ORIENT COLLEGES TALAGANG

Organic Chemistry (BSc-II)

On-Screen Lectures
Aldehydes & Ketones
Lecture # 4
 Reactions of Aldehydes & Ketones

Aldol Condensation
Self condensation of an aldehyde or ketone having
an α-hydrogen atom in the presence of an alkali to
form an aldol or ketol is called aldol condensation
Aldol:β-hydroxyaldehydes are commonly known
as Aldols
Ketol:β-hydroxyketones are commonly known as
Ketols
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 Reactions of Aldehydes & Ketones

Example

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 Reactions of Aldehydes & Ketones

Aldol Condensation:
Mechanism

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 Reactions of Aldehydes & Ketones

Aldol Condensation: Conditions

Aldol condensation is only given those aldehydes
and ketones which contain at least one α-
hydrogen atom
Carbonyl compounds containing no α-hydrogen atom do not
undergo aldol condensation. e.g. formaldehyde,
benzaldehyde, trimethylacetaldehyde etc.

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 Reactions of Aldehydes & Ketones

Another Example

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 Reactions of Aldehydes & Ketones

Dehydration of Aldols/ Ketols

Under vigorous conditions
e.g. higher concentration of
base or higher temperature,
aldols or ketols are
dehydrated to α,β-
unsaturated carbonyl
compound

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 Reactions of Aldehydes & Ketones

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 Reactions of Aldehydes & Ketones

The Mixed Aldol Condensation

When a mixture of two aldehydes/ ketones both
having an α-hydrogen atom is subjected to aldol
condensation, a mixture of four aldol products is
obtained
 Enolate ion of A molecule can add to another A molecule
 Enolate ion of A molecule can add to another B molecule
 Enolate ion of B molecule can add to another B molecule
 Enolate ion of B molecule can add to another A molecule

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 Reactions of Aldehydes & Ketones
Example

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 Reactions of Aldehydes & Ketones

The Mixed Aldol Condensation

However, if one of the two compounds does not
have an α-hydrogen atom or a compound has less
reactive carbonyl group, two aldol products are
obtained.
 Enolate ion of A molecule can add to another A molecule
 Enolate ion of A molecule can add to another B molecule

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 Reactions of Aldehydes & Ketones
Example

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 Reactions of Aldehydes & Ketones

Cannizzaro's reaction
Aldehydes or ketones having no α-hydrogen atom
when treated with conc. NaOH, undergo a
disproportionation reaction self oxidation-
reduction) to form a sodium salt of carboxylic
acid and an alcohol. The reaction is known as
Cannizzaro's reaction

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 Reactions of Aldehydes & Ketones

Cannizzaro's reaction

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 Reactions of Aldehydes & Ketones

Cannizzaro's reaction

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 Reactions of Aldehydes & Ketones

Cannizzaro's reaction: Another example

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 Reactions of Aldehydes & Ketones

The mixed Cannizzaro's reaction

If a mixture of two aldehydes both with no α-
hydrogen atom is subjected to Cannizzaro’s
reaction, all possible products are formed
However, if one of the two compounds is
formaldehyde, the formaldehyde is exclusively
oxidized while the other compound is reduced

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 Reactions of Aldehydes & Ketones

The mixed Cannizzaro's reaction

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 Reactions of Aldehydes & Ketones

The mixed Cannizzaro's reaction

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