9 Aldehyde & Ketone

Ketones and
Aldehydes
Carbonyl Compounds
Chapter 4 2
Carbonyl Structure
 Carbon is sp2 hybridized.

 C═O bond is shorter, stronger, and more
polar than C═C bond in alkenes.
Chapter 4 3
Ketone Nomenclature
O O
1 3 4 1 3 4
CH3 C CH CH3 CH3 C CH CH2OH
2 2 CH
CH3 3
3-methyl-2-butanone 4-hydroxy-3-methyl-2-butanone
 Number the chain so that carbonyl carbon

has the lowest number.
 Replace the alkane -e with -one.
Chapter 4 4
Ketone Nomenclature
(Continued)
1 O
3-bromocyclohexanone
3
Br
 For cyclic ketones, the carbonyl carbon is

assigned the number 1.
Chapter 4 5
Aldehydes Nomenclature
CH3 O
5 2
CH3 CH2 CH CH2 C H
3 1
3-methylpentanal
 The aldehyde carbon is number 1.

 IUPAC: Replace -e with -al.
Chapter 4 6
Carbonyl as Substituent
 On a molecule with a higher priority functional
group, a ketone is an oxo and an aldehyde is
a formyl group.
 Aldehydes have a higher priority than
ketones.
1 COOH
O CH3 O
CH3 C CH CH2 C H 3
4 3 1
CHO
3-methyl-4-oxopentanal 3-formylbenzoic acid

Chapter 4 7
Common Names for Ketones
 Named as alkyl attachments to —C═O.

 Use Greek letters instead of numbers.
O O
CH3 C CH CH3 CH3CH C CH CH3
CH3 Br CH3
methyl isopropyl ketone bromoethyl isopropyl ketone
Chapter 4 8
Historical Common Names
O
C
O CH3
CH3 C CH3
acetone acetophenone
O
C
benzophenone
Chapter 4 9
Boiling Points
 Ketones and aldehydes are more polar, so they have

a higher boiling point than comparable alkanes or
ethers.
 They cannot hydrogen-bond to each other, so their
boiling point is lower than comparable alcohol.
Chapter 4 10
Solubility of Ketones and
Aldehydes
 Good solvent for alcohols.
 Lone pair of electrons on
oxygen of carbonyl can
accept a hydrogen bond
from O—H or
N—H.
 Acetone and
acetaldehyde are
miscible in water.
Chapter 4 11
Oxidation of Secondary Alcohols
to Ketones
 Secondary alcohols are readily oxidized to

ketones with sodium dichromate (Na2Cr2O7)
in sulfuric acid or by potassium
permanganate (KMnO4).
Chapter 4 12
Oxidation of Primary Alcohols to
Aldehydes
 Pyridinium chlorochromate (PCC) is

selectively used to oxidize primary alcohols to
aldehydes.
Chapter 4 13
Ozonolysis of Alkenes
 The double bond is oxidatively cleaved by

ozone followed by reduction.
 Ketones and aldehydes can be isolated as
products.
Chapter 4 14
Friedel–Crafts Reaction
 Reaction between an acyl halide and an

aromatic ring will produce a ketone.
Chapter 4 15
Hydration of Alkynes
 The initial product of Markovnikov hydration is an enol,

which quickly tautomerizes to its keto form.
 Internal alkynes can be hydrated, but mixtures of
ketones often result.
Chapter 4 16
Reaction: Nucleophilic
Addition
 A strong nucleophile attacks the carbonyl carbon,

forming an alkoxide ion that is then protonated.
 Aldehydes are more reactive than ketones.
Chapter 4 17
The Wittig Reaction
 The Wittig reaction converts the carbonyl

group into a new C═C double bond where no
bond existed before.
 A phosphorus ylide is used as the nucleophile
in the reaction.
Chapter 4 18
Preparation of Phosphorus Ylides
 Prepared from triphenylphosphine and an

unhindered alkyl halide.
 Butyllithium then abstracts a hydrogen from
the carbon attached to phosphorus.
Chapter 4 19
Mechanism of the Wittig Reaction
Betaine formation
Oxaphosphetane formation
Chapter 4 20
Mechanism for Wittig (continued)
 The oxaphosphetane will collapse, forming

