the
condensation reaction to regenerate the OH- molecule from the base
catalyst. It is important to note that each condensation reaction must start
with formation of an aldol product that can then be dehydrated to the enone.
The first product formed from part 1 of the experiment was dibenzalacetone.
This is a dimer of benzaldehyde and acetone. The benzaldehyde does not
have an alpha hydrogen and therefore it can only act as an acceptor
reactant, meaning the acetone is the electrophile in this reaction (ref 1).
Usually in aldol reactions there are 4 products, but because one of the
reactants has no alpha hydrogens it can only make 2 products. These two
products are a mixture of stereoisomers. The same principle applies for the
synthesis of benzalacetephenone. This is also a dimer made up of
benzaldehyde and acetophenone.
Melting points are very useful in chemistry. They give us an idea as to
whether a compound contains impurities or not. It the the temperature range
in which a solid melts into a liquid. The melting point range of
dibenzylacetone is 110-111 C (ref 2) and benzylacetophenone is 57-58 C
(ref 3). All of the reactants used in the practical were flammable and some
were skin irritants so it was important to wear gloves to protect our hands.
Sodium hydroxide is classified as corrosive so wearing protective eye wear
was essential.
Procedure:

All essential apparatus was set up accordingly to synthesize both

dibenzylacetone and benzylacetophenone. The practical was completed in
two parts.
For the first part, a mixture of sodium hydroxide (40mL; 2M) and ethanol
(30mL) was made in a clonical flask. To a separate beaker, benzaldehyde
(2.77mL) and acetone (1mL) were added. Half of the benzaldehyde and
acetone mixture was added to the clonical flask with the sodium hydroxide
and ethanol in it. The contents were swirled and left alone for 15 minutes.
After the 15 minutes elapsed, the remaining mixture in the beaker was added
to the clonical flask. This was then swirled again and left for a further 30
minutes.
In the meantime, the calculations were completed for the second part of the
experiment and the same apparatus set up for the synthesis of
benzylacetophenone.
The same approach as the previous part was taken. A mixture of sodium
hydroxide (40mL; 2M) and ethanol (30mL) was made in a clonical flask. In
another beaker, benzaldehyde (2.77mL) and acetophenone (3.15mL) were
mixed. Half of this mixture was added to the clonical flask, swirled and left for
15 minutes. After 15 minutes, the remaining mixture was added to the
clonical flask, swirled and left sit for a further 30 minutes.
After both mixtures were left for 30 minutes they were dried off using a
vacuum filtration. Each product was placed into its own Buchner funnel and
sucked dry. When each product was dry, it was washed with 3 aliquots of
deionised water (3x 60mL).
The crystals formed in each case were recrystallized by dissolving each set in
ethanol and using heat from the hot plates. Both solutions were then placed
in an ice bath and scratched until crystals formed. Both solutions were then
sucked dry again using a vacuum filtration again. The dried crystalline
products were weighed and the melting point ranges determined for each
solid. The percentage yield was then calculated before cleaning and tidying
away all glassware used in the experiment.
Results:
Product A: Yield: 0.07g

Percentage yield: 1.9% (after recrystallization)

Melting point range: 98-102

Product B: Yield: 3.72g Percentage yield: 60.74% (before recrystallization)

**___ I made a few mistake throughout the lab which left me with no valuable
results. These results are my neighbour Ciara O Flynns results. We ran out of
time before we could recrystallize the product and obtain the melting point
range for Product B. I will talk about this further in my discussion on the
experiment.___**
Discussion:
I made a few errors in the practical which left me without my own results. My
first mistake occurred while recrystallizing product A with ethanol. While

trying to wash the product from the inside walls to try and get as much
product in as possible, I think I used too much ethanol. The solution was a
transparent yellow colour when it should have been a cloudy yellow colour. I
may have over diluted the solution which in turn affected the reformation of
crystals. No crystals formed at all even with a lot of scratching.
The second error made was with the formation of crystals in product B.
During the 15 minute waiting period after adding the first half of the
benzaldehyde-acetophenone solution, I accidently threw out the other half
while trying to clean as I went along with the experiment. However, I didnt
realise until it was too late to fix the problem. There was not enough of the
benzaldehyde-acetophenone solution to make the reaction take place. This
resulted with no oil at the bottom of the flask and hence no crystal formation.
Instead I was advised to evaluate my neighbours results. The experiment
took a lot longer than expected. The percentage yield of the product A is very
very low. This could be a result of numerous errors that occurred throughout
the experiment. On a few occasions, the vacuum filtration sucked back
resulting in the loss of some of Product A. Also, during recrystallization, a
slight excess of ethanol may have diluted the solution too much as the
crystals that formed were very small which also explains why the percentage
yield was quite small. The melting point is also not as accurate as we
expected. Its not too off but in theory it should have been 110-111 C when
it was actually 98-102 . This is probably due to impurities still left in the
sample due to inadequate washing with deionised water and also perhaps the
excess of ethanol.
There wasnt necessarily any errors made for product B except for the fact
that we ran out of time to finish the experiment. This resulted in a
reasonable percentage yield that probably would have been a good bit lower
minus the impurities left in the sample. Id also expect the melting point to be
lower than what it is according to the literature value because of these
impurities.
The calculations were fairly straight forward and easy to do. They can be
seen at the back of this report.
Conclusion:
Overall, this was a very educational experiment. It refreshed my memory on
how to conduct aldol reactions. The two products were successfully
synthesized and any errors made were noted and understood.

References:
1. William Reush, Professor Emeritus (Michigan State U.), Virtual Textbook
of Organic Chemistry.
(http://chemwiki.ucdavis.edu/Organic_Chemistry/Reactivity_of_Alpha_H
ydrogens/Aldol_Reaction)
2. Drug Lead (http://www.druglead.com/cds/dibenzalacetone.html)

3. MP Biomedicals (https://www.mpbio.com/product.php?
pid=05209059&country=103)