LABORATORY REPORT

ORGANIC CHEMISTRY

(CHM557)
NAME OF STUDENT : NUR INSYIRAH SHAZRIN BINTI ABIDIN

STUDENT NO : 2020960861

GROUP : AS2221A1

NUMBER :4

TITLE OF EXPERIMENT : THE ALDOL CONDENSATION REACTION (PREPARATION OF

DIBENZALACETONE)

DATE OF EXPERIMENT : 4 JUNE 2020

DATE OF REPORT SUBMISSION : 15 JUNE 2020

NAME OF LECTURER : MADAM NORUL AZILAH BINTI ABDUL RAHMAN

 Laboratory Report Marking Scheme

Full Marks
Mark(s)
(to be filled by lecturer)

Objective of the Experiment 1.0

Introduction 2.0

Experimental Procedure 1.0

Results and Observations 3.0

Calculations 2.0

Discussion 4.0

Conclusion 1.0

Answers to Questions 2.0

References 1.0

Pre-laboratory preparations (lab note book) 2.0

Laboratory techniques 1.0

Total Marks 20.0

EXPERIMENT 4

DATE: 5 JUNE 2020

TITLE: THE ALDOL CONDENSATION REACTION: PREPARATION OF

DIBENZALACETONE

OBJECTIVES:

1. To synthesize dibenzalacetone from aldol condensation reaction of benzaldehyde with

acetone in aqueous base.
2. To determine the melting point of dibenzalacetone.
1
3. To characterize dibenzalacetone using H NMR spectroscopy and 13C NMR
spectroscopy as well as IR spectroscopy.

INTRODUCTION

An aldol condensation is an organic reaction in which an enol or an enolate ion reacts

with a carbonyl compound to form a β-hydroxyketone or β-hydroxyketone, followed by a
dehydration to give a conjugated enone.

Dibenzalacetone or also known as dibenzylideneacetone is an organic compound with

the molecular formula, C17H14O. The structure of dibenzalacetone is a yellow crystal that
does not dissolve in water but in ethanol. Dibenzalacetone is used as a component in
sunscreen and some industrial organometallic compounds because it bonds to metals and
helps form a stable chemical structure. This figure showed the structure of dibenzalacetone:-

Dibenzalacetone

In this experiment, a dibenzalacetone is synthesized from aldol condensation reaction

of benzaldehyde with acetone in aqueous base, sodium hydroxide (NaOH). Acetone contains
α-hydrogen on both sides thus acetone with react with base anion (–OH) to form enolate
anion with two resonance. The benzaldehyde carbonyl is more electrophilic than the acetone.
The alkoxide produced is protonated by solvent, giving a β-hydroxyketone, which undergoes
basic-catalyzed dehydration. The elimination of hydroxide anion from the hydroxylenolate
results the formation of dibenzalacetone. Below is the general equation of aldol condensation
reaction of dibenzalacetone from benzaldehyde and acetone:-

O
H
NaOH
2 + H3C CH3

Benzaldehyde Acetone Dibenzalacetone

General equation of formation dibenzalacetone

APPARATUS

1. Beaker (200 mL)

2. Measuring cylinder (10 mL, 50 mL)
3. Glass Pasteur pipette or plastic Pasteur pipette
4. Stainless steel spatula
5. Buchner funnel
6. Buchner flask
7. Rubber tubing
8. Rubber bung or rubber filter adapter
9. Filter paper
10. Glass rod
11. Aluminium foil
12. Thermometer
13. Sample bottle
14. Watch glass
15. Hot plate
16. Oven
17. NMR Spectrometer
18. Melting point apparatus

CHEMICALS

1. Benzaldehyde
2. Acetone
3. 95% ethanol
4. Sodium hydroxide (NaOH)
5. Distilled water
PROCEDURE

a. 5g of NaOH was dissolved in a mixture of 40 mL 95% ethanol and 50 mL distilled

water in a 200 mL beaker. The beaker was covered and allowed the mixture to cool to
20°C.
b. In another beaker, 5.4 g of benzaldehyde was mixed with 1.5 g of acetone. The beaker
was covered with foil for later use.
c. Half of the mixture in (b) was added into (a) and stirred for 15 minutes until the
solution turns to yellow and a precipitate was formed (the temperature was in the
range of 20 – 25°C).
d. The rest of the mixture in (b) was added and then continued stirring for 30 minutes
(the temperature was kept below 24 °C).
e. The residue was filtered off using vacuum filtration on a Buchner funnel. The residue
was rinsed with water, ethanol and then allowed it to dry for 30 minutes.
f. The solid was weighed and the crude percentage yield was determined.
g. The crude product was recrystallized with 20 mL of hot ethanol. The cooling and
scratching were necessary to initiate crystallization. The solid was collected by
vacuum filtration and dried it in the oven.
h. The dry pure product was weighed and the percentage yield was calculated.
i. The melting point was measured and the FTIR and NMR of the product were obtained.
RESULTS AND OBSERVATIONS

