ORIENT COLLEGES TALAGANG

Organic Chemistry (BSc-II)

On-Screen Lectures
Aldehydes & Ketones
Lecture # 2
 REACTIONS OF ALDEHYDES & KETONES

Structure & Reactivity of Carbonyl group

 The characteristics functional group of aldehydes and
ketones is carbonyl group i.e. C=O
 In C=O, C-atom is sp2 hybridized and C, O and two
other groups attached to C lie in the same plan
 C=O is polar; O-atom being electronegative pulls pi
electrons more towards itself making C-atom e--
deficient

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 Consequences of Structure of Carbonyl Group

 The polarity of carbonyl group makes the carbonyl

double bond strong and hence very stable
Additions reactions of alkenes are exothermic and form
stable products; while many of addition reactions of
aldehydes & ketones are endothermic and do not take
place
 Since C-atom of carbonyl group is e--deficient,
carbonyl group is susceptible to be attacked by the
nucleophilic reagents

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 Consequences of Structure of Carbonyl Group

 Carbonyl group increases the acidity of α-H-atom by

stabilizing the anion formed after removal of α-H-
atom through resonance

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 REACTIONS OF ALDEHYDES & KETONES

Nucleophilic Addition Reactions

Those addition reactions which are initiated
by a nucleophile are called nucleophilic
addition reactions

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 Reactivity of Aldehydes & Ketones in
Nucleophilic Addition Reactions
In nucleophilic addition reactions, when a nucleophilic specie attacks
the carbon, the hybridization of C-atom changes from sp2 to sp3,
resulting in increased crowding on C-atom

 SO, the reaction is expected to be increasingly hindered with the increasing size of R and
R`. It can therefore, anticipated that the the ketones will be the less reactive than aldehydes

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 Mechanism of Nucleophilic Addition Reactions

Nucleophilic addition reactions are catalyzed by both acids and bases

Acid-Catalyzed Mechanism

Base-Catalyzed Mechanism

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 Reactions of Aldehydes & Ketones

Addition of Water
Aldehydes & ketones add a water molecule across
their carbonyl group to form hydrates also called
gem-diols

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 Reactions of Aldehydes & Ketones

Characteristics of hydrates or gem-diols

 They are very unstable substances (stable only in large amount of
water)
 Small amounts of hydrates may be present in equilibrium with some
carbonyl compounds in aqueous solutions

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 Reactions of Aldehydes & Ketones

Characteristics of hydrates
or gem-diols
Since secondary carbocations are more stable
than primary carbocation, therefore dipolar
structure of ketones is more stable than that
of aldehydes. Therefore, large amount of
aldehydes exist as hydrates than ketones

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 Reactions of Aldehydes & Ketones

Addition of Water
Acid-catalyzed mechanism

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 Reactions of Aldehydes & Ketones

Addition of Water
Base-catalyzed mechanism

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 Reactions of Aldehydes & Ketones

Addition of Alcohols
Aldehydes & ketones also add an alcohol
molecule across their carbonyl group to form
hemiacetals/ hemiketals or acetals/ etals also
called gem-diethers

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 Reactions of Aldehydes & Ketones

Addition of Alcohols

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 Reactions of Aldehydes & Ketones

Addition of Alcohols: Acid-catalyzed mechanism

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 Reactions of Aldehydes & Ketones

Addition of Alcohols: Base-catalyzed mechanism

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 Reactions of Aldehydes & Ketones

Addition of Alcohols
If excess of alcohol is
present, another
molecule is added and
acetal or gem-diether is
formed

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 Reactions of Aldehydes & Ketones

Addition of Alcohols: Mechanism of formation of

acetal

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 Reactions of Aldehydes & Ketones

Addition of Alcohols
Ketals are not formed when simple ketones are
treated with alcohols. However when ketones are
treated with dihydric alcohols, cyclic ketals are
formed

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