INTRODUCTION

Generally, condensation is a process which two or more molecules join together

by losing water or alcohol. Aldol condensation can be described as an organic reaction
which join two carbonyl groups with a loss of water involving enolate ions. Enolate
ions reacts with carbonyl compound to form β-hydroxyketone or β-hydroxyaldehyde
which then produces conjugated enone by dehydration reaction. There are few types of
condensation that must be differentiated such as Perkin reaction, Claisen- Schmidt
condensation, Henry reaction, Dieckmann condensation and Japp-Maitland
condensation.

Figure 1.0

Figure shows the reaction of 3-nitrobenzaldehyde with acetophenone which

produces 3-nitrochalcone through aldol condensation.

3-nitrobenzalacetophenone (3-nitrochalcone) is an aromatic compound and

depicts antibacterial properties. In this experiment, aldol condensation is performed to
synthesis 3-nitrochalcone by reacting 3-nitrobenzaldehyde with acetophenone in the
presence of base. The type of aldol condensation performed is Claisen-Schmidt which
the formation of new carbon-carbon bond that depends on the reactivity of a carbonyl
group and intermediate product dehydrates to produce the resonance-stabilised
unsaturated ketone. Generally, formation of β-hydroxyketone or β-hydroxyaldehyde is
due to the addition of conjugate base of an aldehyde or ketone to the carbonyl group of
another aldehyde or ketone. This reaction leads in producing high yield because of the
absence α-hydrogen in benzaldehyde. Therefore, formation of enolate ions could not
be occur which prevent it to react with itself. Hence, in the same way, ketones could
not easily react with benzaldehyde.

The objective of this experiment is to prepare 3-nitrochalcone via aldol

condensation by reacting 3-nitrobenzaldehyde and acetophenone in the presence of
base which is 95% ethanol. Next, to calculate the percentage yield of the crude and
purified chalcone. Lastly, to determine the melting point of the purified 3-
nitrochalcone.

MATERIALS AND APPARATUS

Table 1.0: Shows the materials and apparatus used during the experiment.

Materials Apparatus
 Nitrobenzaldehyde  50mL Erlenmeyer flask
 Acetophenone  Spatula
 95% ethanol  Filter paper
 Sodium Hydroxide solution  Beaker (50mL)
 Buchner funnel
 Flask
 PROCEDURE

A: Preparation of crude Chalcone:

1. 0.75g (5mmol) of 3-nitrobenzaldehyde, 0.60mL of acetophenone and 4.0mL of 95

% Ethanol were placed into a 50 mL Erlenmeyer flask consequently.

2. The mixture was swirled and heated in a steam bath before left to cool to room
temperature.

3. 0.5mL of Sodium Hydroxide solution, NaOH was added in the flask.

4. The mixture was swirled until it turned cloudy.

B: Isolation of crude Chalcone:

1. 10mL of ice water was added into the cloudy mixture.

2. The mixture was stirred by using a spatula before being transferred into a beaker
containing 15mL of ice water.

3. The precipitate formed was collected by using a Buchner funnel and washed with
cold water before left to dry for 30 minutes.

4. The crude product was weighed.

C: Crystallisation of Benzalacetophenone (Chalcone) / Purification:

1. The crude product was dissolve in a hot 95% ethanol with the ratio of 1:4 of
crude:ethanol.

2. The crystal formed was was collected by using a Buchner funnel before being left
to dry and weighed.

3. The melting point of the crystal was determined.

 1. 0.75g 3-nitrobenzaldehyde +
Erlenmeyer Flask 0.60mL acetophenone +
1.0mL 95% ethanol

2. 0.5 mL NaOH

Hot plate

Figure 1(a) : Erlenmeyer flask heated on a hot plate

Washed with cool water during

isolation of crude chalcone and
ethanol during isolation of pure
chalcone.

Figure 1 (b): The setup for vacuum filtration

 DATA AND OBSERVATIONS

Table 1.1: Shows the samples and its mass

Samples Mass (g)

3-Nirtobenzaldehyde C7H5NO3 0.7684
Filter paper 1 1.1250
Filter paper 1 + crude chalcone 4.3185
Crude chalcone, C15H11NO3 3.1935
Filter paper 2 1.2385
Filter paper 2 + pure product 2.4291
Pure chalcone, C15H11NO3 1.1906

Table 1.2: Shows the data of theoretical yield, percentage yield and melting point.