Results:

a. Melting point of product (dibenzalacetone): 74 °C

b. Weight of crude product: 4.56 g
c. Weight of pure product: 4.26 g
d. Appearance of the purified product: yellowish crystals
1
e. H NMR data of the purified product (dibenzalacetone):
Chemical shift, δ Multiplicity Number of Type of proton
(ppm) hydrogen
1.6 Singlet (1) 1 O

H H
aa

CH2 CH2

7.1 Doublet (2) 1 H

Hb

7.8 Doublet (2) 1 H

Hc

Answer: dibenzalacetone
O

H H
Ha

CH HC
Hb Hc
 13
f. C NMR data of the purified product (dibenzalacetone):
Chemical shift, δ (ppm) Type of carbon
187.475 C = O (ketone)
127.487 C = C (alkene)
141.835 Aromatic ring carbons

g. IR data of the purified product (dibenzalacetone):

Wavenumber (cm-1) Type of bond (group)
1651 C = C (alkene)
1497 and 1448 C = C (aromatic)

Observations:

Steps Observations
Adding NaOH into a mixture of ethanol and Clear solution
distilled water.
Mixing benzaldehyde with acetone Clear yellowish solution
After stirring for 30 minutes Milkish yellow solution
Filtration using vacuum filtration Yellow solid is formed on the filter paper
After vacuum filtration (recrystallize) Yellow crystals
Calculations:

a. Chemical equation
O

O
H
NaOH
2 + H3C CH3

Benzaldehyde Acetone Dibenzalacetone

Benzaldehyde Acetone (C3H6O) Dibenzalacetone

(C6H5CHO) (C17H14O)
Molecular weight (g/mol) 106.12 58.08 234.29
Volume (mL) – – –
Density (g/mL) 1.04 0.79 –
Weight used (g) 5.40 1.50 –
Mole n = 5.40/106.12 n = 1.50/58.08 n = 4.26/234.29
n = 0.05/2 n = 0.03 n = 0.02
n = 0.025
Limiting reagent yes – –
Theoretical yield (g) – – 0.025 x 234.29
= 5.857

b. Theoretical yield of product

Theoretical yield (dibenzalacetone) = mole x molecular weight
Theoretical yield = 0.025 x 234.29
= 5.857 g
c. Percentage yield of the crude and purified product.
(i) Crude product

Percentage yield = 77.86%

 (ii) Purified product

Percentage yield = 72.73%

DISCUSSION

In the experiment, the mixture of benzaldehyde and acetone was added into the beaker
containing NaOH, 95% ethanol and water. This results in the appearance of the solution
turned clear yellowish solution. The solution turned to ‘milky’ yellow solution after being
stirred continuously for 30 minutes. Then, the solution was filtered with vacuum filtration.
The filter paper used was rinsed with water to prevent the paper from moving while filtrate
the precipitate. The yellow solid was then recrystallized with hot 95% ethanol. The crude
product only dissolved in ethanol, not in water. The pure product obtained after filtration
using vacuum filtration. Thus, dibenzalacetone appeared as yellow crystals.

In the aldol condensation reaction mechanism, the acetone has α-hydrogens on both
sides and thus can be protonated to give a nucleophilic enolate anion. The aldehyde carbonyl
(benzaldehyde) is much electrophilic than ketone (acetone), therefore it reacts rapidly with
the enolate. The alkoxide produced is protonated by solvent, H2O obtained from the
formation of enolate anion, giving a β-hydroxyketone, which undergoes base-catalyzed
dehydration. The elimination process reacts fast as the alkene is stabilized by conjugation to
not only the carbonyl but also the benzene.

Based on the 1H, 13C NMR and IR spectra obtained, the spectra showed the product is
dibenzylacetone. For IR spectra obtained were showed in this table:-

Wavenumber (cm-1) Type of bond (group)

1651 C = C (alkene)
1497 and 1448 C = C (aromatic)

Based on the dibenzalacetone structure, the IR spectra only showed aromatic bond on
wavenumber 1497 and 1448 cm-1. Other IR wavenumber obtained was 1651 cm-1 with C = C
bond (alkene). The ketone bond cannot be read by the IR spectra due to some error while
preparing the compound.

In 13C NMR spectra obtained shows in this table:-

Chemical shift, δ (ppm) Type of carbon

187.475 C = O (ketone)
127.487 C = C (alkene)
141.835 Aromatic ring carbons

13
All the functional group of dibenzalacetone can be read in C NMR spectra. The
chemical shift obtained for the carbonyl group of ketone was 187.475 ppm. For C=C bond of
alkene, the chemical shift obtained was 127.475 ppm which in range of 100 – 150 ppm.
Lastly, the type of carbon obtained was aromatic ring carbons which in 141.835 ppm.

