Ahmad Zakwan Bin Kassim - CHM557 - Exp4

UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)
SEMESTER 20224
OCTOBER 2022 - FEBRUARY 2023
EXPERIMENT 4:
THE ALDOL CONDENSATION REACTION:
PREPARATION OF BENZALACETOPHENONES
(CHALCONES)
NAME : AHMAD ZAKWAN BIN KASSIM

STUDENT ID : 2021886994
GROUP : AS2533A2
DATE : 29 NOVEMBER 2022
Objective (1M)
Introduction (2M)
Procedure in flowchart (2M)
Calculation (5M)
Discussion (3M)
Conclusion (1M)
Questions (6M)
TOTAL
OCT 2022-FEB 2023_COVID19

OBJECTIVE
1. To synthesize trans-3-nitrochalcone from aldol condensation reaction of 3-
nitrobenzaldehyde with acetophenone in aqueous base.
2. To determine the melting point of trans-3-nitrochalcone.
3. To characterize trans-3-nitrochalcone using 1H NMR spectroscopy and/or IR
spectroscopy.
INTRODUCTION
In this experiment, we will conduct an aldol condensation reaction between a substituted
benzaldehyde and a ketone in the presence of a base to give an α,β unsaturated ketone also
known as a chalcone. It is a cross aldol condensation in which the intermediate dehydrates to
form a resonance-stable unsaturated ketone. The aldol cross-condensation of a hydrogen-
deficient carbonyl molecule cannot produce an enolate ion. This explains why only one
enolate ion will form, which will be taken from another carbonyl molecule. The nucleophilic
enolate ion then attacks the carbonyl carbon, producing a hydroxy carbonyl. The hydroxy
carbonyl product removes a water molecule, resulting in a conjugated system consisting of a
double bond and a carbonyl group.
Then, trans 3-nitrochalcone will be produced by reacting 3-nitrobenzaldehyde with
acetophenone using a base. This is the mechanism of the resulting product.

PROCEDURE
a. Preparation of crude product
1. 3-nitrobenzaldehyde (0.75g) was weighed and placed into a 50mL Erlenmeyer
flask.
2. Acetophenone (0.60mL) and 95% ethanol (4.0mL) were added to the flask
containing the 3-nitrobenzaldehyde.
3. The flask was swirled to mix the reagents and dissolve any solids. The mixture
was warmed gently to dissolve the solids (the solution was heated onto a hot
plate) if necessary. The solution should be cooled to room temperature before
proceeding to the next step.
4. NaOH solution was added (0.5mL) (prepared by the lab assistant using 6.0g of
NaOH in 10mL of water).
5. The mixture was stirred with glass rod until it solidifies or until the entire
mixture becomes very cloudy.
6. Ice water (10mL) was added to the flask. The solid mass was break up by
stirring with a spatula if a solid is present at this point. Cooled and scratched
with glass rod was necessary to initiate crystallization.
7. The solid was collected by vacuum filtration on a Buchner funnel (refer Figure
3.1). The solid was washed with cold water and it was allowed to air dry for
30 minutes.
8. The solid (crude product) was weighed and the weight of solid was calculated.
The percent yield of the solid (crude product) was determined.
b. Recrystallization of crude product

1. The solid (0.5g) which was obtained from the above step was recrystallized
from hot methanol.
2. 20mL of methanol was measured and placed into 50mL beaker. The methanol
was heated on the hot plate until the temperature reach boiling point of
methanol which was 64.5ºC. The hot methanol was transferred into the solid.
3. The solution was cooled at room temperature and then cooling was continued
in an ice bath. Scratched with a glass rod was necessary to initiate
crystallization.
4. The solids/crystals were collected by vacuum filtration. The solids/crystals
were washed with a small amount of cold methanol. The solids/crystals were
allowed to dry by sucking air through them. It was dried in the oven.
5. The dry pure product (solids/crystals) was weighed and the percent yield of
the pure product was determined.
6. The melting point of the pure product (literature melting point is 146ºC) was
measured and a 1H NMR and/or IR spectra of the pure product was obtained.


RESULT
a. Data
1. Weight of crude product: 0.8776g
2. Weight of purified product: 0.2856g
3. Melting point of the purified product: 140°C
4. Appearance of the purified product: pale brown
5. 1H NMR data (in Table) of the purified product:
Chemical shift, δ Number of
Multiplicity Type of proton
(ppm) hydrogens
7.50-7.53 Triplet 2H CH-CH
7.58-7.62 Multiplet 2H Aromatic
7.66 Singlet 1H CH
7.80-7.83 Doublet 1H CH
8.02-8.04 Doublet 2H CH-CH
8.50 Singlet 1H CH
6. IR data (in Table):
Type of Bond
Wavenumber (cm-1)
(Group)
1528.5 N-O
1609.3 C=C
1662.2 C=O
3070.3 Aromatic
b. Observations
Steps Observations
Warm the mixture after the addition of
0.60mL acetophenone and 4.0mL of The mixture turned to a very
95% ethanol into the flask containing pale yellow in colour.
0.75g 3-nitrobenzaldehyde.
The solution turned to very
Addition of 0.5mL NaOH solution. cloudy and brown precipitate is
formed after the reaction.
Addition of 10mL ice water Crystal is formed.