Data Value
Theoretical yield (g) 1.2789 g
Percentage yield (%) 247.96 %
Melting point (℃) 108.4-142.3 ℃

Table 1.3: Shows the observations during the experiment.

Reaction and Product Observations

0.75 g 3-nitrobenzaldehyde + 0.60 ml
acetophenone + 4.0 ml of 95% ethanol
Addition of 0.5 ml NaOH
Crude 3-nitrochalcone.
Purified 3-nitrochalcone
Yellow precipitate is formed
The solution turned cloudy and orange
precipitate is formed.
Pale brown precipitate is formed
Pale yellow
 CALCULATIONS

1. Theoretical yield of 3-Nitrochalcone, C15H11NO3

C 7 H 5 NO3  C8 H 8 O C   C15 H 11 NO3  H 2 O

2 H 5OH

Given :

Mass of C7H5NO3 = 0.7684 g

Molar mass of C7H5NO3 = 151.121 g/mol

Mol of C7H5NO3 =

Mass 0.7684 g

Molarmass 151.121gmol 1
 5.085  10 3 mol
 0.005085mol

(limiting reactant)

Volume of C8H8O= 0.60 mL=0.60cm3

Density of C8H8O= 1.03g/cm3

Molar mass of C8H8O = 120.15g/mol

Mol of C8H8O =

0.6cm 3  1.03g / cm 3
 5.144  10 3 mol
120.15 g / mol
 0.005144mol
 1 mol C7H5NO3 ----> 1 mol C15H11NO3

Mol of C15H11NO3=

0.005085 mol C7H5NO3x 1mol C15H11NO3/ 1 molC7H5NO3

= 0.005085 mol C15H11NO3

Theoretical mass of C15H11NO3

= 0.005085 mol C15H11NO3 X molar mass of C15H11NO

= 0.005085 mol X 253.267 g/mol

= 1.2879 g of C15H11NO3

2. Percentage yield % =

crude
  100
theoretical
3.1935 g
  100
1.2879 g
 247.96%
 DISCUSSION

In this experiment, we performed aldol condensation in order to prepare 3-

nitrochalcone (3-nitrobenzalacetophenone) where 0.75 g of 3-nitrobenzaldehyde reacted with
0.60 ml acetophenone under a base condition which in the presence 4.0 ml of 95% ethanol.
The mixture formed was yellow in colour. Ethanol functions as a solvent which enable the
acetophenone and 3-nitrobenzaldehyde to dissolve and react together. Then, 0.5 ml of sodium
hydroxide which acts as a catalyst was added into the mixture and the mixture was swirled.
The mixture turned to cloudy and orange precipitate was formed as it completely solidified.

The reaction was then proceed with the addition of 10 ml ice water in order to isolate
the crude product which pale brown in colour. The mixture was stirred and transferred to a
beaker with 12 ml of ice water. The pale brown crude 3-nitrochalcone was collected by using
Buchner funnel and the product was washed with cold water and dried for 30 minutes. Then
the mass for crude product was obtained which is 3.1935 g and the percentage yield was
determined which is 247.96%.

The recrystallization of crude 3-nitrochalcone was carried out to remove impurities or

side products that presence in the pale brown precipitate. The solvent used was 12 ml hot 95%
ethanol as the ratio is about 4 ml of ethanol per gram of solid. The mass of pure 3-nitrochalcone
obtained was 1.1906 g and the colour depicted was pale yellow.

The melting point of the purified 3-nitrochalcone was determined which is 108.4 to
142.3 °C. Theoretically, the melting point of 3-nitrochalcone is 143 to 145 °C. Hence, most of
the impurities presence have been removed during recrystallisation of crude 3-nitrochalcone.
So, we can be confirmed that the product obtained is pure 3-nitrochalcone.