The 1H NMR spectra is used to determine the structure of dibenzalacetone. Based on

the spectra, the signal of H mostly located at range 7 – 8 ppm which the chemical shift for
benzene.

In the formation of dibenzalacetone, 2 mole of benzaldehyde is used and reacts with 1

mole of acetone with the help of NaOH as a catalyst. The weight of crude product is 4.56 g
with percentage yield, 77.86%. While the pure product, dibenzalacetone obtained is 4.26 g
that yield 72.73% in the experiment. The benzaldehyde is limiting reagent as the mole
obtained is smaller than the mole of acetone. Both percentage yields are higher than 50%
means that the experiment is a success.

Dibenzalacetone obtained in form of yellow crystals and the melting point obtained is
74°C. The melting point obtain is lower than the theoretical melting point which is 110 -
111°C for trans-dibenzalacetone. This means there are impurities presence in the
dibenzalacetone obtained. This occurs due to experimental errors while conducting the
experiment. The NaOH may be the impurities present in the sample as the yellow solid is not
properly washed with water and ethanol. Some precaution steps are taken while running the
experiment such as wears a proper PPE – goggle, lab coat and cover shoes. This step is to
prevent injuries if there is chemical spill during experiment.
QUESTIONS

1. Give a mechanism for the preparation of the appropriate benzalacetophenone using 3-

nitrobenzaldehyde.
2. Draw the structure of the cis and trans isomer of the compound that you prepared.
Why did you obtain the trans isomer?
O

trans-dibenzalacetone cis-dibenzalacetone

3. Using proton NMR, how could you experimentally determine that you have the trans
isomer rather than the cis one? (Hint: Consider the use of coupling constants for the
vinyl hydrogens)
The coupling constant of trans isomer is bigger than in a cis isomer. The hydrogens in
trans isomer to be slightly more downfield to the left of the spectrum. The prove is
based on the proton NMR spectrum obtained.

4. Provide the starting materials needed to prepare the following compounds:

(Note: all the chemical compound in this lab report are sketched with ChemSketch
application)
CH3

H
H3C

a) H O

Answer:
CH3 CH3
O
H3C NaOH H
+H C H
H3C
H 3
H O
O
 O

H C
C CH3

b) H3C CH3

Answer:
O
O O

H C
C C NaOH
H3C CH3 + H3C CH3
C CH3

C
H3C CH3

Ph C O
C C

c) CH3 Ph

Answer:
O O H

Ph C O
Ph C C NaOH C C
CH3
+ H3C Ph
CH3 Ph
 H
C O
C C H
H3C O H C C
H

d) H3C

Answer:
O H
O C O
2 NaOH
+ C C H
O H3C O H C C
H3C CH3
CH3 H

O
H3C

H O
C C
C
H
O 2N Br
e)
Answer:
H O
H O
NaOH
O CH3 C C
C
+
O 2N Br H
O 2N Br
 O
Cl

f) NO 2
Answer:
O O
Cl Cl
O CH3 NaOH
+
O 2N NO 2

CONCLUSION

In a conclusion, all the objective of this experiment is achieved. In this experiment,

the dibenzalacetone can be determined from the aldol condensation reaction between 2 mole
of benzaldehyde and 1 mole of acetone with aqueous base, NaOH. The melting point of
dibenzalacetone obtained is 74°C which is lower than the actual value, 110 – 111°C due to
impurities presence in the sample. Lastly, the dibenzalacetone was able to characterize using
1 13
H NMR, C NMR and IR spectroscopy. The functional group of dibenzalacetone mostly
can be read in the spectroscopy.
REFERENCES

Angel, J. (2018, January 27). What is dibenzalacetone?. Retrieved June 15, 2020, from
Quora.com website: https://www.quora.com/What-is-dibenzalacetone

Census data revisited.(2019). Chem365 Labbook – 2019.Retrieved June 15, 2020, from:
http://web.mnstate.edu/jasperse/Chem365/Aldol%20Reaction.doc.pdf

Libretexts. (2019, June 05). Nuclear Magnetic Resonance (NMR) of Alkenes. Retrieved June
15, 2020, from
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_
(Organic_Chemistry)/Alkenes/Properties_of_Alkenes/Nuclear_Magnetic_Resonance
_(NMR)_of_Alkenes

UTSC Homepage. (n.d.). Retrieved June 15, 2020, from

https://www.utsc.utoronto.ca/webapps/chemistryonline/production/melting.php

Pavia, Lampman, Kriz and Engel. (2011). Introduction to organic laboratory techniques 3rd
edition. page 669 – 673.
APPENDICES