EXPERIMENT 5

The Robinson Annulations Reaction

OBJECTIVES

Performing Robinson annulations reaction to prepare an α,𝛽-unsaturated cyclic ketone by

using trans-chalcone that have been prepared in Michael addition using sodium-catalyzed
conjugate addition of ethyl acetoacetate. Calculating the percentage yield, obtained the
melting point and NMR-spectrum for the product yield.

INTRODUCTION

The Robinson annulation is the Michael addition followed by a simple aldol condensation
may be used to build one ring onto another. The ring which is produced will be an α,β-
unsaturated cyclic ketone. In this experiment, we will react ethyl acetoacetate with trans-
chalcone prepared in the previous experiment to yield the product 6-ethoxycarbonyl-3,5-
diphenyl-2-cyclohexenone. The product 6-ethoxycarbonyl-3,5-diphenyl -2-
cyclohexenonewill have a structure as below.

6-ethoxycarbonyl-3,5-diphenyl -2-cyclohexenone

An α, β-unsaturated ketone can be prepared by conjugate addition of ethyl acetoacetate to

trans-chalcone followed by an intermolecular aldol condensation reaction and
dehydration.bA Michael reaction is the nucleophilic addition of an α, β-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 β-
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 α-carbon
with at least two hydrogen is deprotonated. The aldol condensation reaction is an
electrophilic substitution at the deprotonated α-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 anddehydrated by the base. Finally, an α, β-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.

APPARATUS

 50mL of round bottom flask

 Boiling stone
 Reflux Condenser
 Stirring Rod
 Measuring Cylinder
 Spatula
 Posture pipette
 Centrifuge
 Heating Mantle.

CHEMICALS

 1.2 g of finely ground trans-chalcone

 0.75g of ethyl acetoacetate
 25mL of 95% ethanol
 Pellet sodium hydroxide
 Water ice
 Acetone
PROCEDURE

1. Assembling the apparatus

I. 1.2g of trans-3-nitrochalcone was added with 0.75g of ethyl acetoacetate
solution and 25mL of 95% ethanol solution.
II. The mixture was mixed well until the solid was dissolved in a round bottom
flask.
III. The boiling chip was added into the mixture followed by 0.09g of sodium
hydroxide,NaOH pellet.
IV. The mixture was refluxed until the mixture was boiled and the mixture was
left to be boiled for 1 hour.
V. The refluxed mixture was left 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 and forming
oil.
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 80°C and weighed
the product.
3. Removal of catalyst
I. The isolated product was transferred into 100mL Beaker and diluted by using
7mL acetone (reagent grade).
II. The mixture was stirred but don’t expect all the solid would dissolve.
 III. The liquid with some solid (as little as can) was transferred into the centrifuge
tube using Pasteur Pipette to separate the liquid and solid more effectively.
IV. The mixture was centrifuged for about 3 minutes at 200rpm.
V. An empty conical flask was weighed and transferred the clear acetone extract
that have been centrifuge into the conical flask.
VI. The solution was heated in hot water bath and was scratched to induce
crystallization. Oily solid products will form.
VII. 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 left 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
15minutes.
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 80°C.
VII. The crystal was weighed and percentage yield was calculated based on the
theoretical yield.
VIII. The melting point of the crystal was taken and was sent for NMR test.
RESULTS & CALCULATION

Mass of trans-chalcone 1.2348 g

Mass of 1 pallet sodium hydroxide 0.0930 g
Mass of crystals (Isolation of crude product) 0.235 g
Mass of crystals (Removal of catalyst) 0.1485 g
Mass of petri dish + filter paper 42.2315 g
Mass of petri dish + filter paper +product 42.3699 g
Mass of Product 0.1384 g

NMR Result

Signal Concentration, ppm

3 H, triplet 1.11 ppm
2 H,quartet 1.66 ppm
1 H, singlet 4.89 ppm
5H, multiplet (benzene ring) 7.71 ppm
2H, doublet 3.14 ppm

Theoretical yield of 6-ethoxycarbonyl-3,5-diphenyl -2-cyclohexenone:

No. mole of ethyl acetoacetate 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑡ℎ𝑦𝑙 𝑎𝑐𝑒𝑡𝑜𝑎𝑐𝑒𝑡𝑎𝑡𝑒

=
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑡ℎℎ𝑦𝑙 𝑎𝑐𝑒𝑡𝑜𝑎𝑐𝑒𝑡𝑎𝑡𝑒
0.75 𝑔
= 𝑔
130.07
𝑚𝑜𝑙

=0.0058 mol

No. mole of chalcone 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐ℎ𝑎𝑙𝑐𝑜𝑛𝑒

=
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐ℎ𝑎𝑙𝑐𝑜𝑛𝑒
1.2348 g
= 𝑔
254.25
𝑚𝑜𝑙

=0.0049 mol
1 mole of chalcone = 1 mole of ethyl acetoacetate

The limiting reactant is chalcone.

