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The individual steps of this mechanism are analogous to those seen earlier. Nucleophilic
attack on a protonated alcohol was encountered in the reaction of primary alcohols with
hydrogen halides (Section 4.13), and the nucleophilic properties of alcohols were discussed
in the context of solvolysis reactions (Section 8.7). Both the first and the last
steps are proton-transfer reactions between oxygens.
Diols react intramolecularly to form cyclic ethers when a five-membered or sixmembered
ring can result.
17.5 CONDENSATIONS
A condensation reaction leads to a product with a new C-C bond. Most often the new bond results from a
nucleophilic addition of a reasonably stable carbanion-enolate to the C=O group (acceptor) of an
aldehyde; less frequently the C=O group belongs to a ketone or acid derivative. Another acceptor is the
C=N group of a nitrile.
ALDOL CONDENSATION
The addition of the nucleophilic carbanion-enolate, usually of an aldehyde, to the C=O group of its p, r t
compound is called an aldol condensation. The product is a P-hydroxycarbonyl compound. In a mixed
aldol condensation the carbanion-enolate of an aldehyde or ketone adds to the C=O group of a molecule
other than its parent. The more general condensation diagrammed above is termed an aldol-type
condensation. Since the C, not the 0, is the more reactive site in the hybrid, the enolate contributing
structure is usually omitted when writing equations for these reactions. This is done even though the
enolate is the more stable and makes the major contribution.
Net Reactions
Aldol condensations are reversible, and with ketones the equilibrium is unfavorable for the
condensation product. To effect condensations of ketones, the product is continuously removed from
the basic catalyst. P-Hydroxycarbonyl compounds are readily dehydrated to give a,P-unsaturated carbonyl
compounds. With Ar on the P carbon, only the dehydrated product is isolated.
The general equation above merely indicates the beginning. The ultimate direction depends on the
environment, temperature, catalyst nature of the aldehyde, and other factors. Though the use of special
names is considered unfortunate from the point of view expressed above, the usage is widespread in
chemical literature, and the student will do well to get acquainted with the specific application of each.
The most important are:
(1) Aldol Condensation. This involves the reaction between two molecules of an aldehyde or a molecule
of aldehyde and ketone, having a-hydrogen. The reaction is catalyzed by many weakly alkaline salts.
The reaction represented by the equation is the first step, which is reversible. Loss of water by the
hydroxyaldehyde results in an unsaturated compound.
A similar reaction may occur between an aldehyde and a ketone to form an unsaturated ketone.