Questions

1. Give the mechanism for the preparation of the benzalacetophenone using the
given aldehyde in the experiment.

The mechanisms of aldol condensation between 3-nitrobenzaldhyde and acetophenone can

be explained as the acetophenone converted into anionic form of enolate to increase its
nucleophile properties in order to initiate the reaction. This is because acetone is a stable and
unreactive compound. When sodium hydroxide dissolves in water, it produces hydroxide ions.
These basic hydroxide ions attack the acidic α-hydrogen in acetophenone to form enolate and
water molecule. The reason why the acetophenone is chosen to be act as a nucleophile rather
than the 3-nitrobenzadehye is because it contained alpha hydrogen which allowed the
formation of enolate, while 3-nitrobenzaldehyde does not contain alpha hydrogen. Later, the
enolate ion which exhibits resonance-stabilized structure act as nucleophile which responsible
to attack the 3- nitrobenzaldehyde in a nucleophilic addition reaction to form tetrahedral
alkoxide ion intermediate. Next, the alkoxide ion intermediate was protonated by the water
molecules to yield neutral aldol product which contained hydroxyl and carbonyl group. Finally,

hydroxyl ion from the ethanol solvent hydrolysed the aldol product by eliminating the alpha
hydrogen in an E2 reaction to expel the OH group forming a double bond. Hence, 3-
Nitrochalcone was formed as shown as in the diagram below.

Figure 2.0: Shows the mechanisms of aldol condensation to prepare 3-nitrochalcone.

 2. Draw the structure of cis and trans isomers of the compound that you prepared.
Why did you obtained trans isomer?

The 3-Nitrochalcone obtained was trans isomer. As shown in the figure (trans and cis) It can
be seen that cis isomer of cis-3-Nitrochalcone has high steric hindrance due to the side-by side
position of the phenyl and the carbonyl group. This steric hindrance reduce the stability of cis-
3 nitrochalcone while the arrangement of trans-3 nitrochalcone has less steric hindrance and
more stable. Hence, trans-isomer was obtain because it is more stable than cis-isomer.

3. Using proton NMR, how could you experimentally determine that you have the
trans isomer rather than the cis-isomer.

Although proton NMR was not conducted during the experiment, but it can be used to
determine whether the chalcone obtain is trans-isomer or cis-isomer. This is because cis and
trans coupling appear in different range on 1H NMR spectrum. We can determine whether the
isomer obtained is trans or cis by referring to the range of the isomer. The range of trans
coupling is 11-19 j (Hz) while the range for cis coupling is 5-14 j (Hz). The trans coupling is
always higher than cis coupling. Sometimes, trans and cis isomer can be determine by referring
to the number of deshielded hydrogen atom they have. Hydrogen is said to deshielded if there
is a movement of electrons in the pi bond of the carbon-carbon double bond.

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

Target Material Starting Material
 During the experiment, there were few precautions step which had been carried out .

Firstly, the the filter papers that contained the crude and pure 3-Nitrochalcone were ensure to

be fully dried before being weighed to obtain accurate mass of products. Secondly, during the

recrytallisation process, the flask was made sure to be scratch first before being place in ice

water bath to prevent longer reaction time needed to initiate the formation of crystal. The error

that occurred during this experiment was using too much of cold ethanol to wash the crude 3-

Nitrochalcone which cause the crude 3-Nitrochalcone to remain dissolve in the cold ethanol.

Next, the flask that contained the pure 3-Nitrochalcone was left in the ice bath for only short

time before being cooled down to room temperature. This cause the crystal formed to have low

purity.

CONCLUSIONS

In conclusions, we were able to prepare pure 3-nitrochalcone through aldol condensation

between 3-nitrobenzaldehyde and acetophenone in the presence 95% ethanol. The mass of the
pure product obtained is 1.1906 g while crude product is 3.1935 g. The percentage yield
calculated for the crude product is 247.96%. Last but not least, the melting point of the pure 3-
nitrochalcone is 108.4-142.3 ℃ which the value is quite close to the theoretical value.
 REFERENCES

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from http://www.chemvista.org/nmrstrchem3.html

[2] Warren, S ＆ Wyatt, P .(2009), Organic Synthesis: The Disconnection Approach (2nd ed.),
Wiltshire: Wiley.

[3] Clayden, J., Geeves, N., Warren, S.,(2000), Organic Chemistry, (1st ed.),Oxford: Oxford
University Press.

[4] Hunt, I. R. (2015). Ch18: Aldol reaction of RCHO. Retrieved from

http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch18/ch18-3-4.html