carbonyl (ketone or aldehyde) and a molecule
of triphenyl phosphine oxide.
Chapter 4 21
Solved Problem 2
Show how you would use a Wittig reaction to synthesize 1-phenyl-1,3-butadiene.
Chapter 4 22
Solved Problem 2 (Continued)
Solution (Continued)
This molecule has two double bonds that might be formed by Wittig reactions. The central double bond
could be formed in either of two ways. Both of these syntheses will probably work, and both will
produce a mixture of cis and trans isomers.
You should complete this solution by drawing out the syntheses indicated by this analysis (Problem 18-
16). Chapter 4 23
Hydration of Ketones and
Aldehydes
 In an aqueous solution, a ketone or an

aldehyde is in equilibrium with its hydrate, a
geminal diol.
 With ketones, the equilibrium favors the
unhydrated keto form (carbonyl).
Chapter 4 24
Mechanism of Hydration of
Ketones and Aldehydes
 Hydration occurs through the nucleophilic addition

mechanism, with water (in acid) or hydroxide (in
base) serving as the nucleophile.
Chapter 4 25
Cyanohydrin Formation
 The mechanism is a base-catalyzed nucleophilic

addition: Attack by cyanide ion on the carbonyl group,
followed by protonation of the intermediate.
 HCN is highly toxic.
Chapter 4 26
Formation of Imines
 Ammonia or a primary amine reacts with a ketone or

an aldehyde to form an imine.
 Imines are nitrogen analogues of ketones and
aldehydes with a C═N bond in place of the carbonyl
group.
 Optimum pH is around 4.5
Chapter 4 27
Mechanism of Imine Formation
Acid-catalyzed addition of the amine to the carbonyl
compound group.
Acid-catalyzed dehydration.
Chapter 4 28
Other Condensations with Amines
Chapter 4 29
Oxidation of Aldehydes
Aldehydes are easily oxidized to carboxylic acids.

Chapter 4 30
Reduction Reagents
 Sodium borohydride, NaBH4, can reduce

ketones to secondary alcohols and aldehydes
to primary alcohols.
 Lithium aluminum hydride, LiAlH4, is a
powerful reducing agent, so it can also
reduce carboxylic acids and their derivatives.
 Hydrogenation with a catalyst can reduce the
carbonyl, but it will also reduce any double or
triple bonds present in the molecule.
Chapter 4 31
Sodium Borohydride
O OH
NaBH4
R R(H) CH3OH R R(H)
H
aldehyde or ketone
• NaBH4 can reduce ketones and aldehydes, but not

esters, carboxylic acids, acyl chlorides, or amides.
Chapter 4 32
Lithium Aluminum Hydride
O OH
LiAlH4
R R(H) ether R R(H)
H
aldehyde or ketone
 LiAlH4 can reduce any carbonyl because it is a very strong

reducing agent.
 Difficult to handle.
Chapter 4 33
Clemmensen Reduction
O
C CH2CH2CH3
CH2CH3 Zn(Hg)
HCl, H2O
O
Zn(Hg)
CH2 C CH2 CH3
H HCl, H2O
Chapter 4 34
Wolff–Kishner Reduction
 Forms hydrazone, then heat with strong base

like KOH or potassium tert-butoxide.
 Use a high-boiling solvent: ethylene glycol,
diethylene glycol, or DMSO.
 A molecule of nitrogen is lost in the last steps
of the reaction.
Chapter 4 35

9 Aldehyde & Ketone

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Ketones and

 Carbon is sp2 hybridized.

 Number the chain so that carbonyl carbon

 For cyclic ketones, the carbonyl carbon is

 The aldehyde carbon is number 1.

3-methyl-4-oxopentanal 3-formylbenzoic acid

 Named as alkyl attachments to —C═O.

methyl isopropyl ketone bromoethyl isopropyl ketone

 Ketones and aldehydes are more polar, so they have

 Secondary alcohols are readily oxidized to

 Pyridinium chlorochromate (PCC) is

 The double bond is oxidatively cleaved by

 Reaction between an acyl halide and an

 The initial product of Markovnikov hydration is an enol,

 A strong nucleophile attacks the carbonyl carbon,

 The Wittig reaction converts the carbonyl

 Prepared from triphenylphosphine and an

 The oxaphosphetane will collapse, forming

 In an aqueous solution, a ketone or an

 Hydration occurs through the nucleophilic addition

 The mechanism is a base-catalyzed nucleophilic

 Ammonia or a primary amine reacts with a ketone or

Aldehydes are easily oxidized to carboxylic acids.

 Sodium borohydride, NaBH4, can reduce

• NaBH4 can reduce ketones and aldehydes, but not

 LiAlH4 can reduce any carbonyl because it is a very strong

 Forms hydrazone, then heat with strong base

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