PART III NAMED REACTIONS 1 Organic Chemistry 2nd Semester

CANNIZZARO REACTION
Introduction:
It is a redox or disproportionation reaction in which two molecules of a non-
enolizable aldehyde are reacted to produce a primary alcohol and a carboxylic acid
using a hydroxide base as reagent.
A non-enolizable aldehyde is an aldehyde lacking alpha hydrogen and does not show
keto-enol tautomerism.
The Cannizzaro reaction is named after its discoverer, an Italian chemist Stanislao
Cannizzaro (1853).

Types of Reaction:
 It is a disproportionation reaction.
It is a redox reaction in which one aldehyde is oxidized to form the acid and the other
is reduced to form the alcohol.
 It is a hydride ion transfer reaction.
It is a reaction involving transfer of a hydride ion from one substrate molecule to the
other.
 It is a nucleophilic addition reaction.

Starting Materials:
A non-enolizable aldehyde such as formaldehyde, benzaldehyde etc.
A single aldehyde is enough for the reaction to complete but a mixture of two
different aldehydes can also be used.

Formaldehyde
PART III NAMED REACTIONS 2 Organic Chemistry 2nd Semester

Benzaldehyde

A non-enolizable
aldehyde

Reaction Conditions:
 A hydroxide base such as NaOH, KOH etc., is used as the reagent. A
concentrated solution of the base is used.
 Water is used as solvent for the reaction.
 A mineral acid such as HCl is required for the conversion of carboxylic acid salt
to its acid form.
 Heating is required.
 Hydroxide base itself acts as a catalyst.

Reaction Products:
Two major products are obtained on completion of the reaction. A primary alcohol,
which is the reduction product and a carboxylic acid which is the oxidation product.

Primary Alcohol

Carboxylic Acid
PART III NAMED REACTIONS 3 Organic Chemistry 2nd Semester

General Reaction:
The reaction is carried out in two phases.

Reaction Mechanism
Reaction completes in two phases and proceeds by following steps.
Phase I: Disproportionation of Aldehyde.
In first phase of the reaction, two molecules of non-enolizable aldehyde undergo
disproportionation reaction to give a primary alcohol and a salt of carboxylic acid in
several steps.

Step 1: Ionization of Base.

Hydroxide base ionizes to hydroxide ion and metal cation.

Step 2: Nucleophilic Addition.

Nucleophilic attack of hydroxide ion occurs on carbonyl carbon of first molecule of
non-enolizable aldehyde forming an anion.
PART III NAMED REACTIONS 4 Organic Chemistry 2nd Semester

Step 3: Deprotonation.
Base removes proton from hydroxyl group of the anion intermediate converting it to
a dianion.

Step 4: Hydride Ion Transfer.

The dianion intermediate releases a hydride anion which proceeds to attack another
aldehyde molecule. Now, the dianion is converted into a carboxylate anion and the
aldehyde is converted into an alkoxide anion.

Step 5: Protonation of Alkoxide.

Water offers a proton to the alkoxide anion which gives rise to the final alcohol
product.
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Step 6: Carboxylic Acid Salt Formation.

The carboxylate ion gives rise to the salt of carboxylic acid by combining with metal
cation.

Phase II: Acid Treatment

In second phase of the reaction, the salt of carboxylic acid is treated with a mineral
acid thus converting it into a carboxylic acid.

Types of Cannizzaro Reaction:

There are three types of Cannizzaro reactions
1. Simple Cannizzaro Reaction:
When only one non-enolizable aldehyde is used as reactant, then the reaction is
called simple Cannizzaro reaction. For example, disproportionation of
formaldehyde.

2. Crossed Cannizzaro Reaction:

When two different non-enolizable aldehydes are used as reactants, then the reaction
is called crossed Cannizzaro reaction. For example, disproportionation of
formaldehyde & benzaldehyde.
PART III NAMED REACTIONS 6 Organic Chemistry 2nd Semester

3. Internal Cannizzaro Reaction (Intramolecular):

When disproportionation reaction occurs within the same non-enolizable aldehyde
molecule, then the reaction is called internal or intramolecular Cannizzaro reaction.
For example, disproportionation of non-enolizable α-keto aldehydes.

Examples:
 Disproportionation of formaldehyde

 Disproportionation of benzaldehyde
PART III NAMED REACTIONS 7 Organic Chemistry 2nd Semester

 Disproportionation of formaldehyde & benzaldehyde

 Disproportionation of isobutyraldehyde

Note: Isobutyraldehyde (2-methylpropanal) undergoes the Cannizaro reaction even

though it has alpha hydrogen atom.

 Disproportionation of pivaldehyde (trimethylacetaldehyde)

 Disproportionation of glyoxal (oxalaldehyde)

PART III NAMED REACTIONS 8 Organic Chemistry 2nd Semester

 Disproportionation of phenylglyoxal

 Disproportionation of o-phthaldehyde

 Disproportionation of furfural

Importance/Uses:
 Synthesis of Mandelic Acid
Phenylglyoxal undergoes intramolecular Cannizzaro reaction to give mandelic
acid. Mandelic acid is used in cosmetic industry for applications to skin. It has
pharmaceutical uses as antibacterial agent for UTIs. The drugs cyclandelate (a
vasodilator) and homatropine (a mydriatic) are esters of mandelic acid.
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 Preparation of Pentaerythritol
Cannizzaro reaction is used industrially for the preparation of polyols such as
pentaerythritol. Pentaerythritol is a building block for the synthesis and production
of explosives, plastics, paints, appliances, cosmetics, and many other commercial
products. It is used as a fire retardant, such as in plastics.

 Synthesis of Neopentyl glycol

Neopentyl gycol is synthesized from isobutyraldehyde and excess formaldehyde by
aldol reaction followed by Cannizzaro reaction. It is used in the synthesis of
polyesters, paints, lubricants, and plasticizers resistant to heat, light, and water.

Drawbacks/Limitations:
 Cannizzaro reaction is limited to aldehydes containing no alpha hydrogen and it
cannot be used for aldehydes containing alpha hydrogen such as acetaldehyde. In
such cases, the aldol condensation reaction takes place preferentially.
 The applicability of Cannizzaro reaction in organic synthesis is limited as in most
cases, the yield is not more than 50% for either acid or alcohol formed.
 The Cannizzaro reaction takes place very slowly when electron-donating groups
are present.