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Reaksi Kondensasi Senyawa Karbonil
Reaksi Kondensasi Senyawa Karbonil
Reaksi Kondensasi Senyawa Karbonil
Carbonyl Compounds
Alpha Substitution
Chapter 22 2
Condensation with an Aldehyde or
Ketone
Tautomerization is an interconversion of
isomers that occur through the migration of a
proton and the movement of a double bond.
Tautomers are not resonance form.
Chapter 22 5
BaseCatalyzed Tautomerism
Chapter 22 6
Acid-Catalyzed Tautomerism
Chapter 22 7
Racemization
Chapter 22 9
Formation and Stability of
Enolate Ions
Chapter 22 12
Base-Promoted Halogenation
Mechanism
Chapter 22 13
Multiple Halogenations
O O O O
Cl Cl Cl Cl Cl Cl
Cl2 Cl Cl Cl Cl
H _
OH , H2O
Solution
In the presence of sodium hydroxide, a small amount of 3-pentanone is present as its enolate.
Chapter 22 18
Acid-Catalyzed Halogenation
Solution
Under acid catalysis, the ketone is in equilibrium with its enol form.
The enol acts as a weak nucleophile, attacking chlorine to give a resonance-stabilized intermediate.
Loss of a proton gives the product.
Chapter 22 21
Alkylation of Enolate Ions
Chapter 22 28
Base-Catalyzed Aldol
Condensation: Step 3
Chapter 22 31
Successful Crossed Aldol
Condensations
Chapter 22 32
Solved Problem 3
Propose a mechanism for the base-catalyzed aldol condensation of acetone (Figure 22-2).
Solution
The first step is formation of the enolate to serve as a nucleophile.
The second step is a nucleophilic attack by the enolate on another molecule of acetone. Protonation
gives the aldol product.
Chapter 22 33
Aldol Cyclization
Chapter 22 34
Retrosynthesis of Aldol
Condensation
Chapter 22 35
Claisen Condensation
Chapter 22 36
Crossed Claisen
Chapter 22 37
Crossed Claisen Condensation
Chapter 22 38
Crossed Claisen Condensation
with Ketones and Esters
Chapter 22 40
Solved Problem 4
Propose a mechanism for the self-condensation of ethyl acetate to give ethyl acetoacetate.
Solution
The first step is formation of the ester enolate. The equilibrium for this step lies far to the
left; ethoxide deprotonates only a small fraction of the ester.
The enolate ion attacks another molecule of the ester; expulsion of ethoxide ion gives ethyl
acetoacetate.
Chapter 22 41
Solved Problem 4 (Continued)
Solution (Continued)
In the presence of ethoxide ion, ethyl acetoacetate is deprotonated to give its enolate. This exothermic
deprotonation helps to drive the reaction to completion.
When the reaction is complete, the enolate ion is reprotonated to give ethyl acetoacetate.
Chapter 22 42
Solved Problem 5
Show what ester would undergo Claisen condensation to give the following b-keto ester.
Solution
First, break the structure apart at the a, b bond (a, b to the ester carbonyl). This is the bond formed in
the Claisen condensation.
Chapter 22 43
Solved Problem 5 (Continued)
Solution (Continued)
Next, replace the a proton that was lost, and replace the alkoxy group that was lost from the carbonyl.
Two molecules of methyl 3-phenylpropionate result.
Now draw out the reaction. Sodium methoxide is used as the base because the reactants are methyl
esters.
Chapter 22 44
Chapter 22 45
Malonic Ester Synthesis
Chapter 22 47
Example of the Malonic
Synthesis
Chapter 22 48
Dialkylation of Malonic Ester
Chapter 22 49
Solved Problem 6
Show how the malonic ester synthesis is used to prepare 2-benzylbutanoic acid.
Solution
2-Benzylbutanoic acid is a substituted acetic acid having the substituents PhCH2 and CH3CH2.
Adding these substituents to the enolate of malonic ester eventually gives the correct
product.
Chapter 22 50
Acetoacetic Ester Synthesis
Chapter 22 51
Alkylation of Acetoacetic Ester
Solution
The target compound is acetone with an n-propyl group and an allyl group as substituents:
Chapter 22 54
Solved Problem 7 (Continued)
Solution (Continued)
With an n-propyl halide and an allyl halide as the alkylating agents, the acetoacetic ester synthesis
should produce 3-propyl-5-hexen-2-one. Two alkylation steps give the required substitution:
Chapter 22 55
Conjugate Additions: The
Michael Reaction
Chapter 22 57
Donors and Acceptors
Chapter 22 58
1,4-Addition of an Enolate to
Methyl Vinyl Ketone (MVK)
Solution
A Michael addition would have formed a new bond at the b carbon of the acceptor. Therefore,
we break this molecule apart at the b,g bond.
Chapter 22 60
Robinson Annulation
Chapter 22 62