Objective

Introduction
Experimental
Procedure
Results and
Observation
Calculation
Discussion
Conclusion
Questions Answer
Reference
Total Marks

Marks
Allocat
ed
1
2
2

Marks

4
4
2
1
3
1
20

FACULTY OF APPLIED SCIENCES

LABORATORY LAB REPORT
ORGANIC CHEMISTRY (II)
Experiment 5 : Robinson Annulation of NItrochalcone
Name : Mohd Nakirudin bin Muhamad Nor
Students ID : 2014595967
Program Code : AS202
Course Code : CHM556
Partners Name : 1) Nor Asyikin
Date Of Experiment : 25th April 2016
Date of Submission : 16th May 2016
Objective

To study the Robinson Annulation Reaction by performing a sodium-catalyzed

conjugate addition of ethyl acetoacetate with a trans-Chalcone to form an ,unsaturated ketone.
Introduction
The Robinson annulation is an organic reaction used to convert a ketone and an ,unsaturated ketone to a cyclohexenone using base. The mechanism begins with
deprotonation with the base of the -hydrogen of the ketone to form an enolate
(Solomon,2013) . The enolate then does a 1,4 addition to the conjugated olefin
(Michael addition), which then abstracks a proton from water to form a diketone.
Deprotonation of the other -hydrogen with base forms another enolate which then
does in intramolecular attack on the ketone group to give a cyclic alkoxy
intermediate. Protonation of the alkoxy and a final elimination step result in the
cyclo-hexenone product(Solomon,2013). The figure below shows the methodology
to produce a new six-membered ring compound.

Methodology
1.Preparation
of solid
Figure
1: Figure
1.2 of trans-3-nitrochalcone
show the was added with 0.73mL of ethyl acetoacetate solution
and 25mL ofmechanism
95% ethanol
The mixture was mixed well until the solid was
forsolution.
the
dissolved in a round
bottom flask. 0.09g of NaOH pellet was added into the mixture
Robinson
and a boilingAnnulation
chip was added.
ProcessThe mixture was refluxed until the mixture was boiled
and the mixture was let to be boiled for 1 hour. The refluxed mixture was was allow
to be cooled at room temperature in order to proceed to the isolation of the crude
product.
2. Isolation of crude product
The mixture was transferred into a small beaker and 10mL of water was added with
scratching to induce crystallization. After some of the product forms the solid, the
scratching is conducted in ice water bath for 30 minutes to increase the rate of
reaction for the crystallization. The solid was filtered by using Buchner funnel
vacuum pump and 4mL of ice cold water was used to aid transfer. The beaker was
rinsed by using 4mL of ice cold ethanol (95%). The solid was dried overnight in the
oven at temperature 80C.
3.Removal of catalyst.
The isolated product was diluted by using 7mL acetone (reagent grade) in a beaker.
The liquid with some solid (as little as can) was transferred into the glass centrifuge
to separate the liquid and solid more effectively. The mixture was centrifuged for
about 3 minutes at 200rpm. The weight of an empty conical flask was taken and the
centrifuged solution (without any solid) was placed into it. The solution was heated
in hot water bath and was scratched to induce crystallization. An oily solid product

will form. 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.
The product was added with 9mL of 95% boiling ethanol solution to dissolve the
product. The dissolved solution in the ethanol was let to cool at room temperature.
After the solution was cooled, the solution was scratched to induce the
crystallization, and then was left undisturbed for a few minutes. The crystal formed,
and the mixture was placed with ice cold for about 15 minutes. The crystal was
filtered by using Buchner funnel vacuum pump with washing of 3 portions of 1mL
ice cold 95% ethanol. The crystal was dried in the oven overnight at temperature of
80C. The crystal (6-ethoxycarbonyl-3,5-diphenyl-2-cyclohexenone) was weighed,
percentage yield was calculated based on the theoretical yield. The melting point of
the crystal was observed. Lastly the product obtained was further analyzed using
NMR Spectroscopy and IR.

