CHM 556

ORGANIC CHEMISTRY II
-BACHELOR (HONS) APPLIED CHEMISTRY, AS245EXPERIMENT 5: ROBINSON ANNULATION REACTION OF 3NITROCHALCONE WITH ETHYL ACETOACETATE

NAME: MOHAMAD NOR AMIRUL AZHAR BIN KAMIS (2014647344)

PARTNERS NAME:
1. MOHAMAD SHAFIQ BIN PARMAN
2. MOHAMAD WAFIY BIN MOHD ZULKIFLEE
3. MOHAMAD HAMIZAN BIN MOHD ISA
4. IZZAH SYAHIRA BT RAMLAN
5. NUR SYAHIRA BT ISHAK
6. EKAEXZELINA BT ABU BAKAR
LECTURERS NAME: PN. FARIDAHANIM BT MOHD JAAFAR
DATE OF EXPERIMENT: 4/11/2014
DATE OF SUBMISSION: 21/11/2014

EXPERIMENT 5: ROBINSON ANNULATION REACTION OF 3-NITROCHALCONE WITH ETHYL

ACETOACETATE.
OBJECTIVE:
Performing Robinson annulation involves a Michael addition reaction followed by an aldol
condensation between 3-nitrochalcone and ethyl acetoacetate in the presence of base
(NaOH), then calculating the percentage yield, obtain the melting point, and NMR spectrum
for the product yield.

INTRODUCTION:
An , -unsaturated ketone can be prepared by conjugate addition of ethyl acetoacetate to
trans-chalcone followed by an intermolecular aldol condensation reaction and dehydration.
A Michael reaction is the nucleophilic addition of an , -unsaturated carbonyl compound.
The substituents on the Michael donor, the nucleophile, are electron-withdrawing carbonyl
groups. This causes the formation of an enolate anion in the presence of a base. The
substituent on the Michael acceptor, the activated alkene, reacts at the -carbon with the
enolate anion. The Michael reaction results in a 1,5-dicarbonyl compound. With the
presence of base, the carbonyl portion of the compound that contains an -carbon with at
least two hydrogen is deprotonated. The aldol condensation reaction is an electrophilic
substitution at the deprotonated -carbon. The aldol condensation reaction forms a new
carbon-carbon bond. The reaction is intramolecular that always causes the formation of
ring. Negative charged oxygen resulting from reaction before is then protonated and
dehydrated by the base. Finally, an , -unsaturated ketone is formed and it is very stable
due to the conjugating of the double bond with the both a carbonyl group and a phenyl
group.

PROCEDURE:
1. Preparation of solid
i.

1.2 of trans-3-nitrochalcone was added with 0.73mL of ethyl acetoacetate

solution and 25mL of 95% ethanol solution. The mixture was mixed well until
the solid was dissolved in a round bottom flask.

ii.

0.09g of NaOH pellet was added into the mixture and a boiling chip was
added.

iii.

The mixture was refluxed until the mixture was boiled and the mixture was
let to be boiled for 1 hour.

iv.

The refluxed mixture was let to be cooled at room temperature to proceed to

the isolation of the crude product.

2. Isolation of crude product

i.

The mixture was transferred into a small beaker and 10mL of water was
added, scratching was done to induce the crystallization process.

ii.

After some of the product forms the solid, the scratching was done in ice
water bath for 30 minutes to increase the rate of reaction for the
crystallization.

iii.

The solid was filtered by using Buchner funnel vacuum pump and 4mL of ice
cold water was used to aid transfer.

iv.

The beaker was rinsed by using 4mL of ice cold ethanol (95%).

v.

The solid was dried overnight in the oven at temperature 80C.

3. Removal of catalyst
i.

The isolated product was diluted by using 7mL acetone (reagent grade) in a
beaker.

ii.

The liquid with some solid (as little as can) was transferred into the glass
centrifuge to separate the liquid and solid more effectively.

iii.

The mixture was centrifuged for about 3 minutes at 200rpm.

iv.

The weight of an empty conical flask was taken and the centrifuged solution
(without any solid) was placed into it.

v.

The solution was heated in hot water bath and was scratched to induce
crystallization. An oily solid product will form.

vi.

The weight of the conical flask with the oily solid product was recorded and
the weight of the oily solid was calculated.

4. Crystallization of product
i.

The product was added with 9mL of 95% boiling ethanol solution to dissolve
the product.

ii.

The dissolved solution in the ethanol was let to cool at room temperature.

iii.

After the solution was cooled, the solution was scratched to induce the
crystallization, and then was left undisturbed for a few minutes.

iv.

The crystal formed, and the mixture was placed with ice cold for about 15
minutes.

v.

The crystal was filtered by using Buchner funnel vacuum pump with washing
of 3 portions of 1mL ice cold 95% ethanol.

vi.

