Base-Catalyzed Oxidation-Reduction of Aldehydes by the Cannizzaro Reaction

Prepared by Mike Tran THEORY The purpose of this experiment is to oxidize and reduce an aromatic aldehyde, 4-chlorobenzaldehyde, and isolated to form benzoic acid and benzyl alcohol. MAIN REACTION(S) AND MECHANISMS The Cannizzaro reaction consists of an oxidation-reduction reaction between a hydroxide ion and aldehydes without -hydrogen atoms.

With the presence of a strong base, the first aldehyde molecule reduces to a second aldehyde molecule and then becomes a primary alcohol. Within this process the molecule oxidizes itself to the carboxylate anion and will result in a carboxylic acid and an alcohol.

PROCESS The course of this experiment was broken up into multiple scenarios: setting up and preparing the reagents for the reaction, the reaction itself, and then the isolation and purification process of the products. To prepare the reagents, potassium hydroxide (5.0 g) was dissolved in distilled water (5 mL) inside an Erlenmeyer flask. 4chlorobenzaldehyde (1.0 g) and methanol (2.5 mL) was added to to a 25 mL round bottom flask with a stir bar and set to dissolve as well. An

apparatus was also set up for heating under reflux and simple distillation. Then, potassium hydroxide (50% aqueous, 1.5 mL) was added to the round bottom flask reaction vessel and set to heat under reflux so that none of the reactants were able to escape during the experiment. A water bath was prepared so that temperature was more easily regulated rather than using sand. This temperature was set to 75 degrees C and the reaction vessel underwent the heating process for 1.5 hours with automatic stirring from the magnetic stir bar. Once the heating under reflux stage was complete, the solution was transferred to a separatory funnel for separation of the two products. Although both solutions were transparent, it was easy to distinguish that the reaction formed two layers of compounds. The lower layer was the organic layer and the upper was the aqueous layer. Each layer was then extracted to separate beakers as the Cannizzaro reaction was not complete. The carboxylic acid was in the aqueous layer and the alcohol was in the methylene chloride (organic) layer. To recover the p-chlorobenzyl alcohol, the methylene chloride layer was wash it with two portions saturated aqueous sodium chloride (2x5 mL) as this will neutralize the solution of residual acid. Once the layer has been extracted, it was dried with several spatula tips of anhydrous sodium sulfate until the solution turned clear. The solution underwent simple distillation to remove the dichloromethane, resulting in 4chlorobenzyl alcohol leftover. To recover the p-chlorobenzoic acid, it was cooled by placement inside an ice-water bath and acidified by adding concentrated hydrochloric acid (2.5 mL) until it was acidic (approximately pH = 3). It was then filtrated with a Hirsh funnel and allowed for collection of the white precipitate product, p-chlorobenzoic acid. This was set out to dry prior to gathering the products weight and melting point.

DATA AND OBSERVATIONS After the chemical components were added to recover the acid and the alcohol layer, I had completely mixed up which was the organic layer and which was the aqueous layer. Hydrochloric acid was added to the

alcohol layer so to make the solution acidic. Litmus paper was used periodically to check the acidity of the solution to make sure it was approximately at the pH level of 3. The acid layer had 5 mL of anhydrous sodium sulfates and 2.5mL of hydrochloric acid added to it before the product was filtrated out of the solution. The product of the alcohol layer was a cloudy white color when extracted and yielded white crystals when weight and melting point were measured.

RESULTS
Product Data for Alcohol Layer Theoretical Actual % Yield Yield Yield 4.03 g 1.25 g 31%

Product p-chlorobenzyl alcohol

Actual m.p 68-69

Literature m.p 70-72

Product p-chlorobenzoic acid

Product Data for Acid Layer Theoretical Actual % Yield Yield Yield 0.215 g 0.11 g 51%

Actual m.p 166-172

Literature m.p 149-150

Percent Yield Aqueous Layer (0.09g / 0.289g) x 100 = 31% recovered Organic Layer (0.1464g / 0.285g) x 100 = 51% recovered CONCLUSION The p-chlorobenzyl alcohol from the alcohol layer was pure within a 1 degree C melting point range and a 3.5% error, however only 31% of the product was retrieved. Such a low percent yield could have been caused by the acid and the other chemicals added to acidify the solution after mistaking the two different layers. The results found with the p-chlorobenzoic acid from the acid layer however did not show

such promising results. The melting point range was 6 degree C, which indicates that the product was not pure and something went wrong in the experiment. Again, this and the 51% product retrieved may be explained by the mix up of the two different layers.