Theoretical yield = Mole of chalcone X Molar mass of 6-ethoxycarbonyl-3,5-

diphenyl -2-cyclohexenone
= 0.0049 mol x 350.4 g/mol
=1.71696 g
Percentage of yield (product) 𝑎𝑐𝑡𝑢𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
= 𝑥 100%
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡
0.1384 𝑔
= X 100%
1.71696 𝑔

=8.0608 %
DISCUSSION

In this experiment, the reaction occurs was robinson annulations reaction. This
reaction needs the product from Michael addition reaction proceeds with aldol
condensation. The product from robinson annulations is α,β-unsaturated cyclic ketone. The
reactions started with trans-chalcone was prepared and reacted with ethyl-acetoacetate in
the presence of ethanol as catalyst to yield the dicarbonyl ester product, this reaction was
Micheal addition reaction. By adding sodium hydroxide the ethyl-acetoacetate will form
enolate ion which is β-hydroxyketo. As we know the micheal addition reaction will reacts
when we have α,β-unsaturated carbonyl will penetrate by the enolate ion. The β-
hydroxyketo then was refluxed to eliminate water which yield an keto compound. From the
keto compound the robinson annulation will undergoes their reaction by adding sodium
hydroxide. The enolate ion of keto compound will form and started to form cyclic. The
simple aldol condenstation will form and produce α,β-unsaturated cyclic ketone, which is 6-
ethoxycarbonyl-3,5-diphenyl -2-cyclohexenone.

There is some precaution we should take seriously while handling the experiment to
prevent from contaminates and lose the product. Firstly, during reflux make sure the
product not over boiled to prevent from splash into the condenser. Next, error 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 solid can pass through the filter paper
and flow into the conical flask. This can affect the actual yield of the product.

CONCLUSION

The Robinson annulations reaction was done to yield 6-ethoxycarbonyl-3,5-diphenyl-2-

cyclohexenone and was confirmed the structure by using NMR spectrum. The percentage
yield of the product is 8.0608% and the melting point is 160°C.

REFERENCES
  L.Hunt.(n.d) Department of chemistry university of Calgary: The robinson
annulations reaction. Retrieved from
http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch18/ch18-4-4.html
 1) Donal L . Pavia ; Gary M. Lampman;George S Kriz;Randall G Engel (2013). A
microscale approach to organic laboratory techniques.(5th). published by
Belmont/Cole , Cengage Learning
 T.W.Graham Solomons & Craig B.Fryhle (2011);Organic Chemistry,(10th)

QUESTION

1. Why was it possible to separate the product from sodium hydroxide using acetone?

Its possible to separate the product from sodium hydroxide using acetone because
the organic product, 6-ethoxycarbonyl-3,5-diphenyl-2-cyclohexenone dissolve in
acetone, while sodium hydroxide is insoluble in acetone. Thus, sodium hydroxide will
precipitate turn cloudy and using the centrifuging sodium hydroxide will separated
from the product.

2. The white solid that remains in the centrifuge tube after acetone extraction fizzes
when hydrochloric acid is added, suggesting that sodium carbonate is present.How
 did this substance form? Give a balanced equation for its formation. Also give an
equation for the reaction for the reaction of sodium carbonate with hydrochloric
acid.
Na2CO3 (aq) + HCl (aq)  NaHCO3 (aq) + NaCl (aq)
NaHCO3 (aq) + HCl (aq)  NaCl (aq) + CO2 (g) + H2O (l)
Sodium carbonate and hydrochloric acid that produces salt, carbon dioxide and
water.
3. Draw a mechanism for each of the three steps in the preparation of the 6-
ethoxycarbonly-3,5-diphenyl-2-cyclohexenone.You may assume that sodium
hydroxide functions as a base and ethanol serves as a proton source

QUESTION EXPERIMENT 2 : Reduction of Cyclohexanone

1. How do you confirm that the cyclohexanone has been reduced to cyclohexanol using
IR analysis ?
By looking for the wavenumber for cylohexanol functional group . For the
cyclohexanone there must must be peak for ketone C=O at 1780-1650 cm-1 while for
the cyclohexanol the alchol O-H at 3650-3200 cm-1.

2. What is the function of anhydrous sodium sulphate in the experiment?

To acts as the drying agent to adsorb all the excess water moisture in the
cyclohexanol solution.
 3. If you have the following compound, can you reduce the ketone using sodium
borohydride without affecting the ester functional group ? explain your answer.

The sodium borohydride only can reduce ketone into alcohol but will not reduce and
affect the ester functional group. This is because the ester is much less reactive to
reduction than the ketones and sodium borohydride is too weak reducing agent to
them.sodium borohydride is preferred to reduce the ketones to alcohol because it
does not react violently with water, H2O.

EXPERIMENT 3 : Esterification of vanillin

1. Under different reaction media, vanillin undergoes esterification with acetyl chloride
yielding two different products.
a) Based on the IR spectrum of vanillin, at what range should you observe the
absorption signal of the hydroxyl group?
The absorption signal of hydroxyl group is within the range of 2700cm-1 to 3200cm-1.

b) Based on its H NMR spectrum, what is the expected chemical shift value for the
methoxy group (OCH3)? What is its multiplicity?

3.8 ppm to 3.9 ppm, singlet

c) Draw the structures of the major product for the esterification of vanillin with acetyl
chloride in :
i. 10% NaOH solution

ii. 1.0 M H2SO4 solution.

2. Write the mechanism for the reaction between vanillin and acetyl chloride in 10%
NaOH solution.
 CHM 556

Organic Chemistry II ( Laboratory Report)

 Experiment 5

The Robinson Annulations Reaction

Name : Rasyiqah Binti Abdul Rani

Student No. : 2017442676

Date of experiment : 29 st October 2018

Date of submission : 12 nd November 2018

Lab Partner’s Name : Nur Afiqah Nadhiah Binti Ammar Rusdan

(2017442658)
Lecturer’s Name : Dr. Syahrul Imran Bin Abu Bakar