CHEM 2120 W15

CHEM 2120 Experiment 5

Crossed-Aldol Condensation
Objectives
i. To synthesize dibenzalacetone from benzaldehyde and acetone using the important
Aldol condensation reaction (carbon-carbon coupling) on the microscale:
CHO

OH-

benzaldehyde

dibenzalacetone

ii. To purify the microscale product by recrystallization.

Introduction
The most characteristic reaction of the carbonyl group is the addition of nucleophiles at
the electron-deficient carbon. If the nucleophile is a carbanion (or at least an electronrich carbon atom) we have one of the most convenient ways of making CC bonds for
the synthesis of complex carbon skeletons. In the aldol condensation, an aldehyde or
ketone is able to provide both components for such an addition, since the -hydrogens
are acidic, and in a sodium hydroxide solution a small amount of the nucleophilic
enolate ion is formed.
The aldol reaction involves several steps (see figure 2 below):
i. base-catalysed generation of an enolate anion
ii. nucleophilic attack of this anion on a carbonyl carbon
iii. protonation of the resulting anion to yield the initial aldol product

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Note that each step in the sequence is in equilibrium and the entire reaction is therefore
reversible. Treatment of the -hydroxy carbonyl compound with base causes the
reverse aldol (retro-aldol) reaction to occur.

O
R1

C CH3

OH

R1

O
CH2

R1

CH 2

an "enolate" anion

O
R2

C R3

H 2C

O
R1

R2

C R1

CH2

R3
nucleophilic attack

OH
R2

CH2

C R1

R3
aldol product
(a beta-hydroxy carbonyl compound)

Figure 2. Generalized Aldol reaction mechanism.

H 2O

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Aldols readily lose water (dehydration) to complete the condensation process (of which
the above addition is the first stage).

OH
R2

C
R3

CH2

C R1

R2
C

CH2

C R1

H2O

R3

Note that the C=C bond and the C=O bond are conjugated, this resonance stabilization
provides the driving force for the dehydration. The dehydration is usually acid catalysed
but it can also occur in neutral or even basic conditions especially when the newly
forming C=C bond is conjugated (for example, in the product of this experiment).
In a self condensation there is only one type of carbonyl compound (e.g. acetaldehyde
(where R1, R2 = H and R3 = CH3 in figure 2) that reacts with itself. In crossed or
mixed aldol condensations, two different reacting carbonyl compounds (aldehydes or
ketones) are used. Crossed aldols are usually synthetically poor reactions since they
yield product mixtures (why a mixture?). However, they can be useful synthetically if
one component has no -hydrogens (and hence cannot generate an enolate ion). In
addition, the aldehyde carbonyl is more reactive towards nucleophiles than is the ketone
and this fact may be used to advantage.
In this experiment, propanone (acetone) condenses with 2 moles of benzaldehyde (in 2
separate condensations) giving 1,5-diphenyl-1,4-pentadien-3-one (dibenzalacetone)
via a crossed aldol reaction (Figure 1 above). Note that the intermediate alcohols lose
water spontaneously to give the unsaturated product. This reaction is one of many
variations, known collectively as BASE-CATALYSED CONDENSATIONS.

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Prelab Preparation
1. Reading. Read Lehman's Student lab Companion (2nd ed) p. 280 on alkene C=C stretches
and p. 284-285 on ketone and aldehyde C=O stretches. As per the write up questions below,
refer to the posted IR spectra of pure dibenzalacetone and identify the C=O and C=C
stretching bands of dibenzalacetone (give the frequencies).
View the following YouTube videos on the Aldol mechanism and laboratory method:
http://www.youtube.com/watch?v=3XiHrsZNZko (active 2014)
http://www.youtube.com/watch?v=xYvzciNQiao (active 2014)

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2. Write the Introduction for the lab report before the lab and submit a copy to the TA at the
beginning of the lab; only this version will be marked by the TA and included in the report
mark, ie. any changes made to the Introduction after the lab will not be marked. Details on
what to include in the Introduction are given in the Lab Report section of the Lab Outline file
and also specific comments in the write-up instructions in the procedure file.
3. Reagent data. Before the lab,
Make up a complete Reagent Data table in your lab notebook before the lab and submit a
copy to the TA at the beginning of the lab; this version will be marked by the TA as part of
the report mark. For your report, edit the table to give the actual amounts used for the lab;
no other changes from the originally submitted version will be marked (e.g. changing the
MW of a compound). Note that you can either (i) hand write the data table into the lab
notebook and submit a photocopy to the TA or (ii) make up the table in Excel (or WORD)
and print two copies, one to submit to the TA and one to staple into the lab notebook.
Record the following data in your hardcover labbook for each reagent and additive in the
reaction:
chemical name ; structure ; molar mass ; amount to be used (grams and mol) ;
density (of liquids) ; m.p. / b.p. ; hazards and required safety precautions

stoichiometry of the reagents and theoretical yield of product

draw the reaction equation

The reagent data and safety info can be found in the MSDS:

