Solvent Free Synthesis of an ,-

Unsaturated Ketone
Authors Name
Putramica Winarto
putrahhh@gmail.com
ABSTRACT
The formation of ethyl 2-oxo-4,6-dip-tolylcyclohex-3-enecarboxylate stemmed from the Microwave Irradiation of the
chalcone (E)-1,3-dip-tolylprop-2-en-1-one that resulted in a Robinson Annulation and the formation of the product
was not completely successful.
This experiment consisted of two parts, first among which
involved the creation of the chalcone by grinding
equimolar 4-methylbenzaldehyde and 4-
methylacetophenone in porcelain mortar with the use of
solid sodium hydroxide as the base catalyst.
1
After the
chalcone was created the melting point and the IR was
obtained. The melting point of the chalcone was 124C
and the literature melting point is 127C which indicates
that the product was relatively pure. IR of the chalcone
presented peaks at 1652.87

cm
-1
which is indicative that
the product has a conjugated ketone. There is also a peak
at 1591.09

cm
-1
which belongs to the aromatic rings and
at 809.36 cm
-1
there is a peak that suggests the benzene is
disubstituded and the groups are para to each other. Once
the chalcone product was verified, converting the
chalcone via Robinson Annulation could proceed. In the
second part of the experiment, the product was placed
into a microwave after being mixed with ethyl
acetoacetate and potassium carbonate.
2
After mixing the
reactents together, the solid was microwaved for 3
minutes on medium power which changed the color of the
solid to more a white color rather than a yellow color.
Robinson Annulation via microwave irradiation resulted
in a 33.33% product yield. IR of the product presented a
peak at 1738.73 cm
-1
which comes from the carbonyl of
an ester and one at 1653.91 cm
-1
from the conjugated
ketone carbonyl. At 1241.69 cm
-1
there is a carbon to
oxygen stretch that arises from the ester as well as a peak
that results from the aromatic rings at 1594.11 cm
-1
. The
IR of the crude procut was obtained and it offered a peak
at 1715.81 cm
-1
which indicates that the crude contains
unreacted ethyl acetoacateate. Because it was so,
recrystallization of the product in 95% ethanol was
necessary as ethanol-dioxane solvent was not readily
available. The crude was recrystallized using an ice bath,
cold ethanol, and a vacuum filtration and the IR obtained
lacked the 1715.81 cm
-1
peak which means
recrystallization of the crude was successful. Obtaining
the crude was a journey in and of its own because the
crude product melted in the oven after being filtered and
turned into a yellow, pasty, goopy liquid/solid mix. As a
result, the crude had to be dried through other means.
First the crude was dissolved completely in
dichloromethane and then it was dried with anhydrous
magnesium sulfate. After the crude was dried and
decanted, the remaining liquid was evaporated off in the


hood through the use of a stream of air until only solid
remained. The solid was then dissolved in hot ethanol and
recrystallized as stated above. The final solid was not
dried in the oven at first for fear that the end result would
mimic that of the crude, and the IR was taken after letting
it air dry. The IR showed an OH peak because of the
ethanol and an executive decision to put the final product
in the oven was made. After being in the oven for an
entire day the IR of the final product was taken once
again and it revealed a smaller OH peak which means the
ethanol has yet to dry completely. After the IR was taken,
the melting point followed suit. However, this proved to
be a problem as well.The final product did not melt at all,
instead it burned inside the melting point device; it
changed from a white-yellow color to a solid yellow color
before turning into a golden yellow color. The yellow got
darker and darker until eventually it turned black.
Because the first melting point was not successful another
melting point was taken and unfortunately the results
were the same. It can be deduced from the experiment
form that the melting point of the product should be in the
110s-120s as the form indicated a compound of similar
build (except it had OH instead of methyl for its R group)
and the melting point was 111-112C.
3
This of course,
indicates that the product isnt pure at all and something
must have happened during the procedure, chief among
which, the microwave irradiation bit. The crude was set in
the 500-wat microwave for 3 minutes on medium and
resulted in little color change, however, when the crude
was set in the oven on high for 4-5 minutes, a massive
color change was observed. This lack of color chang e
indicates that perhaps the crude did not react completely
with the ethyl acetoacetate. Regarldess of the result, the
final product is at least, not the chalcone that was used as
a reactant in this experiment.
(1) Palleros, Daniel R. Solvent-free Synthesis of
Chalcones. PDF file.
(2) Priya V Frank, B'alakrishna Kalluraya, and
Shobhitha Shetty. Microwave Assisted
Robinsons Annulation: Synthesis of some novel
cyclohexanones under solvent free conditions.
PDF file.
(3) Casale, Kristin. Preparation of an ,-unsaturated
ketone via Michael and Aldol Condensation
Reactions. Chemistry 421 Lab Manual.
Chemistry Department, American River College.









Experimental Procedure. This experiment started off
with the addition of 0.00286 moles of ethyl acetoacetate
(0.360 mL) to .3362 grams (.00142 moles) compound 1.
0.00571 moles or .7897 grams of potassium carbonate
was also added. All three reactants were crushed by a
pestle in a mortar and then put inside a microwave under
medium heat for 3-4 minutes. Afterwards the crude
product was put under vacuum filtration and a small
amount of cold water was ran through it (<20 mL). After
letting the solid dry under suction for 3 minutes, place the
crystals in the oven to dry for 20-30 minutes. Chop up the
solid to ensure even drying. After 20-30 minutes have
passed, take the product out of the oven and let it cool to
room temperature before placing it inside a small beaker
or Erlenmeyer flask. As the product is cooling, acquire
20-30 mL of 95% ethanol and set some aside to put into a
centrifuge tube as cold ethanol will be needed. Prepare an
ice bath to put the centrifuge tube in. Place the remaining
ethanol on a hot plate and wait until it bubbles. Once the
solution is bubbling or near bubbling, use a Pasteur
pipette to transfer minute amounts of hot solvent to the
crude. Remember that the crude shold be dissolved in the
minimum amount of solvent to lessen yield loss. Once the
crude is completely dissolved by the hot ethanol, allow
the mixture to room to cool temperature. At this point you
may fill a beaker up with room temperature water and
place the beaker or Erlenmeyer flask inside for faster
cooling. After the product is cooled to room temperature,
place the beaker or flask inside the ice bath and swirl it
around. To aid in the recrystallization process, proceed to
scratch the inside of the beaker or flask with a glassrod to
induce crystallization. Repeat this process as many times
as necessary while swirling the beaker or flask when
required. You may also add in tiny tiny chunks of ice to
help. When the mixture has recrystallized completely,
pour the contents onto a Buchner funnel and vacuum
filtrate the solid. Wash the glassware with small portions
of cold ethanol and pour contents over the funnel. You

may also wash the solid inside the funnel with cold
ethanol. Allow solid to be under suction for at least 3
minutes. Place the solid in a preweighed beaker or watch
glass and place it inside the oven. Let it dry for 20-30
minutes again. Remove the product from the oven and
allow it to cool to room temperature before taking the
mass. Obtain the IR and melting point once the mass has
been taken. The IR and melting point should indicate that
compound 2 has been created.
Acknowledgment I would like to acknowledge
Michael Tomolillo who encountered the same unfortunate
fate as I when drying the crude product. Id also like to
thank Ariel, Beverly, Carol, and Don who were all more
than willing to share the vacuum filtration system that
they had set up. And to Kristin Casale who hath put up
with onslaughts of questions and is this ok?