Jacob Lytle

CHEM 2020-PA
March 23, 2010
Preparation of an α,β-Unsaturated Ketone
via Michael and Aldol Condensation Reactions
Introduction

An α,β-unsaturated ketone can be prepared by conjugate addition of ethyl acetoacetate to

trans-chalcone followed by an intermolecular Aldol condensation reaction and dehydration.
A Michael reaction is the nucleophilic addition of an α,β-unsaturated carbonyl compound. The
substituents on the Michael donor, the nucleophile, are electron-withdrawing carbonyl groups. This
causes the formation of an enolate anion in the presence of a base, (step 1). The substituent on the
Michael acceptor, the activated alkene, reacts at the β-carbon with the enolate anion, (step 2). The
Michael reaction results in a 1,5-dicarbonyl compound.

Then, in the presence of base, the carbonyl portion of the compound that contains an α-carbon
with at least two hydrogens is deprotonated, (step 4). The Aldol condensation reaction is an electrophilic
substitution at the deprotonated α-carbon. The Aldol reaction forms a new carbon-carbon bond. In this
case, the reaction is intramolecular, which always causes the formation of a ring, (step 5). Then resulting
negatively charged oxygen is then protonated and dehydrated by the base, (step 6,7). The result is an
α,β-unsaturated ketone. Here, the α,β-unsaturated ketone is very stable due to the conjugation of the
double bond with the both a carbonyl group and a phenyl group.
Procedure

Chemical Amoun
t
trans-chalcone 1.212 g Apparatus and Material
ethyl acetoacetate 0.750 g 50 mL round bottom flask
sodium hydroxide 0.120 g Centrifuge and tube
ethanol 30 mL Vacuum filter
reagent- grade 7.0 mL
Oven
acetone
water 10 mL Buchner funnel
Spatula
Pasteur pipette
Hot plate

Assembling the apparatus. To a 50-mL round bottom flask, add 1.2g of finely ground trans-chalcone,
0.75 g of ethyl acetoacetate, and 25 mL 95% ethanol. Swirl the flask until the solid dissolves and place a
boiling stone in the flask. Add 1 pellet (between 0.090 and 0.120g) of sodium hydroxide. Weigh the
pellet quickly before it begins to absorb water. Attach a reflux condenser to the round-bottom flask and
heat the mixture to reflux using a hot plate or heating mantle. Once the mixture has been brought to a
gentle boil, continue to reflux the mixture for at least 1 hour. During this reflux, the mixture will become
very cloudy and solid may begin to precipitate. The mixture may bump during the reflux. If this happens,
the solid in the reaction flask starts to “erupt” and throws solid up into the reflux condenser. You will
need to reduce the temperature of the hot plate or heating mantle to avoid this problem.
Isolation of the Crude Product. After the end of the reflux period, allow the mixture to cool to room
temperature. Add 10 mL of water and scratch the inside of the flask with a glass stirring rod to induce
crystallization (an oil may form; scratch vigorously). Place the flask in an ice bath for a minimum of 30
minutes. It is essential to cool the mixture thoroughly in order to completely crystallize the product.
Because the product may precipitate slowly, you should also scratch the inside of the flask occasionally
over the 30-minute period and cool it in an ice bath.

Vacuum filter the crystals on a Buchner funnel, using 4 mL of ice-cold water to aid in the transfer. Then
rinse the round-bottom flask with 3 mL of ice-cold 95% ethanol to complete the transfer of the
remaining solid from the flask to the Buchner funnel. Allow the crystals to air dry overnight.
Alternatively, the crystals may be dried for 30 minutes in an oven set at 75-80°C. Weigh the dry product.
The solid contains some sodium hydroxide and sodium carbonate, which are removed in the next step.

