Experiment #5: ALDOL CONDENSATION: SYNTHESIS OF DIBENZALACETONE

Cecilia, Jasmin S. (1), Fami, Isabela N. (2), Marteja, Alexandra Leigh M. (3), Pangilinan, Dianne G. (4)
Group 3, CHEM 36, LB2B, Mr. Mark Jeremiah Cleofas
October 24, 2019

I. ABSTRACT
Aldol condensation is an organic reaction in which an enol or an enolate ion reacts with a carbonyl
compound to form β-hydroxy aldehyde or β-hydroxyketone, which is then dehydrated to become a conjugated
enone. This reaction is used extensively for the synthesis of new C-C bonds; and thus make larger organic
molecule. Claisen-Schmidt condensation is a crossed-aldol reaction involving an aldehyde or ketone enolate
with an aromatic carbonyl compound that lacks an α-hydrogen. In this experiment, acetone was reacted with
benzaldehyde, dissolved in ethanol and catalyzed by 10% NaOH. The precipitates formed were vacuum
filtered and crystallized using cold ethanol as the solvent. The synthesized dibenzalacetone crystals were light
yellow in color. A percent yield of 45.80% and melting point of 104°C to 113°C was obtained which implies the
presence of impurities in the yielded product caused by side reactions and errors in procedure. Slower cooling
and use of minimal amount of solvent are recommended to increase the yield of dibenzalacetone.

II. KEYWORDS: aldol condensation, carbanion, carbonyl, enolate, Claisen-Schmidt condensation,

dibenzalacetone

III. INTRODUCTION The reaction may be catalyzed by acids or

Aldehydes and ketones are organic bases. The intermediate formed is frequently not
compounds with a carbonyl functional group, C=O, isolated due to water being eliminated to form a
of which its polarity attributes to the reactivity of stabilized conjugate system, the α,β-unsaturated
aforementioned compounds.[1,2] In line with its compound. The product results in the addition of
structure, a base such as hydroxide can abstract one molecule of an aldehyde or ketone to the
these ɑ-hydrogen atoms to form a carbanion second aldehyde or ketone wherein the α-carbon,
(negatively charged carbon) and water. However, in the form of an enolate ion, of the first molecule
this form is unstable; hence, resonance becomes attached to the carbonyl carbon of the
stabilization is achieved through enolate. In second molecule.[6]
addition, under acidic conditions, enols are formed
in which one ɑ-hydrogen has been abstracted and
replaced on the oxygen atoms of the carbonyl.[3]
Consequently, the formation of enols and enolates
(Figure 1) is an important source of carbon
nucleophiles; in this case, carbanion, to make new
C-C bonds in the future reactions.[4]

