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Hoa-Huu-Co - Phan-Thanh-Son-Nam - Chapter-11-2013-Aldehydes-Ketones - (Cuuduongthancong - Com)

This document discusses organic chemistry concepts related to aldehydes and ketones. It covers nomenclature rules for aldehydes and ketones. Common preparation methods are described, such as oxidizing alcohols or alkenes. Key reactions of aldehydes and ketones are summarized, including addition, reduction, oxidation, and reactions at the alpha carbon. Specific reactions covered include reactions with Grignard reagents, amines, water, alcohols, and aldol additions and condensations.

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Nguyen Hoai Duc
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53 views42 pages

Hoa-Huu-Co - Phan-Thanh-Son-Nam - Chapter-11-2013-Aldehydes-Ketones - (Cuuduongthancong - Com)

This document discusses organic chemistry concepts related to aldehydes and ketones. It covers nomenclature rules for aldehydes and ketones. Common preparation methods are described, such as oxidizing alcohols or alkenes. Key reactions of aldehydes and ketones are summarized, including addition, reduction, oxidation, and reactions at the alpha carbon. Specific reactions covered include reactions with Grignard reagents, amines, water, alcohols, and aldol additions and condensations.

Uploaded by

Nguyen Hoai Duc
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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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: [email protected]
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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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