Result and Calculation

Mass of Nitrochalcone (g) 0.0001g
Mass of Empty Conical Flask (g)

: 1.2426g
: 78.6390

0.0001g
Mass of Conical Flask with Product (g)

: 80.5462

0.0001g
Mass of Impure Product (g) 0.0001g
: 1.9072
Table 1: The figure shows the mass of Impure product form upon addition of
Nitrochalcone with Ethyl Acetoacetate and Ethanol.
Mass of 3 filter paper (g) 0.0001g
Mass of 3 filter paper + Product (g)

: 0.8385g
: 2.3108

0.0001g
Mass of Product (g) 0.0001g
: 1.4723
Melting Point 0C (0.250C)
: 111 0C
Table 2: The figure shows the mass of product form after the product being washed,
dried with a night at 800C
Observation
1. During the addition of isolated mixture with 7mL of acetone, it is observed
yellow, lumpy-sticky product is soluble in acetone and producing a clear
brown upon the addition. During the heating process being conducted, the
yellow lumpy-sticky product liquefied and the liquid is also observed solidified
during the cold nitrogen air is introduced.
Calculation

Nitrochalcone
diphenyl-2-cyclohexenone
Number
of Mole
of: Nitrochalcone:
Molar
Mass
253g/mol

6-ethoxycarbonyl-3,5Molar Mass : 365g/mol

= (1.2426g)/(253g/mol)
= 4.911E-3 mole
Theoritical Mass of 6-ethoxycarbonyl-3,5-diphenyl-2-cyclohexenone formed :
= 4.911E-3 mole X (365g/mol)
= 1.7925g
Percentage of Error
= ((1.7925 1.4723)/1.7925) X 100%
= 17.86%

Discussions
A Michael reaction followed by an aldol condensation produced 6ethoxycarbonyl-3,5-diphenyl-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 of yield is found to be at 82.17%.
From the IR Spectroscopy, it is found that there are presence of these functional
group at stated wavelengths: Functional Group
(R)-C=0-(R)
Aromatic Ring
C=C
C-O
C-O-C

Wavelength (cm-1)
1732.28
1659.69
1531.70
1351.72
1206.92

It can be deduced that, the product from this analysis may contained the Ester,
Aromatic Ring, Alkene, C-O and C-O-C bond. It is also found that there is still
presence of Hydroxyl functional group at 3650.31 cm-1. This trace analysis is may
be due to the product is not 100% dry. In order to determine the structure of the
compound, NMR Analysis is conducted, and the result is found to be stated
below :Proton Observed
-CH3
-CH2O
-Ph

Chemical Shift (ppm)

0.9-1.8
3.0-4.4
7.5-8.2

It not sufficient for us to evaluate the structure of the product, due to NMR
Spectroscopy is found to be producing broad peak, still certain prediction can be

made from the spectrum. The product may contain 2 aromatic ring, since the
spectrum shows that the peak is quite abundance at 7.5-8.2 ppm, -CH 3 -CH2 at
1.1-1.7ppm and may contain either a Methyl-O or Ethyl-O. Nevertheless,
understanding the concept of Robinson Annulation may provide us what is the
final product likely to form from the known starting material which is NitroChalcone.
Conclusion
The Robinson annulation reaction was done to yield 6-ethoxycarbonyl-3,5diphenyl-2-cyclohexenone and was confirmed the structure by using NMR
spectrum. The percentage yield of the product is 82.14%, and the melting point
is 111C.
Reference
1. T.W. Graham Solomon, Craig B. Fryhle, Organic Chemistry, Asia, John Wiley
and Sons, 2011.
2. Aldol condensation,
13/5/2106, http://en.wikipedia.org/wiki/Aldol_condensation.
3. Chalcone, 11/5/2106, http://en.wikipedia.org/wiki/Chalcone.
4. Robinson annulation,
13/5/2106, http://en.wikipedia.org/wiki/robinson_annulation.

Questions

1. Due to the fact that only one of them is soluble in acetone. After separation it
is then possible to evaporate the acetone to get the two substances
completely separate.
2. .

3. .

.
4. Chalcones can be prepared by an aldol condensation between
benzaldehyde and acetophenone in the presence of sodium hydroxide as
a catalyst.

This reaction has been found to work without any solvent at all - a solidstate reaction. The reaction between substituted benzaldehydes and
acetophenone.