CHEM 2425. Chapter 23. Carbonyl Condensation Reactions (Homework) W
CHEM 2425. Chapter 23. Carbonyl Condensation Reactions (Homework) W
CHEM 2425. Chapter 23. Carbonyl Condensation Reactions (Homework) W
Exhibit 23-1
Draw the structure of the aldol self-condensation product for each of the following compounds. If a
compound does not undergo aldol self-condensation, explain why it does not.
1.
2.
3.
4.
Exhibit 23-2
Consider the reaction below to answer the following question(s):
5. Refer to Exhibit 23-2. Write the complete stepwise mechanism for the reaction above. Show all intermediate
structures and all electron flow with arrows.
a. a , -unsaturated aldehyde
b. an , -unsaturated ketone
c. an , -unsaturated aldehyde
d. an enol
Exhibit 23-3
Consider the data below to answer the following question(s):
The Friedlander Quinoline Synthesis, first reported in 1882, is the base-catalyzed condensation of
2-aminobenzaldehydes with ketones to form quinoline derivatives.
8. Refer to Exhibit 23-3. The first step of the Friedlander Quinoline Synthesis is a mixed aldol condensation.
Write the complete stepwise mechanism for this reaction.
9. Refer to Exhibit 23-3. The second step of the Friedlander Quinoline Synthesis is a nucleophilic addition of a
primary amine to a ketone yielding an imine. Write the complete stepwise mechanism for this imine forming
reaction. Show all electron flow with arrows and show all intermediate structures.
Exhibit 23-4
Each of the following compounds can be prepared by a mixed aldol condensation reaction. Give the structures
of the aldehyde and/or ketone precursors for each aldol product and formulate the reaction.
11.
12.
13.
Exhibit 23-5
Consider the reaction below to answer the following question(s).
14. Refer to Exhibit 23-5. Which carbonyl compound functions as the electrophile in this reaction?
Exhibit 23-6
Draw the structure of the product you would expect to obtain by Claisen condensation of each of the
following esters. If an ester does not undergo Claisen condensation, explain why it does not.
17.
18.
Exhibit 23-7
Consider the reaction below to answer the following question(s):
Acetoacetic ester can be prepared by the Claisen self-condensation reaction of ethyl acetate.
19. Refer to Exhibit 23-7. Write the complete stepwise mechanism for this reaction. Show all electron flow with
arrows and draw all intermediate structures.
20. Ethyl acetate can be prepared from ethanol as the only organic starting material. Show all reagents and
structures for all intermediates in this preparation.
21. Give the structures of the ester precursors for the following Claisen condensation product and formulate the
reaction.
Exhibit 23-8
Consider the compound 2-methyl-2-carboethoxycyclopentanone, whose structure is shown below, to answer
the following question(s).
23. Refer to Exhibit 23-8. When 2-methyl-2-carboethoxycyclopentanone is treated with sodium ethoxide in
ethanol solution followed by a mild aqueous acid work-up, 5-methyl-2-carboethoxycyclopentanone is isolated
as the major product. This reaction proceeds by a reverse Claisen condensation mechanism followed by a
recyclization. On the structures provided below, show electron flow with arrows in this interesting reaction.
24. Oxaloacetic acid is an important intermediate in the biosynthesis of citric acid. Synthesize oxaloacetic acid
using a mixed Claisen condensation as a key carbon-carbon bond forming reaction.
Exhibit 23-9
Draw the structures of the precursors to each of the following Michael reaction products. Label the Michael
donor and the Michael acceptor in each case and formulate the reaction.
25.
26.
28.
29.
Exhibit 23-10
Consider the reaction below to answer the following question(s).
The Stork enamine reaction is a variation on the Michael reaction which utilizes an enamine nucleophile.
30. Refer to Exhibit 23-10. On the structures above, draw arrows indicating electron flow in each step of this
reaction.
31. Refer to Exhibit 23-10. Draw the structures of the Ketone + Amine products of this reaction.
32. Refer to Exhibit 23-10. Show how you might use a Stork enamine reaction to prepare the following
compound.
Exhibit 23-11
Give the major organic product(s) for each of the following reactions or reaction sequences.
34.
35.
36.
38. A multistep synthesis can be used to prepare 3,3-dimethylindanone. From the list provided below, choose the
best reagent(s) for each step in this sequence. Place the letter in the box over the reaction arrow.
39. Consider the following molecular model. Atoms other than carbon and hydrogen are labeled.
40. Draw the products of the Claisen condensation of the following substance. Atoms other than carbon and
hydrogen are labeled.
1. ANS:
PTS: 1
2. ANS:
Benzophenone does not undergo aldol self-condensation because it has no -hydrogens.
PTS: 1
3. ANS:
PTS: 1
4. ANS:
2,2-Dimethylpropanal does not undergo aldol self-condensation because it has no -hydrogens.
PTS: 1
5. ANS:
PTS: 1
10 CHEM 2425. Chapter 23. Carbonyl Condensation Reactions (homework) W
6. ANS:
b
PTS: 1
7. ANS:
c
PTS: 1
8. ANS:
PTS: 1
9. ANS:
PTS: 1
10. ANS:
When cyclohexanone is placed in a solution of sodium ethoxide in ethanol, the enolate is generated in small
amounts in the presence of large amounts of ketone-ideal conditions for an aldol self-condensation.
Consequently, aldol self-condensation competes with alkylation of the enolate, and product mixtures result.
PTS: 1
11. ANS:
PTS: 1
12. ANS:
PTS: 1
13. ANS:
PTS: 1
14. ANS:
A
PTS: 1
15. ANS:
d
PTS: 1
16. ANS:
PTS: 1
17. ANS:
PTS: 1
18. ANS:
PTS: 1
19. ANS:
PTS: 1
20. ANS:
PTS: 1
22. ANS:
PTS: 1
23. ANS:
PTS: 1
24. ANS:
PTS: 1
26. ANS:
PTS: 1
27. ANS:
PTS: 1
PTS: 1
29. ANS:
PTS: 1
30. ANS:
PTS: 1
31. ANS:
PTS: 1
32. ANS:
PTS: 1
34. ANS:
PTS: 1
35. ANS:
PTS: 1
37. ANS:
PTS: 1
38. ANS:
step 1 = b; step 2 = g; step 3 = e; step 4 = i
PTS: 1
39. ANS:
Benzaldehyde and its derivatives, such as p-bromobenzaldehye shown, will not undergo Aldol reactions
because they do not possess -hydrogens.
PTS: 1
40. ANS:
PTS: 1