Unit 8 Carbonyl Reaction 2017

DBU,CHEMISTRY DEPARTMENT
ORGANIC CHEMISTRY FOR MEDICINE STUDENTS 2017EC
10/10/2024 Compiled by Gezu Feleke(MSc,Ass prof) 1

10/10/2024 Compiled by Gezu.F(MSc,Ass prof) 2
The major carbonyl reactions are:
Carbonyl addition
Addition Elimination
Enolization-Ketonization
Carbonyl Reactions Carboxylic acid
derivatives
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The reactions of aldehydes and ketones can be divided into two main categories:
– Reactions of the carbonyl group
– Reactions involving the α-carbon
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Carbonyl addition
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Carbonyl Addition Elimination reactions
Enolization-Ketonization
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Application of Addition reactions
Hydrate formation
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Hemiacetals and Hemiketals
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Cyanohydrins formation
➢Hydrogen cyanide adds to aldehydes and ketones to form
cyanohydrins.
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Addition of organometallic reagents
▪ When these Grignard reagents (or organolithium) are reacted with ketones or
aldehydes, alcohol products are obtained. The type of alcohol obtained is dependent
upon the ketone or aldehyde used.
Formaldehyde yields 1˚ alcohols
Aldehydes yield 2˚ alcohols
Ketones yield 3˚ alcohols

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Wittig reaction and its mechanism
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Application of addition-elimination reactions
Reactions of Aldehydes and Ketones with Amines and related compounds

▪ Aldehydes and ketones react with primary amines to form imines, or Schiff bases.
An imine is a compound with a

C=N double bond ( a nitrogen
analog of an aldehyde or ketone
▪ Aldehydes and ketones react with secondary amines to form enamines.
Enamines have a nitrogen bound to a

carbon which is part of a C=C double bond. 26
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enamine
An enamine is an Alpha-Beta -unsaturated tertiary
amine—a tertiary amine with a double bond in the -
position relative to the nitrogen atom.
Aldehydes and ketones react with a secondary

amine(R2NH) to form an enamine (pronounced“ENE-
amine”).
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Acids and their derivatives
❖Reactivity with z nucleophile
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Generally represented by:
where Y is the leaving group
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Acid chlorides
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Acid anhydrides
Loss of water from two molecules of a carboxylic acid results in an acid anhydride.
“Anhydride” means “without water.”
Conversion of Acid Anhydrides to Other Carboxylic Acid Derivatives
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Reactions of Carbon Nucleophiles with Carbonyl Compounds
The reactions described in this chapter include some of the most useful methods
for carbon-carbon bond formation:
▪All of these reactions begin with the addition of a stabilized carbon
nucleophile to a carbonyl group nucleophile to a carbonyl group.
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8.9 Mannich condensation
The Mannich reaction is an organic reaction which
consists of an amino alkylation of an acidic proton placed
next to a carbonyl functional group by formaldehyde and a
primary or secondary amine or ammonia. The final
product is a β-amino-carbonyl compound also known as a
Mannich base
Scheme 1. Ammonia or an amine reacts with formaldehyde and an alpha acidic proton of a carbonyl compound to a beta amino carbonyl compound
10/10/2024 Compiled by Gezu.F(MSc,Ass prof) 41

8.6 enolization-Ketonization reactions and Application of
enolization-Ketonization reactions Home reading!

8.6.1 Halogenation
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8.6.2 Alkylation
➢Since the carbanion-enolates are ambident ions with
two different nucleophilic sites, they can be alkylated at C
or at O.
EXAMPLES
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8.6.3 Aldol condensation
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8.6.4 Claisen-Schmidt condensation
8.6.4 Claisen-Schmidt condensation
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8.6.5 Mannich condensation
The Mannich reaction is an organic reaction which
consists of an amino alkylation of an acidic proton placed
next to a carbonyl functional group by formaldehyde and a
primary or secondary amine or ammonia. The final
product is a β-amino-carbonyl compound also known as a
Mannich base
Scheme 1. Ammonia or an amine reacts with formaldehyde and an alpha acidic proton of a carbonyl compound to a beta amino carbonyl compound
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The mechanism of the Mannich reaction starts with the formation
of an iminium ion from the amine and the formaldehyde
Mannichreactionmech1.svg
The compound with the carbonyl functional group (in this case a ketone) can t
automerize to the enol form, after which it can attack the iminium ion.
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8.6.6 Perkin condensation
The Perkin condensation is the condensation of an aromatic
aldehyde and acetic anhydride.
❖Activity: show its mechanism
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8.6.7 Claisen condensation
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THANK YOU
10/10/2024 GEZU.F 54

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DBU,CHEMISTRY DEPARTMENT

ORGANIC CHEMISTRY FOR MEDICINE STUDENTS 2017EC

10/10/2024 Compiled by Gezu Feleke(MSc,Ass prof) 1

Formaldehyde yields 1˚ alcohols

Aldehydes yield 2˚ alcohols

Ketones yield 3˚ alcohols

Reactions of Aldehydes and Ketones with Amines and related compounds

An imine is a compound with a

▪ Aldehydes and ketones react with secondary amines to form enamines.

Enamines have a nitrogen bound to a

Aldehydes and ketones react with a secondary

Conversion of Acid Anhydrides to Other Carboxylic Acid Derivatives

10/10/2024 Compiled by Gezu.F(MSc,Ass prof) 41

enolization-Ketonization reactions Home reading!

8.6.4 Claisen-Schmidt condensation

❖Activity: show its mechanism

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