Preparation of dibenzalacetone

Li Xuanji

Aim

The aim of this experiment was to synthesize dibenzalacetone via aldol condensation.

Introduction

Dibenzalacetone has the chemical formula C17 H14 O and can be written as CO(CH=CH(C6 H5 ))2 . It is a yellow solid that can form crystals. It is soluble in ethanol but not in water. It is used as a sunseen component. In organic reactions it can be used as a ligand for Pd(0) as Pd(0) complexes to the (conjugated) alkene double bond without changing oxidation state [?]. In this experiment we aim to synthesize dibenzalacetone via base-catalysed aldol condensation with acetone and 2 equivalents of benzaldehyde. The solid was then redissolved for recrystalisation and the crystals dried and weighed.

Procedure

Approximately 2.5 g of solid NaOH was dissolved in 25 mL of water and 25 mL of ethanol. In a separate 100 mL conical ask, 2.5 mL of benzaldehyde was collected from a pre-adjusted dispenser and 0.9 mL of acetone was added using a syringe. The NaOH solution was then added to the benzaldehyde-acetone mixture, which was the swirled at intervals for the next 15 minutes. A yellow precipitate was observed after about 10 minutes; after that, some orange-yellow precipitate began forming. The yellow solid was then collected by suction ltration as follows. A bchner ask was attached to a suction u pipe and a bchner funnel with lter paper was placed on the bchner ask. The solid u u and the contents of the conical ask were poured onto the lter paper. The ask was rinsed with cold deionised water. The solid was washed with cold water a few times. The red solid (which accounted for about 20% of the total volume of the solid) was then removed. The yellow solid was then transfered into a clean 100 mL conical ask which was placed on a hot plate. 2 mL of ethyl acetate was added and the mixture was warmed to a gental boil. More ethyl acetate was added dropwise to the mixture until all the solid 1

had just fully dissolved. The solution was then set aside to cool at room temperature, then immersed in an ice water bath. The resulting yellow crystals were then collected via suction ltration. The crystals were thene dried under an IR lamp. The melting point and mass of the crystals was then determined. The same recrystallisation procedure was performed with the red solid but it did not recrystallise.

Results

Mass of sample: 2.5115 g Melting point range: 104.1 C- 106.4 C

Yield Calculation
Mass of benzaldehyde = (1.045g/mL)(2.5mL) = 2.613g 26.13g 106.12g/mol = 0.0246mols

Mols of benzaldehyde =

Mass of acetone = (0.7925g/mL)(0.9mL) = 0.713g 0.713g 58.08g/mol = 0.0123mols

Mols of acetone =

Acetone is the limiting reagent. If all of it reacted, Mass dibenzalacetone = (0.0123mols)(234.30g/mol) = 2.88g 1.6068g 100% 2.877204g = 55.8%

Yield =

Discussion

We have synthesized dibenzalacetone with a 55.8% yield. This is below the expected yield. The melting point range is 2.3 K which means that it is not very pure. 2

The experiment design could be improved by adding the benzaldehyde and acetone mixture slowly as described in [?]. Experimental error for this experiment came mainly from the presence of the orange-red solid which we believe was martian rock an unwanted side-product. This could have been avoided by doing the ltration faster, before side products could form (as the red solid was only observed after the yellow precipitate formed) or less NaOH could be added.

Post-lab
What product would you expect if you were to use half the calculated number of equivalents of benzaldehyde? I would expect to get benzylideneacetone, molecular formula C10 H10 O (C6 H5 CH=CC(O)CH3 ). This is because the reaction would stop after a single aldol condensation after the benzaldehyde is used up.

Geometric isomers of dibenzalacetone There are 3 isomers in total

Other than using melting point determination, suggest another method that can be used to check the purity of your product . I would use H-NMR to check the purity of the product. As dibenzaldehyde has conjugated double bonds and contains both the benzyl group and alkene group the hydrogen atoms will experience strong anisotropic eect and will be shifted downeld on the H-NMR spectra. Most side products will not have this and this should show up clearly on the spectra when we attempt to assign the protons. If more purity is desired the H-NMR spectrum of commercial dibenzaldehyde could be obtained and compared to that of our compound.

Mechanism

Conclusion

We have successfully synthesized dibenzaldehyde and performed recrystallization to obtain pure crystals with a melting point range of 2.3 K.

References
[1] Clayden, Jonathan et. al. Organic Chemistry. Oxford University Press, USA. [2] Conard, C. R.; Dolliver, M. A. Dibenzalacetone. Org. Synth., Last accessed at http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv2p0167 on August 5, 2012 [3] Takahashi, Y.; Ito, Ts.; Sakai, S.; Ishii, Y. A novel palladium(0) complex; bis(dibenzylideneacetone)palladium(0). Journal of the Chemical Society D: Chemical Communications: 1065. (1970)