ORGANIC CHEMISTRY

Dr Nam T. S. Phan
Faculty of Chemical Engineering
HCMC University of Technology
Office: room 211, B2 Building
Phone: 38647256 ext. 5681
Email: ptsnam@hcmut.edu.vn
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Chapter 11: ALDEHYDES-KETONES
C=O C=C

SP2 carbon

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NOMENCLATURE OF ALDEHYDES
Common names: carboxylic acid Æ “aldehyde”
is substituted for “ic acid”

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IUPAC names: hydrocarbon + al
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Lower priority than ester Æ “oxo” group 4

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NOMENCLATURE OF KETONES
Derived names: alkyls + ketone

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IUPAC names: hydrocarbon + one
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 PREPARATION OF ALDEHYDES &
KETONES

Aldehydes & ketones from alkenes

In the presence of an oxidizing agent, the products

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will be ketones / carboxylic acids
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Aldehydes & ketones from alkynes
Markovnikov’s rule

Anti-Markovnikov
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Aldehydes & ketones from alcohols

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 Can NOT be isolated

PCC: pyridinium chlorochromate

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Aldehydes from esters, acyl chlorides

Note: LiAlH4 Æ alcohols

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Preparation of aromatic ketones

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Gatterman-Koch synthesis of benzaldehyde

Can NOT be
prepared &
isolated

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REACTIONS OF ALDEHYDES &
KETONES I

The partial positive

carbon can be attacked
by nucleophiles

The addition of nucleophiles to the carbon

atom of the carbonyl group in nucleophilic
addition reactions
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Reactions with Grignard reagents

Only for the reaction of HCHO

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Numbers 1 & 2 are used to indicate that the acid is not added
until the reaction with the Grignard reagent is complete

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Reactions with acetylide ions

Weak acid, will NOT react with the triple bond 18

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Reactions with hydrogen cyanide

Converted back to carbonyl in basic solutions

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 Nitriles Æ carboxylic acids

Nitriles Æ amines 20

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Reactions with primary amines

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Reaction mechanism:

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Reactions with secondary amines

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Reaction mechanism:

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Reactions with water

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Reactions with alcohols

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Reaction mechanism:

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Reactions with sulfur nucleophiles

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Reduction reactions – with hydride ion

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• NaBH4 can reduce aldehyde, ketones, acyl chlorides, but
NOT alkenes & alkynes
• LiAlH4 is a stronger reducing agent than NaBH4, but NOT
safe to use for aldehydes & ketones

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Reduction reactions to hydrocarbons

NOTE:

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Oxidation reactions

Aldehydes are generally easier to oxidize than

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primary alcohols

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 Tollens reagent

Too weak to oxidize an

alcohol or any other
functional groups

Should be used when oxidizing aldehydes

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containing double bond
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REACTIONS OF ALDEHYDES &
KETONES II – REATIONS AT α-C

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Aldol additions

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Reaction mechanism:
Nucleophilic additions

Aldol additions occur more slowly with ketones

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Aldol condensations = Additions + dehydrations
Easier to dehyrate than other alcohols because the double
bond is conjugated with the carbonyl group

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Aldol condensations sometimes occur under the aldol
addition conditions without additional heating

NOT isolated

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Mixed / crossed Aldol additions

4 addition products

NOT useful 39

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Very strong base

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Halogenations at α-C

Only 1
hydrogen
is replaced
in acidic
solution

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The haloform reactions

Only for
methyl
ketones

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