Figure 2. Simple aldol reaction, from

Figure 1. Formation of enol and enolate,
http://research.cm.utexas.edu/nbauld/teach/ch610bnotes/ch19
.htm[3]
Aldol condensation is an organic reaction in
which an enol or an enolate ion reacts with a
carbonyl compound to form β-hydroxy aldehyde or
β-hydroxyketone, which is then dehydrated to
become a conjugated enone (Figure 2). This
reaction is used extensively for the synthesis of
new C-C bonds and thus make larger organic
molecules.[5,6]
https://commons.wikimedia.org/wiki/File:Simple_aldol_reaction
.png[7]
from
A crossed-aldol reaction is a reaction wherein
reactants come from different compounds and
yields multiple products due to the possible
formation of two or more enolate nucleophiles and
carbonyl electrophiles. Further, Claisen-Schmidt
condensation is a reaction mechanism involving an
aldehyde or ketone enolate with an aromatic
carbonyl compound that lacks an α-hydrogen is
called a (Figure 3). Albeit, this condensation
reaction forms only one product since there is only
one enolate and one electrophile required for this
process. The synthesis of dibenzalacetone, used
as a component for sunscreen and industrially
utilized in organometallic compounds, undergoes
this reaction mechanism; in which acetone is
condensed with two equivalent of
benzaldehyde.[6,8]
Figure 2. Formation of chalcone by Claisen-Schmidt
condensation
https://www.pharmatutor.org/articles/chalcone-versatile-
chemical-entity[9]
The experiment aimed to: (1) comprehend the
reaction mechanism of aldol condensation; and (2)
synthesize dibenzalacetone by aldol condensation
reaction.
IV. EXPERIMENTAL
In a 50 mL Erlenmeyer flask, 0.80 mL (0.82 g,
8mmol) of benzaldehyde, 0.30 mL (0.24 g, 4mmol)
of acetone, and 2 mL of 95% ethanol was mixed.
About 2 mL of 10% NaOH was added and swirled
for 20 minutes.
The precipitate was collected by suction
filtration and the filtrate was discarded. To the
residue, 3 mL of distilled water was added. It was
allowed to stand for 60 seconds and the suction
was reapplied; this was done twice. The solid was
then recrystallized using cold 95% ethanol. The
melting point and the percent yield were
determined.
V. RESULTS
The yielded product from the synthesis of
dibenzalacetone crystals were light yellow in color,
as seen in Figure 4 The crystals weigh 0.4985 g
with a percent yield of 45.80% (calculations are in
the appendix section).
Figure
Synthesized dibenzalacetone
Moreover, the melting point of the product
obtained ranges from 104°C to 113°C, which
deviates from the 110°C to 111°C theoretical
melting point of the compound.[10]
VI. DISCUSSION
Condensation is a process which joins two or
more molecules usually with the loss of a small
molecule such as water or an alcohol. Aldol
condensation is a process in which two organic
compounds with carbonyl groups fuse together
with a loss of water molecule in order to form β-
hydroxyketone. The product is known as adol
because it contains an aldehyde (or ketone) group
and an alcohol group. [11]
In this experiment, dibenzalacetone was
from
produced using a base-catalyzed cross aldol
condensation, known as Claisen-Schmidt reaction.
[8]
It is synthesized from the reaction between an
acetone molecule and two benzaldehyde
molecules dissolved in ethanol and catalyzed by
sodium hydroxide (See Figure 5).
Figure 5. Reaction scheme for the preparation of
dibenzalacetone, from
http://www.organicchem.org/oc2web/lab/exp/aldol/aldoldes.ht
ml [5]
In this reaction, sodium hydroxide functioned
as a catalyst while ethanol acted as a solvent
which allows the acetone and benzaldehyde to
dissolve and react with each other. Subsequently,
upon the addition of acetone and benzaldehyde in
the solvent, the solution turned into a yellow
colored solution. Eventually, the product was
formed with a yellow precipitate appear in the
reaction after the 20 minute swirling. To obtain a
higher yield of the product, the yellow precipitate in
ethyl acetate was immersed into an ice-bath in the
recrystallization process. This step is fundamental
since the precipitation formation is an exothermic
reaction, the heat energy in the precipitate needs
to be immediately released to maximize the
formation rate of the product. The product yielded
is light yellow in color as it absorbs at 315 to 400
nm due to its extended conjugated structure. [11,12]
Since acetone is a relatively stable and
unreactive compound, there is a need to convert it
into its anionic form to increase its nucleophile
properties for the initiation of the reaction. The
hydroxide ion produced from sodium hydroxide
tends to attack the α-hydrogen in acetone to form
water molecule, an excellent leaving group. The
deprotonation of acetone gives a nucleophilic
4.
enolate anion used in the synthesis of
dibenzalacetone (See Figure 6).

