Experiment 4 : The aldol condensation reaction : Preparation of Benzalacetophenones (Chalcones )

OBJECTIVE: To synthesis benzalacetophenones (chalcones) by aldol condensation reaction. To determine the percentage yield of the crude product. To identify the melting point of the purified product. To characterize benzalacetophenones (chalcones) from the H1 NMR spectrum. . INTRODUCTION: An aldol condensation is an organic reaction in which an enol or an enolate ion reacts with a carbonyl compound to form a -hydroxyaldehyde or -hydroxyketone, followed by a dehydration to give a conjugated enone. Benzaldehyde reacts with a ketone in the presence of base to give ,-unsaturated ketones. This reaction is an example of a crossed aldol condensation where the intermediate dehydrates to produce the resonance-stabilized unsaturated ketone.

As illustrated for the reaction of benzaldehyde with a general ketone, the ketone looses a proton

from an -carbon to form an enolate ion, which attacks the carbonyl carbon of the aldehyde to yield, after protonation, a -hydroxy ketone. This intermediate is, for aromatic aldehydes at least, instable and undergoes base-catalyzed dehydration to yield the unsaturated product.

PROCEDURES: To run the reaction, 0.75g of 3-nitrobelzaldehyde is placed in a 50mL Erlenmeyer flask. Then, 0.60mL of acetophenone and 4.0mL of 95% ethanol are added to the flask. The flask is swirled to mix the reagent and dissolved any solids present. The flask is warmed on the hot plate to dissolve the solids. Then, it is cooled at room temperature. 0.5mL of sodium hydroxide is added into the mixture and swirled until it solidified or the mixture become very cloudy. For isolation of the crude product, 10mL of ice water is added into the flask. The mixture is stirred if solids or oil is present to break up the solid mass. The mixture is transferred to a beaker with 15mL ice water. The precipitate is stirred to break it up and the solid is collected on B chner funnel. The product is washed with cold water. The solid is allowed to dry for 30minutes. The solid is weighed and the percentage yield is determined. For the crystallization, 0.50g of sample is crystallized from 20mL of hot methanol. The flask is gently scratched to induce crystallization while cooling. The literature melting point is 146oC.

RESULT: Mass of 3-nitrobenzaldehyde = 0.7677 g Mass of crude product Melting point = 0.4195 g =140 oC

Calculation: Mass of 3-nitrobenzaldehyde = 0.7677 g No. mol of 3-nitrobenzaldehyde = Mass of 3-nitrobenzaldehyde / MW = 0.7677g / 151.12 g/mol = 0.005 mol

From the above reaction equation, 1 mol 3-nitrobenzaldehyde 1 mol 3-nitrochalcone Therefore, no.mol of 3-nitrochalcone is 0.005 mol. Mass of 3-nitrochalcone (theoretical) = No.mol of 3-nitrochalcone x MW = 0.005 mol x 253.26 g/mol = 1.2663 g (theoretical)

Mass of 3-nitrochalcone (actual) = 0.5136 g Percentage yield = (Actual yield / Theoretical yield )x 100% = (0.5136 / 1.2663 )x 100% = 40.56%

Percentage error = (Theoretical yield Actual yield) / Theoretical yield x 100% = (1.2663 0.5136) / 1.2663 x 100% = 59.44 %

DISCUSSION: In this experiment, benzalacetophenones (chalcones) are prepared by the reaction of a substituted benzaldehyde with acetophenone in aqueous base. Based on the chemical equation, the limiting reactant for the reaction is 3-nitrobenzaldehyde. By comparing the number of mol of both compound, the theoretical mass of 3nitrochalcone can be calculated. From the result, quite small percent of crude product have been obtained. The product seems to be not pure enough since the percentage yield obtained is only 40.56%. The melting point of the purified product is 140oC that is quite close to the literature melting point which is 146oC. We did not get result closes to the theoretical, due to several errors that occur while doing this experiment. Firstly, error while collecting the solids by using Buchner funnels. The pressure that we use to collect the solids is too high and causes the filter paper full of holes. That will cause the amount of crude product become less and give effect to their weight. The temperature of the oven should be below 50oC to avoid the bond between molecule break and give bad effect for our result. We have to make sure that the crude product is dry enough before being weighed to avoid error while weighing. Based on our H1 NMR spectrum result, there are 4 basic types of H present in the ratio of 4:1:1:1:5. Using the chemical shift charts, the H can be assigned to the peaks approximately as below: 7.4ppm (4H) : ArH 5.3ppm (1H) : CH=CH 3.4ppm (1H) : CHC=OAr

2.5ppm (3H) : ArH We observed that there are 4 distinct signals, with chemical shift of approximately 7.4, 5.3, 3.4 and 2.5ppm. One of the signal (7.4ppm) is noticeably downfield of the others, indicates hydrogen atom that are likely to be near an electronegative group that deshield the ArH group. The presences of 4 distinct signals suggest that there are three distinct proton environments in the molecule. The signal at 7.4ppm is multiplet. Since the signal is more downfield and has 4 hydrogen on a benzene ring with nitrogen oxide substituent, we conclude that this signal is from ArH group and next to CH group. The signal at 5.3 and 3.4ppm is to be a duplet since the adjacent carbon has 1 hydrogen atom. At signal 3.4ppm, we conclude that it is ketone (CHC=OAr) and 5.3ppm as carbon double bond since there is only 1 hydrogen attach to each carbon. Lastly, at signal 2.5ppm, it seems to be a quartet since there is 3 hydrogen at the aromatic compound (ArH). The ArH group is said to occur upfield since the C=O is less electronegative than NO. Electronegative groups attached to the C-H system decrease the electron density around the protons, and there is deshield so the chemical shift increases.

CONCLUSION: From this experiment, 3-nitrochalcone is prepared by aldol condensation reaction between substituted benzaldehyde (3-nitrobenzaldehyde) and acetophenone in aqueous base. The percentage yield of the crude product obtained is 40.56% and the melting point of the purified product is 140oC. The 3-nitrochalcone has been successfully characterized from the H1 NMR spectrum. . REFERENCES: T.W. Graham Solomons & Craig B. Fryhle Organic Chemistry, 9th Edition (2007)

 Donald L. Pavia, Gary M. Lampman, George S. Kriz, & Randall G. Enge Introduction of Organic Laboratory Techniques, 2nd Edition (2005) http://en.wikipedia.org/wiki/Aldol_condensation http://www.cis.rit.edu/htbooks/nmr/inside.htm http://en.wikipedia.org/wiki/Chalcone

NAME : MUHAMMAD NAIM BIN MOHD RASHID

ID NUMBER : 2012216634

INSTRUCTOR S NAME : DR. NORIZAN AHMAT

PARTNERS NAME : MUHAMMAD FAID BIN A. KADIR

DATE OF EXPERIMENT : 11. 11 .2013

DATE OF SUBMISSION : 25. 11. 2013