ORGANIC CHEMISTRY

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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  “aldehyde”
is substituted for “ic acid”

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IUPAC names: hydrocarbon + al
Lower priority than ester  “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

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
A mild oxidant such as PCC converts:
- 1o alcohols to aldehydes
- 2o alcohols to ketones.

anhydrous solvent

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A strong oxidant such as Na2Cr2O7 or H2CrO4 converts:
- 1o alcohols to carboxylic acids.
- 2o alcohols to ketones.

3o alcohols are NOT oxidized under usual conditions

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Aldehydes from esters, acyl chlorides

Note: LiAlH4  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 OF ALDEHYDES &
KETONES I
nucleophilic addition

The partial positive

carbon can be attacked
by nucleophiles
nucleophilic addition-
elimination

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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

racemic mixture
Reactions with acetylide ions

Weak acid, will NOT react with the triple bond 20

Reactions with hydrogen cyanide

Converted back to carbonyl in basic solutions

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Nitriles  carboxylic acids

Nitriles  amines 22
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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Protection of “C=O” group
Reactions of aldehydes or ketones with diols would form
cyclic acetals or ketals, as protecting groups for “C=O”.

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Ketone is
protected Bronsted acid catalyst

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Exercise
From starting materials and other chemicals,
prepare following compounds:
Reactions with sulfur nucleophiles

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Witttig reaction

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Reaction mechanism:

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SN2  Using
less sterically
hindered alkyl
halide

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Stereoselectivity of Witttig reaction  depends
on the ylide structure

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Reduction reactions – with hydrides
from H3O+ or H2O

from LiAlH4 or NaBH4

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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
as safe and easy to use as NaBH4 so LiAlH4 is never used
if NaBH4 can be used instead

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Reduction reactions – catalytic hydrogenation

• Catalytic hydrogenation can reduce aldehyde, ketones,

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acyl chlorides, and ALSO alkenes & alkynes
Reduction reactions to hydrocarbons

Be careful
when
choosing
method
This group is also
react under reaction 42
conditions
Oxidation reactions

Aldehydes are generally easier to oxidize than

primary alcohols 43
 Tollens reagent

Too weak to oxidize an

alcohol or any other
functional groups

Should be used when oxidizing aldehydes

containing double bond 44
Exercise
Determine structures of starting materials
(what is “R”) and reagents needed for
following reactions:
Exercise
Complete following reactions:
Exercise
Complete following reactions
(disregarding stereoisomerism):
Exercise
Complete following reactions
(disregarding stereoisomerism):
Exercise
From ethanol as carbon source and other
chemicals, prepare following compounds:
Exercise
From starting materials and other chemicals,
prepare following compounds:

Hint: PCC not only is selective

for the oxidation of primary
alcohols to aldehydes but
also has little effect on carbon-
carbon double/triple bonds
Exercise
From benzene and alcohols with
no more than 4 carbons as carbon source,
prepare following compounds
(can use other chemicals):
Given carbon sources
do not include this ylide
=> need to prepare
REACTIONS OF ALDEHYDES &
KETONES II – REATIONS AT a-C

electrophile
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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 = Aldol additions + dehydrations
If heating is applied, dehydration may occur to form
a conjugated product
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

the new double bond is conjugated not only with

the carbonyl group but also with the benzene ring 63
Mixed / crossed Aldol additions

4 addition products

NOT useful 64
One carbonyl
compound does not
have a-hydrogens

Very strong base

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Intramolecular aldol addition

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FIVE or SIX membered ring is favored
 Halogenations at a-C
Only 1 a-
hydrogen is
replaced in
acidic
solution

All a-
hydrogen
is replaced
in basic
solution
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The haloform reactions

Only for
methyl
ketones

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Exercise
Complete following aldol condensations:
Exercise
Complete following aldol condensations:
Exercise
From styrene, cyclohexane, piperidine,
benzylamine, CH3OH, Br2, HBr, peroxide, Mg,
Li, CuI, H2SO4, PCC, CH2Cl2, H2CrO4, O3, Zn,
H2O, B2H6, dry THF, H2O2, NaOH and ethylene
oxide, prepare following compounds:

Note:
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Exercise
Determine reagents needed for following
reactions (disreagarding stereoisomerism):
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 Exercise
From cyclohexane, Br2, CH3OH, PBr3, Mg, dry
ether, Li, CuI, H2SO4, PCC, H2CrO4, O3, Zn, H2O,
NaOH, CH2Cl2, pyridine, ethylene oxide, NaBH4
and C6H5CH2NH2, prepare following compounds:
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