Figure 6. Deprotonation of acetone to form an enolate ion,
from http://1chemistry.blogspot.com/2011/11/objective-
1.html[8]
The acetaldehyde enolate ion attack to the α-
carbon of benzaldehyde via nucleophilic addition
which produces an alkoxide (Figure 7).
Figure 7. Intermediate formed upon the attack of
acetaldehyde enolate ion to the benzylic carbon of
benzaldehyde, from
http://1chemistry.blogspot.com/2011/11/objective-1.html[8]
The oxygen attached to the benzylic position
of carbon tends to attract one proton from a water
molecule to form a hydroxide group in the
intermediate, which forms the aldol. Under basic
conditions, the hydroxide ion tends to remove one
proton from the α-carbon resulting the formation of
C=C double bond at the α and β carbon. At the
same time, the hydroxide group attached to the β
carbon forms a leaving group. Benzalacetone then
is formed as the alkoxide is protonated by the
solvent (Figure 8).
Figure 8. Formation of benzalacetone after condensation,
from http://1chemistry.blogspot.com/2011/11/objective-1.html
[8]
The benzalacetone tends to form
benzalacetone enolate ion upon the attack made
by the hydroxide group to the proton attached to
the carbon at benzylic position (Figure 9).
Figure 9. Formation of benzalacetone enolate ion from
http://1chemistry.blogspot.com/2011/11/objective-1.html[8]
Similar to the afore discussed mechanism, the
benzalacetone enolate ion acts as a nucleophile
which attacks another benzaldehyde. The
protonation of the aldol takes place followed by the
elimination of the hydroxide groups. As a result, the
nucleophilic addition and base-catalyzed
dehydration lead to the formation of the desired
product which is dibenzalacetone. The full reaction
mechanism for the synthesis of dibenzalacetone is
seen in Figure 10.
Figure 10. Reaction mechanism for the synthesis of
dibenzalacetone, from
http://1chemistry.blogspot.com/2011/11/objective-1.html[8]
Since the observed melting point of the
synthesized dibenzalacetone had a range of 9, it
can be implied that the yielded product may
contain impurities. Impurities in a sample widens
the melting point range since the compound is not
homogeneous and different areas will start to melt
before purer areas in the solid.[13] The melting point
of the product obtained ranges from 104°C to
113°C, which deviates from the 110°C to 111°C
theoretical melting point of the compound which
further confirms that the sample is impure. This
experimental result can be attributed to the fact
that some impurities don't make good
intermolecular forces in the compound they're in.
These impurities then work as barriers for the
molecules of the compound to make
intermolecular forces with themselves. Less IMF
means that there would be less energy needed for
overcoming the activation energy; thus, a lower
melting point. [14]
These impurities in the product can be
addressed through recrystallization. However,
lower product yield could be attributed to the
repetitive filtration and recrystallization process
because over washing of the sample may dissolve
the compound of interest.
VII. CONCLUSIONS AND
RECOMMENDATIONS
Apparently, from the results, the synthesis
of dibenzalacetone through the base-catalyzed
aldol condensation of acetone and benzaldehyde
can be concluded successful. The recrystallized
crude product weighed 0.4985 g accounting for a
45.80% percent yield. However, the obtained
melting point of the experimental product ranges
from 104°C to 113°C which deviates from the
theoretical melting point range of 110°C to 111°C
which further confirms that the sample was impure.
These impurities in the product can be addressed
through recrystallization where pure acetone and
minimal amount of ethanol should be used and the
recommended rate of cooling should be slowed
down to facilitate crystal growth instead of
nucleation.
In addition, a higher melting point range
may be caused by side reactions and errors in the
procedure or use of equipment. For these to be
minimized, the reagents should be properly
handled and stored to prevent contamination.
VIII. REFERENCES
Properties. Journal of Chemical Education, 87(12),
1384-1387. doi:10.1021/ed1004867
[13] Forsey. Retrieved from
https://www.ibchem.com/root_pdf/melting_point_
depression.pdf
[14] Leen Ayyoub, ‘Why do the impurities increase
or decrease the melting point?’, Quora, 01
December 2017, https://www.quora.com/ Why-do-
the-impurities-increase-or-decrease-the-melting-
point.
CERTIFICATION OF CONTRIBUTION
I hereby certify that I have given substantial
contribution to this report:

