Mixed Aldol Condensation (Claisen-Schmidt Reaction)

Preparation of Benzalacetophenone (1,3-diphenyl-2-propen-1-one)

O H O

O OH-1

+ +

H3C

benzaldehyde

acetophenone

benzalacetophenone

In a 125 mL Erlenmeyer flask place 20 mL of 10% NaOH solution, 12 mL of ethanol, and 4.8 g of acetophenone. Begin constant stirring with a magnetic stirring device, and carefully add 4.2 g of benzaldehyde. Have a cold water bath ready if necessary as you maintain the internal temperature at 25-30o and stir the mixture vigorously for a period of 70 min. (Be sure to keep the stirring bar far away from the bulb of the thermometer). Crystallization may be aided by scratching the inside of the flask with a stirring rod if it has not started already or add a seed crystal of benzalacetophenone given by the instructor. Then chill the reaction mixture in an ice bath for thirty minutes to complete crystallization. If the crystals tend to clump, break them up with a stirring rod. Collect the solid product with suction filtration and wash the solid thoroughly with cold water until the washings are neutral to litmus. Then wash the crystals with ice-cold ethanol and press dry on the filter. Reserve a few seed crystals, and recrystallize the crude product with warm ethanol (approx. 45-50oC). Use approx. 4mL of ethanol per gram of product. Suction filtrate again and maintain suction long enough to thoroughly dry the crystals with air. Again, break up any clumps. Determine the % yield of the product. Theory: An extension of a simple aldol condensation reaction is the mixed aldol condensation reaction. A mixed aldol reaction leads to a number of different products unless one of the carbonyl compounds involved cannot form an enolate ion (i.e. the compound has no -hydrogens). A good choice for such a compound is an aromatic aldehyde. Even more specificity can be accomplished by having the other carbonyl compound form only one possible enolate ion (ex. acetophenone as opposed to 2-butanone). Once formed, the nucleophilic enolate ion attacks carbonyl carbon to form a hydroxy carbonyl product (aldol addition product).The -hydroxy carbonyl product then eliminates a molecule of water to form a conjugated system composed of a double bond and the carbonyl group. If the case of todays

experiment, the conjugation is extended through two benzene rings as well, producing a very stable product, benzalacetophenone. This compound exists in different forms, the most prominent being a trans- form about the C=C double bond.

O H3C

OH-1

.. H2C

-1

HOH

alpha-H compound

enolate ion

.. H2C

-1

OH H C H2 H O - H2O

+
no alpha-H

aldol addition product O

aldol condensation product

Data Sheet for Preparation of Benzalacetophenone Mass of benzaldehyde Mol of benzaldehyde Mass of acetophenone Mol of acetophenone Theoretical mol of benzalacetophenone Theoretical mass of benzalacetophenone Actual mass of benzalacetophenone Percent yield of benzalacetophenone __________ g __________ mol __________ g __________ mol __________ mol __________ g __________ g __________%

Description of product ___________________________________________ _________________________________________________________________ Comments during preparation ________________________________________ _________________________________________________________________ _________________________________________________________________ Calculations: