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15.

7 CONVERSION OF ALCOHOLS TO ETHERS


Primary alcohols are converted to ethers on heating in the presence of an acid catalyst,
usually sulfuric acid.

This kind of reaction is called a condensation. A condensation is a reaction in which


two molecules combine to form a larger one while liberating a small molecule. In this
case two alcohol molecules combine to give an ether and water.
When applied to the synthesis of ethers, the reaction is effective only with primary
alcohols. Elimination to form alkenes predominates with secondary and tertiary alcohols.
Diethyl ether is prepared on an industrial scale by heating ethanol with sulfuric
acid at 140C. At higher temperatures elimination predominates, and ethylene is the
major product. A mechanism for the formation of diethyl ether is outlined in Figure 15.2.

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.

In these intramolecular ether-forming reactions, the alcohol may be primary, secondary,


or tertiary.

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.

CONDENSATIONS OF CARBONYL COMPOUNDS


(Preparation of Benzalacetophenone, Benzoin,
and Cinnamic Acid)
NOTE: The directions for the experiments are for semimicro work. For macro work, use five times the
quantities given; instead of an eight-inch tube, use a 250-500 ml flask, a Liebig condenser instead of a
micro condenser, a distilling flask instead of a distilling tube. Use the same directions and allow about 50
per cent more time.
Introduction. The preceding experiments illustrated a type of reaction which is often referred to as a
condensation. The term condensation is used in a general manner at times to designate any reaction which
involves a union of one carbon atom to another. The term is also used in a restricted manner to designate
certain types of reactions in which more complex substances are obtained from one or two simpler
substances, usually accompanied by elimination of water or another simple inorganic compound. As
previously noted in connection with Experiment 34, aldehydes and ketones react .with other aldehydes,
acids, esters, and amines, and give rise to more complex substances. Many of these reactions are
named after the investigator or with reference to the product, followed by the word condensation,
synthesis or reaction. Thus we have Claisen condensation, Perkins synthesis or reaction, Schiff's
reaction, Knoevenagel reaction, benzoin condensation, aldol condensation, Cannizzaro reaction,
Tischtschenko reaction, and other names.
This practice is rather unfortunate, for it leads to the erroneous conclusion that there is little relation
between these reactions. A careful study will disclose that many of these reactions involve union (a) of
aldehydes with other aldehydes or ketones; (6) of aldehydes and acids; (c) of aldehydes and esters.
Therefore, all these reactions are essentially reactions which involve union of the carbonyl group of one
molecule with a carbon atom of another molecule which is situated in an a-position to another carbonyl or a
carboxyl:

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.

This latter reaction is sometimes called Claisen condensation.


(2) Tischtschenko Reaction. This involves the reaction between two molecules of an aldehyde which
may or may not have a-hydrogen, accompanied by oxidation of one carbonyl to carboxyl and the
reduction of the other carbonyl to alcohol. The product is an ester. The reaction is catalyzed by alkoxides.

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