Removal of Catalyst. Place the solid product in a 100-mL beaker. Add 7 mL of reagent-grade acetone
and stir the mixture with a spatula. 2 Most of the solid dissolves in acetone, but do not expect all of it to
dissolve. Using a Pasteur pipet, remove the liquid and transfer it into one or more glass centrifuge
tubes, leaving as much solid as possible behind in the beaker. It is impossible to avoid drawing some
solid up into the pipet, so the transferred liquid will contain suspended solids, and the solution will be
very cloudy. You should not be concerned about the suspended solids in the cloudy acetone extract
because the centrifugation step will clear the liquid completely. Centrifuge the acetone extract for
approximately 2-3 minutes, or until the liquid clears. Using a clean, dry Pasteur pipet, transfer the clear
acetone extract from the centrifuge tube to a dry, preweighed 50 mL Erlenmeyer flask. If the transfer
operation is done carefully, you should be able to leave the solid behind in the centrifuge tube are
inorganic materials related to the sodium hydroxide originally used as the catalyst.

Evaporate the acetone solvent by carefully heating the flask in a hot water bath while directing a light
stream of dry air or nitrogen into the flask. Use a slow stream of gas to avoid blowing your product out
of the flask. When the acetone has evaporated, you may be left with an oily solid in the bottom of the
flask. Scratch the oily product with a spatula to induce crystallization. You may need to redirect air or
nitrogen into the flask to remove all traces of acetone. Reweigh the flask to determine the yield of this
partially purified product.

Crystallization of Product. Crystallize the product using a minimum amount (approximately 9 mL) of
boiling 95% ethanol.3 After all the solid has dissolved, allow the flask to cool slightly. Scratch the inside
of the flask with a glass stirring rod until crystals appear. Allow the flask to sit undisturbed at room
temperature for a few minutes. Then place the flask in an ice-water for at least 15 minutes. Collect the
crystals by vacuum filtration on a Buchner funnel. Use three 1-mL-portions of ice-cold 95% ethanol to
aid in the transfer. Allow the crystals to dry until the next laboratory period or dry them for 30 minutes
in a 75-80°C oven. Weigh the dry 6-ethoxycarbonyl-3,5-diphenyl-2-cyclohexenone and calculate the
percentage yield. Determine the melting point of the product (literature value, 111-112°C). Submit the
sample to the instructor in a labeled vial.
Procedural Data Tables

Molecular Weight
Compound Mass (g) Moles (mol) Melting point (C)
(g/mol)
Ethyl acetoacetate 130.14 0.750 5.76 x 10^-3 -45
Charlcone 208.26 1.212 5.82 x 10^-3 55-57
6-ethoxycarbonyl-3,5-
diphenyl-2- 320.21 0.011 3.44 x 10^-5 111-112
cyclohexenone

Results Data

Experimental
Actual Yield Theoretical Yield Percent Yield
Melting Point
0.011 g 1.86 g 0.596 % 107.3-107.8 C

Theoretical Yield

0.750 g
Ethyl
1 mol 320.21 g
acetoacetat
e = 1.845 g limiting reagent
130.14g
Ethyl
1 mol
acetoacetate

1.212 g = 1.864 g
1 mol 320.21 g
Chalcone
208.26 g
1 mol
Charlcone

Percent Yield

Actual Yield
% Yield = Theoretical Yield X 100
 0.011 g X 100=0 .596 %
1.845 g
Discussion

A Michael reaction followed by an Aldol condensation produced 6-ethoxycarbonyl-3,5-diphenyl-2-

cyclohexenone. The reaction was a one to one ratio and the theoretical yield was determined by finding
the limiting reagent. In this case, it was ethyl acetoacetate. The theoretical yield was 1.845g and the
experimental yield was 0.011 g. Therefore the percent yield was 0.596 %. The low percentage yield was
due to the container with the product being dropped and spilled near the end of the experiment, just
before being weighed. The 0.011g of product was the only amount recovered.
The melting point of the product was between 107.3-107.8 C°. However, the literature melting
point was 111-112 C°, which indicates that the product had some impurities present.
In a Michael and Aldol reaction, the base is a catalyst. In the experiment the base was sodium
hydroxide. The first two steps of the mechanism, the Michael reaction and step three through seven is
the Aldol reaction.