The crystal was dried in the oven overnight at temperature of 80C.

vii.

The crystal (6-ethoxycarbonyl-3,5-diphenyl-2-cyclohexenone) was weighed

ad percentage yield was calculated based on the theoretical yield.

viii.

The melting point of the crystal was taken and was sent for NMR test.

CALCULATION:
Molar mass of 3-nitrochalcone = 253g/mol
Molar mass of ethyl acetoacetate = 130g/mol
Molar mass of product (6-ethoxycarbonyl-3,5-diphenyl-2-cyclohexenone) = 365g/mol
1. Calculation for volume of ethyl acetoacetate:
1.03kg/L

0.75g

1030g/L xL = 0.75g
xL = 0.0007282L
x = 0.73mL

2. Calculation of theoretical yield:

Mol of 3-nitrochalcone =
= 0.004743mol
Mol of ethyl acetoacetate =
= 0.005769mol
Limiting reactant = 3-nitrochalcone
Theoretical yield = 0.004743mol 365g/mol
= 1.7312g

RESULT AND OBSERVATION:

i.

Observation

During the reflux, the mixture turns cloudy and form precipitate.

During scratching, yellow precipitate form.

The final product gives clearer colour than before the recrystallization
process.

Mass of oily product = 1.0427g

Mass of final product = 0.6116g
Melting point of product = 106C
Percentage yield =
Percentage yield =
= 35.33%

100%
100%

ii.

NMR data for Robinson annulation product

structure

Chemical shift (ppm)

C=C

4.8

CH2-COR

2.4

CH3-R

1.3

R-O-CH2-R

3.0

DISCUSSION:
The mechanism for the Robinson annulation reaction:
O

H
1.

H3C

O
OH

O
H3C

O
..

CH3

H3C

CH3

CH3

OH
H3C
O

O
H3C

+
CH

..

CH3
O

2.
H3C

CH3
O

H
O
3.H3C

CH3
O

O
O

H3C

H3C

H3C

CH3
O

+ H3C

4.

O
CH3
O

+ H3C

H3C

H3C

OH

O
CH 2
O

5.
H3C

O
CH 2
O

H3C

+
O

6.

H3C

H3C

H3C

H3C

H3C

OH

H3C

7.
H3C

H3C

HEAT

+H C
3

OH

+ HO -

OH

A Michael reaction followed by an aldol condensation produced 6-ethoxycarbonyl-3,5diphenyl-2-cyclohexenone. The reaction was one to one ratio and the theoretical yield was
determined by finding the limiting reagent, in this case is the 3-nitrochalcone. The
percentage yield of the product was 35.33% that is quite low. This may be cause by some of
the product spilled out or some remaining in the transferred container. Errors also may
occur during the filtration process by using the Buchner funnel vacuum filtration. The
pressure used to collect the solid is too high until the filter paper form holes that can pass
through the solid with the liquid into the conical flask. This then will make the actual yield
mass will decrease. The melting point of the product is 106C that is little bit different from
the theoretical value that lies between 111C to 112C. This shows that the product is not
100% pure and contains impurities.

CONCLUSION:
The Robinson annulation reaction was done to yield 6-ethoxycarbonyl-3,5-diphenyl-2cyclohexenone and was confirmed the structure by using NMR spectrum. The percentage
yield of the product is 35.33%, and the melting point is 106C.

QUESTIONS:
1. Why do you add sodium hydroxide pellet instead of its solution in your reduction
procedure?
Theoretically the pellet of sodium hydroxide has higher purity and higher
concentration, so that it will provide sufficient hydroxide ions to form the enolate
ion form ethyl acetoacetate.

2. Why did you add 10mL of water into the sample after refluxing?
The water is added into the sample to ease the crystallization process by scratching
the inside of the flask.

3. Why did you scratch the inside of the flask for the crystallization process?
Scratching will induce the crystallization process.

4. What is the important of adding boiling chip before refluxing the reaction mixture?
Boiling chip is added to prevent bumping during the refluxing process.

5. Give the IUPAC name of the product.

The IUPAC name of the product yielded is 6-ethoxycarbonyl-3,5-diphenyl-2cyclohexenone.

REFERENCES:
1. CHM 556 Organic Chemistry 2 lecture notes prepared by Prof. Faujan.
2. T.W. Graham Solomons, Craig B. Fryhle, Organic Chemistry, Asia, John Wiley and
Sons, 2011.
3. Aldol condensation, 16/11/2014, http://en.wikipedia.org/wiki/Aldol_condensation.
4. Chalcone, 16/11/2014, http://en.wikipedia.org/wiki/Chalcone.
5. Robinson annulation, 18/11/2014, http://en.wikipedia.org/wiki/robinson_annulation