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In the presence of a strong base, two molecules of aldehyde or ketone may combine to form a b-hydroxyaldehyde or a b-hydroxyketone. This reaction is called the aldol condensation.
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OH R CH2 C H
O CH C R H
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Example
O CH3 C H + O NaOH CH3 C H OH CH3 C H "Aldol" O CH2 C H
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Another Example
O CH3 CH2 C H + O NaOH CH3 CH2 C H OH CH3 CH2 C H CH CH3 O C H
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One More:
O CH3 C CH3 + O NaOH CH3 C CH3 OH CH3 C CH3 "Diacetone alcohol" O CH2 C CH3
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an enolate ion
acceptor
: O:
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_ O
1. It provides a site for nucleophilic attack by the enolate ion. 2. It makes the a-hydrogens sufficiently acidic to enable the formation of reasonable concentrations of enolate ion.
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Without a-hydrogens, the only possible reaction is the Cannizarro reaction (Chapter 17, Section 17.3 -- we skipped this)
Note here that iodine is a sufficiently strong Lewis acid to bring about dehydration.
H2O
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OH CH3 CH
O CH2 C + OH O CH CH3 + C H H
CH3 CH2 CH
O C H
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CH2 C
acceptor
OH NaOH O CH2 C H
+ O CH3 C H
C H
donor
- H2O (spontaneously)
O CH CH C H
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Cannizzaro Reaction The disproportionation reaction of aldehydes without -hydrogens in presence of a strong base to furnish an alcohol and a carboxylic acid is called Cannizzaro reaction. One molecule of aldehyde is reduced to the corresponding alcohol, while a second one is oxidized to the carboxylic acid.
The applicability of Cannizzaro reaction in organic synthesis is limited as the yield is not more than 50% for either acid or alcohol formed. In case of aldehydes that do have -hydrogens, the aldol condensation reaction takes place preferentially. The ,,-Trihalo aldehydes undergo haloform reaction in strongly alkaline medium. E.g. Choral will give chloroform in presence of an alkali. WWU -- Chemistry
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NOTE: The alkoxide should match the alkyl group of the ester in order to avoid a competing transesterification.
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.. _ :O : CH2 C OC2H5
HO
C2H5
C2H5
2)
O CH3 C _ : CH2
CH2 C
donor
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C2H5
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Dieckman Condensation
An intramolecular Claisen condensation
O Et O OEt O Die thyl h exanedioate (Dieth yl adipate) 1 . Et O Na
+
Et OH
Perkin reaction The Perkin reaction is an organic reaction developed by William Henry Perkin that can be used to make cinnamic acids i.e. --unsaturated aromatic acid by the aldol condensation of aromatic aldehydes and acid anhydrides in the presence of an alkali salt of the acid.
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MANNICH REACTION
ketone formaldehyde O O excess .. pH 6-8 Et NH + C + 2 C
R CH3 H H O C CH2 CH2 NEt2 R
O C .. CH2 R
A variety of R groups may be used
+ Et C N H Et
Cl
iminium salt
Mannich Base Schiffs Base
Aldehydes other than formaldehyde may be used. The reaction works best with methyl ketones. Et2NH - HCl is generally used in excess, hence the chloride counter ion. Other secondary amines sometimes work in place of diethylamine.
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Darzens reaction The Darzens reaction (also known as the Darzens condensation or glycidic ester condensation) is the chemical reaction of a ketone or aldehyde with an -haloester in the presence of base to form an ,-epoxy ester, also called a "glycidic ester".
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