Experiment No.
05
Preparation of Aldol Condensation Products
(Post-Lab Report)
CHEM – 5301 – 08
Modern Laboratory Practices (Dr. Nguyen)
Department of Chemistry & Biochemistry
Lamar University
Submitted by:
Md Arif Rafid (L20338972) &
Jyothirmai Potha (L20340070)
Group: 10
Date: Oct-24-2014
Purpose
To synthesize dibenzalacetone via an aldol condensation reaction between acetone
(ketone) and benzaldehyde (aldehyde). The end product will be recrystallized using
ethanol, and then characterize”an organic reaction in which an enol or an enolate
ion reacts with a carbonyl compound to form a β-hydroxyaldehyde or β-
hydroxyketone, followed by a dehydration to give a conjugated enone.
Introduction
Condensations are reactions that add together two or more molecules often with
the loss of a small molecule such as water or an alcohol. In its simplest form the
aldol condensation combines to carbonyl compounds to give a beta hydroxyl
aldehyde or ketone. The product is also called as aldol as it contains both aldehyde
group and an alcohol.
A crossed aldol condensation is an aldol condensation in which an aldhyde or
ketone adds to the carbonyl group of a different compound. It is much effective if
only one of the reactants can form the enolate and the other reactant is particularly
electrophyllic towards enolates. Benzaldehyde is an excellent reagent for crossed
aldol condensation because it has no alpha hydrogen so it cannot form an enolate.
Theory
The experiment involves the reaction of aromatic aldehyde with aliphatic ketones
in the presence of base to form condensation products.
(Benzaldehyde) (Acetone) (Dibenzalacetone)
In the presence of excess aldehyde, each mole of ketone can condense with two
moles of the aldehyde, the reaction above explains the condensation reaction
between acetone and benzaldehyde is done by mixing the two reactants with
NaOH and ethanol, then allowing the reaction to sit for thirty minutes. The crystals
were then washed with water three times and recrystallized using ethanol. It was
then characterized using melting point analysis.
Reaction Mechanism
Aromatic aldehydes react with aliphatic ketones in the presence of base to form
condensation products. The mechanism of reaction involved is deprotonation of
hydrogen adjacent to carbonyl, by a base.
Resonance-stabilized enolate acts as a nucleophile on the aldehyde.
The alkoxide is then protonated to regenerate base.
The base deprotonates the α-carbon again to form an enolate.
Enolate forms unsaturated α,β-carbonyl with loss of hydroxide.
Table
Physical properties:
Compound Formula weight(gms) Density(g/ml)
Aldehydes benzaldehyde 106.1 1.045
4-methylbenzaldehyde 120.2 1.019
4-methoxybenzaldehyde 136.2 1.119
Trans-cinnamaldehyde 132.2 1.050
Ketones acetone 58.1 0.791
cyclopentanone 84.1 0.951
cyclohexanone 98.2 0.948
4-methylcyclohexanone 112.2 0.91
Equipments
Ring stand and clamps, round bottom flask 25ml, stir bar, separating funnel, watch
glass, vacuum filtration apparatus, ice bath, 100ml flask, thermometer, test tubes,
water bath for heating.
Chemicals Used
Aldehyde (sample C and sample D), ketone (4-metylcyclohexanone and
cyclohexanone), 1M sodium hydroxide, 95% ethanol, acetic acid
Procedures
2mmol of ketone was taken in a Erlenmeyer flask and dissolved in 4ml of 95%
ethanol. 8mmol of aldehyde was taken and dissolved in 3ml of 1M NaOH.
Aldehyde and ketone were mixed and the reaction mixture was allowed to stand at
room temperature for 10 minutes with occasional shaking. As precipitate was not
formed, the reaction mixture was to be heated in boiling water bath until formation
of precipitate occurs. Then the reaction tube was cooled on ice bath. The aldol
condensation product can be collected by vacuum filtration by washing it with 2ml
of either 4% cold acetic acid or 95% ethanol. The precipitate was collected and
dried. The percentage yield was calculated and its melting point was measured.
Calculation
Aldehydes (unknown sample C and D)
Amount of sample taken
8mmol x 1mol/1000mmol x 124g/1mol x 1ml/1.06g = 0.94ml ≈ 1ml
Ketones
For 4-methylcyclohexanone:
2mmol x 1mol/1000mmol x 112g/1mol x 1ml/0.91g = 0.25ml ≈ 5drops
For cyclohexanone:
2mmol x 1mol/1000mmol x 98.2g/1mol x 1ml/0.948g = 0.21ml ≈ 4drops
Percentage yield
For 4-methylcyclohexanone and sample D:
Melting point: 1340 C, so the aldehyde was 4-methylbenzaldehyde
Weight of the aldol product: 0.06 gm
Theoretical yield = 2 mmol = {(120.2*2 + 112.2 - 36) / 1000} * 2 gm = 0.6332 gm
Percentage yield = 0.06gm/0.6332gm * 100% = 9.47%
For cyclohexanone and sample C:
Melting point: 1550 C, so the aldehyde was 4-methoxybenzaldehyde
Weight of the aldol product: 0.24 gm
Theoretical yield = 2 mmol = {(136.2*2 + 98.2 - 36) / 1000} * 2 gm = 0.6692 gm
Percentage yield = 0.24gm/0.6692gm * 100% = 35.86%
Observation
Addition of sample D aldehyde to test tube 1 containing 4-methylcyclohexanone
changed the color to dark yellow and addition of sample C aldehyde to
cyclohexanone present in test tube 2 changed the color to pale yellow. Addition of
NaOH to both test tubes resulted in formation of precipitate in both the tubes. Mass
of aldol condensed product in test tube 1 (4-methylcyclohexanone + sample D
aldehyde) was 0.006 gm and melting point was found to be 134 0 C. Mass of aldol
condensed product in test tube 2 (cyclohexanone + sample C aldehyde) was 0.24
gm and melting point was found to be 1550C.
Discussion
The aldehyde samples reacted with ketones to give aldol products. In the
experiment, some sample was lost during filtration and transfers. Moreover, some
portion of reactants may not be converted into products, especially in test tube 1
the reaction took some time to yield precipitation. This explains why the
experimental yield was significantly less than the theoretical value. Melting point
of the product obtained from 4-methylcyclohexanone and sample D was 134 0 C.
From the melting point measurement we can say that the unknown aldehyde in
sample D was 4-methylbenzaldehyde. Melting point of the product obtained from
cyclohexanone and sample C was 1550 C from which the unknown aldehyde in
sample C was identified as 4-methoxybenzaldehyde. From the reaction
stoichiometry, we got the molecular weight of the product (2 molecules of
aldehyde plus 1 molecule of ketone and deduction of 2 molecules of water) from
which the percentage yield was calculated.
Conclusion
Measurement of melting points of the two aldol products was useful to identify the
unknown aldehydes. Melting point of the product obtained from 4-
methylcyclohexanone and sample D was 134 0 C which indicates the aldehyde used
was 4-methylbenzaldehyde, percentage yield of the product was 9.47%. Melting
point of the product obtained from cyclohexanone and sample C was 155 0 C which
indicates the unknown aldehyde in sample C was 4-methoxybenzaldehyde,
percentage yield of the aldol product was 35.86%.
Reference
1. Dr. Nguyen’s protocol
2.
http://cnx.org/contents/04f682cf-6e60-4db6-9d49-f1cdab7375f0@3/Aldol_Conden
sation
3. http://www.xula.edu/chemistry/documents/orgleclab/Aldol_notes.pdf