MSDS benzaldehyde (Aldrich web site):

http://www.sigmaaldrich.com/catalog/ProductDetail.do?N4=B1334|
SIAL&N5=SEARCH_CONCAT_PNO|BRAND_KEY&F=SPEC
MSDS acetone (Aldrich web page):
http://www.sigmaaldrich.com/catalog/ProductDetail.do?N4=179124|
SIAL&N5=SEARCH_CONCAT_PNO|BRAND_KEY&F=SPEC
MSDS dibenzalacetone (Aldrich web page):
http://www.sigmaaldrich.com/catalog/ProductDetail.do?N4=246425|
ALDRICH&N5=SEARCH_CONCAT_PNO|BRAND_KEY&F=SPEC

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Procedure
Safety Note: sodium hydroxide in ethanol solutions are highly corrosive - wear gloves
and safety goggles. (If you get sodium hydroxide on your hands, wash them with
water until the soapy feeling has gone, including around your fingernails).
Synthesis
Pipette 240 L of benzaldehyde and then 90 L of acetone into a 20 mL sample vial
containing a magnetic spin vane. Keep the vial capped to avoid evaporation of the
acetone. Next add 3 mL of the NaOH catalyst solution (pre-prepared for you).
note: the NaOH catalyst solution is prepared by dissolving 0.4 g of NaOH in 4.0 mL of water
then adding 3.0 mL of 95% ethanol.

Stir the reaction at room temperature for 30 minutes. During this time, solid yellow
product should precipitate from solution.
note: good stirring is necessary in order to avoid the formation of large clumps of product
containing partially condensed materials and trapped NaOH solution.

Collect the crude dibenzalacetone precipitate by suction filtration using a Hirsch funnel
(material coated on the spin vane should be scraped off and included to avoid product
loss). Wash the filter cake with three portions (~ 2 mL each) of distilled water to remove
NaOH (the filtrate should be neutral by the time of the last wash).
note: it is essential to remove the NaOH completely. If it is not removed well, the
recrystallization will be difficult.

Air-dry the product by maintaining the suction on the Hirsch funnel for approximately 10
min. Remove the product from the suction funnel and, if there is enough material,
gently press the solid on a small clean dry piece of filter paper (clean spatula) to dry it
as well as possible. Set aside a small portion (~ 5 mg) of the crude to be spotted on the
TLC plate. Transfer the solid crude product to a pre-weighed 50 mL E-flask (or 20 mL
sample vial) for recrystallization and record the yield.
note: if you had only a microscale amount (< 25 mg) of material, it would likely absorb into
the filter paper and be lost; therefore, instead of filtering, you would decant the
reaction solution and try using the Craig tube for recrystallization with the help of your
instructor.

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(SAFETY: DO NOT use the centrifuge without first showing your instructor that the
tubes are correctly balanced).

Recrystallization
Recrystallize the crude product from hot 95% ethanol (up to ~ 2 mL is usually needed
but it depends on your yield so you must add the hot solvent in portions; if there are
solids that do not dissolve even after adding 2 mL, use the pipette filter plug technique
to remove them). Bring the ethanol to boiling to dissolve the product, then cool to room
temp, then use an ice bath to cool further. The crystalline product should form fairly
quickly from the 95% EtOH upon cooling. After crystallization is complete, decant or
filter the solution and allow the crystals to dry then record the yield. Show your
recrystallized product to your instructor.
Analysis of Recrystallized Product
1. TLC analysis. Run TLC of (i) benzaldehyde, (ii) crude product, (iii) recrystallized
product and (iv) pure dibenzalacetone standard using 20% ethyl acetate in pentane
as the mobile phase.
note: dissolve small amounts of each of the compounds in 1 mL or less of acetone. It is very
important to dissolve the liquid benzaldehyde sample in acetone because a neat sample of
a liquid is much too concentrated to give a good TLC result. Dissolve about a half a drop or
a drop of the benzaldehyde in ~ 1 - 1.5 mL of solvent.

2. Melting Point. Record the melting point of the dry recrystallized product and
compare to the literature value.
3. Infrared Spectra. There will be time to run IR spectroscopy of several
representative student samples; your instructor will divide the class into three groups
of five students. Note that 2nd year students are not permitted to use the IR
instrument due to risk of damage to the $1500 Ge crystal; instead, your instructor
will run the samples and demonstrate the instrument to you. An example Infrared
spectrum of the benzaldehyde reagent and a genuine dibenzalacetone sample will
be posted on Blackboard for analysis.

