CLEMMENSEN REDUCTION 109

3. The reaction has also been used in the preparation of long-chain conjugated aldehydes, which are
useful dye intermediates.

4. A technical route to cinnamic acid is the oxidation of benzalacetone with sodium hypochlorite.

5. Test for the presence of - CH2CO - group

The reaction has been used to detect the presence of - CH2CO - group in the natural products, for only
if a compound contains - CH2CO - group, it will undergo the condensation.

CLEMMENSEN REDUCTION
The reduction of carbonyl groups of aldehydes and ketones to methylene groups with amalgamated zinc and
concentrated hydrochloric acid is known as Clemmensen reduction.

The reduction consists in refluxing the carbonyl compounds with amalgamated zinc and excess of
concentrated hydrochloric acid. The reduction is useful especially for ketones containing phenolic or
carboxylic groups which remain unaffected. Ketones are reduced more often than aldehydes. Such reduction
is also observed in Wolff–Kishner reduction but Clemmensen reduction is easier to perform. The reduction,
however, fails with acid-sensitive and high molecular weight substrates. The a, b-unsaturated ketones
undergo reduction of both the olefinic and carbonyl groups. However, the reduction is specific for carbonyl
groups of aldehydes and ketones containing other functional and reducible groups.

Mechanism
Various mechanisms have been suggested which are so contradictory that no conclusion can be drawn. A
mechanism suggesting the intermediate formation of alcohol was rejected since the reagent fails to reduce
most alcohols to hydrocarbons.
Nakabayaski has suggested a mechanism on the assumption that the reduction under acid condition
involves protonated carbonyl group to which electrons are transferred from the metal.
110 REACTIONS, REARRANGEMENTS AND REAGENTS

Certain types of aldehydes and ketones do not give the normal reduction products alone. Thus,
a-hydroxy ketones give either ketones through hydrogenolysis* of OH group or olefins and 1, 3-diketones
give exclusively monoketones with rearrangement.

Certain cyclic 1, 3-diketones give under Clemmensen reduction a fully reduced product along with a
monoketone with ring contraction.

CH 3 CH 3 CH 3 CH 3 CH 3 CH 3

Zn–Hg
+
HCl
O O O CH 3
5, 5-Dimethyl 1, 1-Dimethyl 2, 4, 4-Trimethyl
cyclohexane-1, 3-dione cyclohexane cyclopentanone

The latter probably is formed through a diradical with subsequent intramolecular C < C bond formation and
pinacol-type rearrangement.

Applications
The reduction has important synthetic applications.
1. Reduction of aliphatic and mixed aliphatic–aromatic carbonyl compounds.

(a)

(b)

The reaction is useful for introducing straight-chain (without rearrangement) alkyl groups in aromatic rings by
acylation and subsequent reduction.
2. Reduction of keto acids

a- and b-keto acids are generally not reduced.

* Cleavage of carbon-hetero atom bond by catalytic hydrogenation.

 CLEMMENSEN REDUCTION 111

3. Reduction of phenolic carbonyl compounds

4. Reduction of cyclic ketones

(a)

(b) In the synthesis of naphthalene

5. Reduction with ring expansion

6. Reduction with ring contraction

CH3 CH3 CH3 CH3

Zn–Hg
HCl
O O O CH3
5, 5-Dimethyl cyclohexane-1, 3-dione 2, 4, 4-Trimethyl cyclopentanone

7. Synthesis of cycloparaffins