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Aldol Condensation Synthesis of Dibenzalacetone
Purpose
Use a base-catalyzed reaction to condense acetone with benzaldehyde, forming a colored, crystalline product.
Introduction
Aldol Condensation is an extremely useful carbon-carbon bond-forming reaction in organic chemistry. An aldol condensation is a reaction that is named based on the type of product formed when two aldehydes (or ketones), in the presence of dilute base, yields a molecule having both aldehyde (ald-) and alcohol (-ol) functional groups. The aldol products are -hydroxyaldehydes (or -hydroxyketones). This reaction is used extensively for the synthesis of new CC bonds and to make larger organic molecules. The reaction of an aldehyde with a ketone employing sodium hydroxide as the base is an example of a mixed aldol condensation reaction. You will do a double mixed-aldol condensation reaction between acetone and benzaldehyde to produce Dibenzalacetone. Dibenzalacetone is a conjugated molecule. This conjugation allows the molecule to absorb sunlight and UV rays. Thus, when dibenzalacetone is used in sunscreen, the conjugation in the molecule allows the dibenzalacetone, and thus the sunscreen, to absorb the sunlight before it reaches the skin, thus preventing sun burns from occurring. Acetone has -hydrogens (on both sides) and thus can be
63 deprotonated to give a nucleophilic enolate anion. The aldehyde carbonyl is much more electrophilic than that of a ketone, and therefore reacts rapidly with the enolate. The alkoxide produced is protonated by solvent, giving a -hydroxyketone, which undergoes base-catalyzed dehydration. The elimination process is particularly fast in this case because the alkene is stabilized by conjugation to not only the carbonyl but also the benzene. In todays experiment you will use excess benzaldehyde, such that the aldol condensation can occur on both sides of the ketone. Mechanism for Aldol Condensation
Experimental Calculations: 1. Calculate the volume required to produce 0.0125 mol of acetone. 2. Calculate the volume of 2.2 equivalents of benzaldehyde. (In other words, 2.2 times as many moles of benzaldehyde as of acetone.) Note: the equation involves a simple 2:1 stoichiometry.
64 By using an actual 2.2:1 ratio, it ensures that the benzaldehyde is surplus and that the acetone is limiting. This is helpful for several reasons: a. Aldehyde oxidation. Aldehydes are often impure, because oxidation to carboxylic acid is fairly facile. By using 2.2 equivalents of benzaldehyde, then even if 10% of the benzaldehyde is corrupt we ensure that we still have enough to fully react with the acetone. b. Reaction Time. By having an excess of benzaldehyde, it makes it easier for the reaction to go to completion. Otherwise late in the reaction there isnt much benzaldehyde left to react, so the reaction slows down a lot. By intentionally putting in some extra, it maintains at least a minimal concentration of electrophilic till the very end, such that getting 100% conversion of the ketone isnt so hard and doesnt take so long. c. Ease of Product Purification: Disubstitution versus monosubstitution. Enabling complete conversion greatly simplifies purification. If complete conversion does not occur, either because benzaldehyde runs out or because insufficient time is used, the desired disubstitution product dibenzalacetone, in which two benzaldehydes have been incorporated, is contaminated by benzalacetone, the monosubstitution product in which only one benzaldehyde has been incorporated. Since the mono- and disubstituted products arent that different, its not that easy to remove the undesired side-product from the main desired product. But if you just make sure the reaction goes all the way to the desired product, then you dont need to worry about it! Doing the Reaction: 1. Use a 125-mL Erlenmeyer flask with a magnetic stirring bar. 2. Add 5 mL of (3M NaOH), 10 mL H2O and 20 mL EtOH (or MeOH). 3. Place the solution on the magnetic stirrer and adjust the stirring dial to get a nice, even stirring action. 4. To this add the calculated amount of benzaldehyde
65 5. Add the calculated amount of acetone, last. (The acetone should go in last, after the benzaldehyde electrophile is already available. If the acetone goes in first, it could do aldol condensation on itself, in which enolate anions just attacks neutral acetone carbonyls. Ketone carbonyls arent competitive with aldehyde carbonyls as electrophiles, but if there are no aldehydes available, ketones are better than nothing!) 6. Watch the solution carefully, with a watch, at the beginning of the reaction, so that you can keep good observational records. How long does it take for the solution to turn yellow? Given that all the reactants are colorless, what does the yellow color mean? How long does it take for the solution to become cloudy, and for solid to then accumulate? 7. Let the solution stir for 30 minutes. (Calculate, write report, etc.) 8. Add 20 mL of cold water, and then filter the mixture 9. Pour the filtrate into the waste container. 10. Wash the crystals three times with 50-mL of cold water each time. The product is so organic that it has essentially no solubility in water. Water washes are no threat to your yield. The initial product is contaminated by sodium hydroxide. The extensive water washes removes all traces of sodium hydroxide. 11. If the crystals are still pretty wet, press them drier by pressing a filter paper on top to absorb water. 12. Purify the bulk of your crystals by recrystallizing from ethanol 13. After you dry the crystals weigh them, calculate the % yield and give the product to the TA.
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Aldol Condensation
Synthesis of Dibenzalacetone Report Sheet Write the chemical equation that represents your experiment.
Name:-----------------
- moles of benzaldehyde used = ---------- moles of acetone used = ----------------
67 What is the limiting reactant? (Show calculations).
Calculate the theoretical yield of dibenzalacetone.
Mass of your product (experimental yield=actual yield) = ------------- Percentage yield = Questions: 1. Propose a mechanism for the base-catalyzed condensation of cyclohexanone with two molecules of benzaldehyde to give dibenzalcyclohexanone.
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2. Predict the product of the aldol condensation of acetophenone.

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Aldol Condensation Synthesis of Dibenzalacetone

- moles of benzaldehyde used = ---------- moles of acetone used = ----------------

67 What is the limiting reactant? (Show calculations).

Calculate the theoretical yield of dibenzalacetone.

2. Predict the product of the aldol condensation of acetophenone.

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