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Alpha Carbon Chemistry: Enols and Enolates (Klein, Chapter 22) Part 2
These notes cover Ch 22.2-3. Do all in-chapter problems for the sections covered. Recommended end-ofchapter problems: 22.71-22.74, 22.81, 22.85. Do the practice problems provided in this packet. Practice
mechanisms and work on your reaction index/maps.

1. What two functional groups are present in the product of this reaction?
Does it make sense that the product is called an aldol?

Notice the stoichiometry of the reaction is usually never shown (its implied; get used to it!)
Devise a mechanism for how two acetaldehydes produce the product above under basic
conditions.

Practice 22.15: Predict the aldol product for each of these aldehydes in NaOH. Highlight the
new C-C bond that is formed in each case.

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22.17: When treated with NaOH (aq), 2,2-dimethylbutanal does not undergo aldol addition
reaction. Explain.

22.18: A C4 alcohol was treated with PCC to produce an aldehyde with exactly 3 signals in
the 1H-NMR. Predict the aldol product that is obtained when this aldehyde is treated with
NaOH(aq).

Retrosynthetic analysis:

Use the retrosynthesis approach to find the new C-C bond. What single molecule can be
used in each case to create the aldol product shown below?

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Explain why each of these cannot undergo aldol reaction with itself.

So far you have used only one starting material (with NaOH) to make an aldol product. If
two carbonyl compounds are used, you could get mixed (or crossed) aldol reactions.

Determine the four different products possible from the reaction above.

Practice 22.23: Identify the reagents you need to produce these aldol products.

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Based on the energy diagram below, which aldol products are generally in higher yield,
those from ketones or aldehydes?

Explain why aldehydes would be more reactive for addition than ketones.

In a mixed aldol of acetaldehyde (ethanal) with acetone (2-propanone), only two of the
following four possible products are observed. Cross out the ones that are not produced in
high yield and explain your choice.

Predict the most likely product from these mixed aldol reactions:

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For the last reaction on the previous page, product A is preferred because acetaldehyde is a
better nucleophile and electrophile compared to benzaldehyde.

One of these procedures can help form more product B, however. Which one and why?
Procedure X: Add a small amount of benzaldehyde to a acetaldehyde and base
Procedure Y: Add a small amount of acetaldehyde to benzaldehyde and base

Aldol Condensation When heat is present, condensation may occur.

Notice that acid is not required in this reaction (as in previous E1 eliminations). This is
because of the carbonyl group and the presence of an alpha hydrogen.
In the mechanism, the enolate forms (deprotonation) then the leaving group leaves. (This is
called E1cb.) Deduce a mechanism for this reaction.

What conditions are required for aldol addition product, versus aldol condensation?

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22.20 Draw the condensation product from each of these carbonyls:

22.21 Identify the starting aldehyde or ketone for these products:

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When two carbonyls are present, you could get an intramolecular aldol condensation.
What is the product if it happens here? Show the mechanism as well.

The aldol condensation could also occur under acidic conditions (though its not as
common to see this). Deduce the mechanism for this reaction:
(Hint: First step is tautomerization)

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Section 22.4: Claisen Condensation (for esters):

Deduce a mechanism for this reaction.

Crossed-Claisen products can be formed, just as with aldol. Determine the products of these
reactions:

For this one, LDA is formed to make a lot of enolate, then another ester is added dropwise
to maximize yield of one product:

(If this was not carefully directed, then what side product could be formed?)

Intramolecular Claisen reaction (Dieckmann cyclization):

Show electron pushing arrows above to explain formation of this product.

22.29 Predict the major product if these undergo Claisen condensation:

22.31 Predict the Dieckmann cyclization product for these:

22.32 Two possible intramolecular reactions occur with this. What are the products?

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Practice Problems:
1. Give an example of an aldehyde and a ketone that cannot undergo aldol reaction in base,
and an aldehyde and ketone that can. What is the requirement (in terms of structure) of an
aldehyde/ketone to undergo aldol in basic solution?

2. Predict the aldol product for each of these (by itself) with NaOH (aq).

3. Under basic solution, carbonyls could undergo aldol but they can also form hydrates in
solution.

4.

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5. Draw an aldol/ketol for each ketone below treated with NaOH (aq). For ketones marked
with a 2, draw two different products that are constitutional isomers (ignore
stereoisomerism).

6.

7. Draw aldehydes or ketones needed to make the following aldol products:

8. Draw the most likely product or write no reaction.

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9.

10. Draw the best mechanism leading to 5- or 6-member ring formation in each of these:

11.

12.

13. For each, draw all the products that could occur (via aldol, Claisen, etc.)

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