[1] William Reusch, ‘Aldehydes and Ketones’, 23

October 2019, https://www2.chemistry.msu. ______________________________
edu/faculty/reusch/VirtTxtJml/aldket1.htm. Cecilia, Jasmin S.
[2] Jim Clark, Introducing Aldehydes and Ketones’,
November 2015,
https://www.chemguide.co.uk/organicprops/carbo ______________________________
nyls/background.html. Fami, Isabela N.
[3] NA, ‘Chapter 19: Enols and Enolates of
Carbonyl Compounds and their Reactions’, 23
October 2019, http://research.cm.utexas.edu/ ______________________________
nbauld/teach/ch610bnotes/ch19.htm. Marteja, Alexandra Leigh M.
[4] NA, ‘Formation of Enols and Enolates, Organic
Chemistry Help, 23 October 2019,
https://www.studyorgo.com/blog/formation-of- ______________________________
enols-and-enolates/. Pangilinan, Dianne G.
[5] Korry Barnes, ‘Aldol Addition: Mechanism and
Reaction’, 23 October 2019, https://study.com/
academy/lesson/aldol-addition-mechanism-
reaction.html.
[6] NA, ‘Aldol Condensation’, 6 June 2019,
https://chem.libretexts.org/Bookshelves/Organic_
Chemistry/Supplemental_Modules_(Organic_Che
mistry)/Reactions/Organic_Reactions/Aldol_Cond
ensation.
[7] NA, ‘Simple Aldol Reaction’, 24 December
2014, https://commons.wikimedia.org/wiki/
File:Simple_aldol_reaction.png.
[8] Goh Kokv, ‘Synthesis of Dibenzalacetone by
Aldol Condensation’, One Part of Chemistry, 16 APPENDIX A
November 2011, http://1chemistry.blogspot.com/
2011/11/objective-1.html. Calculation for the Theoretical Yield
[9] Sarthak Dave, ‘Chalcone: A Versatile Chemical
Entity’, 23 October 2019, Limiting reagent:
https://www.pharmatutor.org/articles/chalcone- 𝟏. 𝟎𝟒𝟏𝟓 𝒈 𝒃𝒆𝒏𝒛𝒂𝒍𝒅𝒆𝒉𝒚𝒅𝒆
𝟎. 𝟖𝟎 𝒎𝑳 𝒃𝒆𝒏𝒛𝒂𝒍𝒅𝒆𝒉𝒚𝒅𝒆 𝒙
versatile-chemical-entity. 𝟏 𝒎𝑳 𝒃𝒆𝒏𝒛𝒂𝒍𝒅𝒆𝒉𝒚𝒅𝒆
[10] PubChem. (2004). Dibenzalacetone. 𝟏 𝒎𝒐𝒍 𝒃𝒆𝒏𝒛𝒂𝒍𝒅𝒆𝒉𝒚𝒅𝒆 𝟏 𝒎𝒐𝒍 𝒅𝒊𝒃𝒆𝒏𝒛𝒂𝒍𝒂𝒄𝒆𝒕𝒐𝒏𝒆
𝒙 𝒙
Retrieved from 𝟏𝟎𝟔. 𝟏𝟐 𝒈 𝒃𝒆𝒏𝒛𝒂𝒍𝒅𝒆𝒉𝒚𝒅𝒆 𝟐 𝒎𝒐𝒍 𝒃𝒆𝒏𝒛𝒂𝒍𝒅𝒆𝒉𝒚𝒅𝒆
https://pubchem.ncbi.nlm.nih.gov/compound/Dib 𝟐𝟑𝟒. 𝟐𝟗 𝒈 𝒅𝒊𝒃𝒆𝒏𝒛𝒂𝒍𝒂𝒄𝒆𝒕𝒐𝒏𝒆
enzalacetone 𝒙 = 𝟎. 𝟗𝟏𝟗𝟖 𝒈
𝟏 𝒎𝒐𝒍 𝒅𝒊𝒃𝒆𝒏𝒛𝒂𝒍𝒂𝒄𝒆𝒕𝒐𝒏𝒆
[11] Donald Robertson, ‘Aldol Condensation:
Preparation of Dibenzalacetone (1, 5-Diphenyl- Calculations for the Percent Yield
1,4-pentadien-3-one)’, 14 November 2012,
http://home.miracosta.edu/dlr/211exp5.htm. 𝒑𝒆𝒓𝒄𝒆𝒏𝒕 𝒚𝒊𝒆𝒍𝒅
[12] Huck, L. A., & Leigh, W. J. (2010). A Better | 𝟎. 𝟒𝟗𝟖𝟓 𝒈 − 𝟎. 𝟗𝟏𝟗𝟖 𝒈|
Sunscreen: Structural Effects on Spectral = 𝒙 𝟏𝟎𝟎%
𝟎. 𝟗𝟏𝟗𝟖 𝒈
= 45.8%
 than any other hydrogen in the alkyl
chain?
APPENDIX B: ANSWERS TO GUIDE
QUESTIONS It is because of the stability of the
1. Write the mechanism for the base- resulting anion or enolate formed after the
catalyzed aldol condensation of abstraction of hydrogen, due to resonance
dibenzalacetone. Do the same for acid- and the delocalization of negative charge
catalyzed aldol condensation. from carbon to oxygen which is
electronegative.
Base-catalyzed aldol condensation
4. Why is the 𝛼-hydrogen in an 𝛼, 𝛼-
unsaturated carbonyl compounds also
acidic?

Since it is vinylic, it is also affected

by resonance therefore making it more
acidic.

5. Ketones with non-equivalent 𝛼-

hydrogens are not usually made to
undergo aldol condensation. Explain
the rationale behind this.

Acid-catalyzed aldol condensation Ketones with non-equivalent

alpha - hydrogens usually don't undergo
aldol condensation because it would
produce products with similar properties
making the products hard to separate and
will cause the reaction to be inefficient and
synthetically unuseful.

2. Write the side reactions that may take

place during the synthesis. How are
these reactions minimized or avoided?

Cannizzaro reaction of
benzaldehyde may take place at the same
time producing benzyl alcohol and benzoic
acid. Self-aldol condensation of acetone
may also happen producing diacetone
alcohol (4-hydroxy-4-methylpentan-2-one)
and mesityl oxide (4-methylpent-3-en-2-
one). In order to minimize self-
condensations, generally one reactant is
chosen which has no a-hydrogens, and
that reactant is maintained in large excess
over the second reactant (which will have
a-hydrogens and can form the enolate
anion).

3. Why is the 𝛼-hydrogen in a carbonyl

compound considerably more acidic