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WRITE-UP
Full report as the "Lab Outline" file ("Laboratory Reports" section).
Introduction: Do only the following for your introduction:
Explain what an Aldol reaction is. Draw and describe each step of the mechanism for
the 2 benzaldehyde + acetone reaction to give the initial bis-(-hydroxy)carbonyl
product:
OH

Ph

OH

Ph

Make sure you use the proper terminology ie. nucleophilic attack, deprotonation, etc.,
and use the correct arrow conventions for electron movements (reproduce the same
steps shown in the generalized mechanism above in the introductory material, but give
the specific case of this product, ie. explicitly identifying the R groups etc). What is
function of the NaOH in this reaction (draw the reaction step)?
Propose and draw a reasonable mechanism for how the initial bis-(-hydroxy)carbonyl
product forms the final product dibenzalacetone.
Why is benzaldehyde + acetone synthetically useful whereas acetaldehyde + acetone
would give a complicated mixture?
What apparatus and conditions (solvent, temp., reaction time, etc) will be used for the
reaction? How will the dibenzalacetone product be isolated from the reaction mixture
and how will it then be further purified? How will the product be characterized?
Procedure: as per the "Lab Outline" file.
Data and Results: as per the "Lab Outline" file.
A reagent data and yield table is required; if, for some reason, the yield was not
obtained, you must give example yield calculations for 0.235 g crude and 0.123 g
recrystallized product.
Discussion: as per the "Lab Outline" file; in addition, address the following items:
Does the TLC show product; if so, is it pure? Are there impurities or reactants present?

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Compare the melting point of the recrystallized product with the literature melting point
for dibenzalacetone (to get the m.p., go to the Aldrich chemical company weblink listed
in the prelab prep MSDS section above)?
A concluding statement concerning whether or not your data shows that
dibenzalacetone was produced in your experiment.
Questions on IR spectra (3 marks allotted, 1 mark per question)
i. Refer to the posted IR spectra of pure dibenzalacetone and identify the C=O and
C=C stretching bands of dibenzalacetone (give the frequencies); refer to McMurry
lecture textbook chap12 and Lehman's Student lab Companion (2 nd ed) p. 280-285.
ii. An IR spectrum of a student dibenzalacetone product will be posted, compare it to
the pure dibenzalacetone, acetone and benzaldehyde spectra and comment on (i)
whether it shows product and (ii) whether it is pure product or contaminated with
reactants.
iii. Why does the dibenzalacetone C=O stretching vibration occur at a lower frequency
than the 1720 cm-1 ketone C=O peak in acetone? (hint: it is the same reason that the
benazaldehyde C=O peak at 1700 cm -1 is at lower frequency than the 3methylbutanal C=O peak at 1727 cm -1 shown on p. 284 of Lehman's text; also note
that the answer is given on p. 284 of Lehmans text).
Questions on NMR Analysis - 3 BONUS MARKS
Below are bonus questions on the interpretation of the NMR spectra for the
dibenzalacetone product. It is not required to do these for the lab report but the marks
indicated below will be awarded as bonus marks if they are done and answered
correctly. At most universities, 2nd year chemistry students are expected to be able to do
this level of interpretation, therefore it is recommended that the chemists go through
these questions to gain valuable experience and to prepare for the structure elucidation
course, CHEM 3220U. Refer to the McMurry (8th ed) chapter 13 and Lehman's Student
Companion text p. 301 - 306 which discusses interpretation of NMR spectra.
1

H and 13C-NMR NMR spectra posted to Blackboard:

pure dibenzalacetone (Aldrich)
student dibenzalacetone product W13 (pure)
a selected student dibenzalacetone product made this term

H-NMR.
note: do not attempt to interpret the splitting patterns of the aromatic 1H-NMR peaks
(7.6 and 7.4 ppm) because they violate the n+1 rule (due to long range coupling

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10

between Hs meta to each other) and there is an overlap of two multiplets at 7.4
ppm.
i. Identify the chemically inequivalent and equivalent Hs in the dibenzalacetone
structure and how many 1H-NMR peaks are expected. Explain what symmetry
features cause what Hs to be equivalent.
[1 bonus mark]
ii. Does the student benzalacetone product 1H-NMR spectrum posted to Blackboard
(from this year) show pure product or are there significant impurity or side product
peaks? Does the NMR spectrum show any unreacted reactants?
[0.5 bonus marks]
13

C-NMR.
note: the three closely spaced peaks at 77.0 ppm in the 13C-NMR spectrum are caused
by the CDCl3 solvent that the sample is dissolved in, thus they have nothing to do
with the product and should be ignored.
i. Identify the chemically inequivalent and equivalent Cs in the dibenzalacetone
structure and how many 13C-NMR peaks are expected. Explain what symmetry
features cause what Cs to be equivalent. Does the 13C-NMR of pure benzalacetone
give the number of peaks expected?
[1 bonus mark]
ii. Does the posted student benzalacetone product 13C-NMR spectrum show the
expected peaks? Is the product pure or are there significant impurity or side product
peaks? Does the NMR spectrum show any unreacted reactants?
[0.5 bonus marks]