CALCULATION

DISCUSSION
In this experiment, 3-nitrobenzaldehyde is synthesized to trans-3-nitrochalcone by
condensing aldol with acetophenone. The resulting product has a theoretical yield of 1.2589g.
The result seems to be not pure enough when the exact melting point, 140°C, is compared
with the theoretical melting point mentioned above. The crude yield is 69.71%, while the
pure yield is 14.74%. The yield percentage of each product varies widely. Some errors may
occur during the experiment, such as product may be spilled or left in the beaker during
filtration with a Buchner funnel.
IR spectroscopy results show that the product contains some functional groups. Initially, there
is a peak at 3070.3cm-1 suggesting the presence of an aromatic ring. Then there is a sharp
peak appearing at 1662.2cm-1, indicating the conjugated ketone C=O, and another sharp peak
appearing at 1609.3cm-1, indicating the C=C alkene. Finally, at 1528.5cm-1, a sharp and
strong peak was observed, indicating the presence of N-O bonding.
According to the NMR results, two hydrogens were detected at 7.50-7.53ppm with single
group multiples, confirming CH-CH. Then, at about 7.58-7.62ppm, a multiplex signal
develops, showing that the product consists of an aromatic ring as well as two hydrogens.
Then there is a signal with hydrogen representing single group multiples at 7.66ppm and
8.50ppm, as well as double multiples of hydrogen at 7.80-7.83ppm, 7.90-7.91 ppm and 8.23-
8.25ppm, indicating CH. Finally, there is a signal with two hydrogens with a doubling factor
at 8.02-8.04ppm, indicating CH-CH. According to the scientific report, the signal frequency
for the trans compound seems to be between 11Hz and 18Hz, so the yield of the compounds
is this trans compound.
CONCLUSION
In conclusion, the synthesis of trans-3-nitrochalcone was achieved and obtained from the
aldol condensation reaction of 3-nitrobenzaldehyde and acetophenone in aqueous base. The
yields of crude and purified products are 69.71% and 22.69%, respectively. The melting point
of trans-3-nitrochalcone was also determined and was 140°C.


QUESTIONS
1. Draw the structure of the cis and trans isomers of the compound that you
have prepared.
2. Using proton NMR, how could you experimentally determine that you
have the trans isomer rather than cis isomer? (Consider the use of
coupling constants for the vinyl hydrogen)
We can determine whether the isomer is trans or cis by referring to the range of
isomers. The trans coupling range is 11 to 18 J (Hz) while the cis coupling range is 6
to 14 j (Hz). Remember that cis coupling is always better than trans coupling. Trans
and cis isomers are sometimes distinguished by the amount of degassed hydrogen
atoms they contain. If the electrons move in the pi bond of the carbon-carbon double
bond, the hydrogen will not be shielded because the bond content in the cis isomer is
lower than in the trans isomer. Subsequently, the NMR spectra of the two different
isomers indicated that the hydrogen in the cis isomer is slightly upstream and the
hydrogen in the trans isomer slightly further downstream.


3. Draw the full mechanism for the aldol condensation of benzaldehyde and
acetone (in the presence of NaOH/H2O).

a. What type of elimination occur for an aldol condensation reaction?
Type of the elimination occur is dehydration.
b. What product must form before the elimination reaction can occur?
Product that must be form is conjugated enone.

REFERENCES
1. Pavia, Lampman, Kriz and Engel, Introduction to Organic Laboratory Techniques 3rd
Edition (2011). page 669-673.
2. Libretexts. (2020, July 14). 23.8: The aldol reaction and condensation of ketones and
aldehydes.
Chemistry LibreTexts. Retrieved December 5, 2021, from
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Map
%3A_Organic_Chemistry_(Wade)/
23%3A_Alpha_Substitutions_and_Condensations_of_Carbonyl_Compounds/
23.08%3A_The_Aldol_Reaction_and_Condensation_of_Ketones_and_Aldeh
ydes.
3. International, D. P. (1970, January 1). Cis trans isomers and NMR. CIS TRANS
ISOMERS
AND NMR. Retrieved December 5, 2021, from
https://orgspectroscopyint.blogspot.com/2014/11/cis-trans-isomers-and-
nmr.html.

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UNIVERSITI TEKNOLOGI MARA (UiTM) ORGANIC CHEMISTRY (CHM556/557)

NAME : AHMAD ZAKWAN BIN KASSIM

Procedure in flowchart (2M)

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b. Recrystallization of crude product

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a. What type of elimination occur for an aldol condensation reaction?

Type of the elimination occur is dehydration.

Product that must be form is conjugated enone.

OCT 2022-FEB 2023_COVID19

OCT 2022-FEB 2023_COVID19

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