12/5/2017

Aldehydes and Ketones

• Aldehydes and ketones are carbonyl

containing compounds.

1
 12/5/2017

Nomenclature
1. Aldehydes are named by replacing the end -e
of the corresponding alkane name with-al.
(Some aldehydes have common names).
2. Cyclic aldehydes are named by adding the
suffix carbaldehyde to the ring name.
3. Ketones are named by replacing the end –e of
the alkane by –one.

2
 12/5/2017

Physical Properties: Boiling Point

• The carbonyl group is a polar group; therefore,

aldehydes and ketones have higher boiling
points than hydrocarbons of the same
molecular weight.
• However, since aldehydes and ketones cannot
have strong hydrogen bonds between their
molecules, they have lower boiling points than
the corresponding alcohols.

Physical Properties: Boiling Point

3
 12/5/2017

Physical Properties: Solubility

• The carbonyl oxygen atom allows molecules of

aldehydes and ketones to form strong
hydrogen bonds to molecules of water.
• As a result, low-molecular-weight aldehydes
and ketones show appreciable solubilities in
water (e.g. acetone and acetaldehyde).

Physical Properties: Solubility

• Hydrogen bonding (shown in red) between

water molecules and acetone.
8

4
 12/5/2017

Synthesis of Aldehydes
• Aldehydes can be prepared by:

1. Oxidation of primary alcohols

2. Reduction of carboxylic acid derivatives

(esters, acyl chlorides)

1. Oxidation of primary alcohols:

PCC is used to prevent overoxidation.

10

5
 12/5/2017

2. Reduction of carboxylic acid derivatives:

• LAH reduces carboxylic acids to 1° alcohols.
• Esters are more easily reduced than acids.
• DIBAL-H is less reactive than LAH.
• Aldehydes are achieved in high yield.

11

Mechanism

12

6
 12/5/2017

Synthesis of Ketones

1. Ozonolysis of alkenes.
2. Friedel-Crafts acylations.
3. Oxidation of secondary alcohols.

13

1. Ozonolysis of Alkenes

• For synthesis of both ketones and aldehydes.

14

7
 12/5/2017

2. Friedel-Crafts Acylations

• Electrophilic aromatic substitution reaction.

15

3. Oxidation of Secondary Alcohols

• This is Jone’s reagent.

• KmnO4 alkaline , K2CrO7 acidic can also be used.

16

8
 12/5/2017

Reactions of Aldehydes and Ketones

• Nucleophilic addition.
• Oxidation of aldehydes.
• Reduction.

17

Structure of the Carbonyl Group

• Hybridization is sp2.
• Trigonal planar.
• Angle is ≈ 120°.
• Highly polarized.

18

9
 12/5/2017

Reaction of Aldehydes and Ketones with

Nucleophiles

• Being highly polarized, carbonyl group

nundergoes nucleophilic addition.
• The sp2-hybridized carbon of the carbonyl
accepts electron pairs from a nucleophile.
• Electrons of carbon–oxygen π bond shift out
to the oxygen.
• The carbon atom changes to tetrahedral
geometry and sp3 hybridiaztion.

19

Nucleophilic Addition

• The most characteristic reaction of aldehydes

and ketones is nucleophilic addition to the
carbon–oxygen double bond.

20

10
 12/5/2017

Nucleophilic Addition

• When strong nucleophiles are used.

• Proton source is needed.
21

Acid-Catalyzed Nucleophilic Addition

• The reaction is generally carried out under

acidic conditions especially when weak
nucleophiles are used.

22

11
 12/5/2017

Mechanism: Step 1

23

Mechanism: Step 2

24

12
 12/5/2017

Examples of Nucleophilic Addition Reactions

• Addition of alcohols.
• Addition of ammonia derivatives.
• Addition of HCN.
• Reduction with hydride ion (H–).
• Reaction with organometallic reagents.
• And others.

25

Relative Reactivity: Aldehydes vs Ketones

• Aldehydes are more reactive in nuclephilic

additions than are ketones.
• Both steric and electronic factors favor
aldehydes.
26

13
 12/5/2017

The Addition of Alcohols: Hemiacetals

• The hemiacetal results by nucleophilic

addition of the alcohol oxygen to the carbonyl
carbon of the aldehyde or ketone.
27

The Addition of Alcohols: Hemiacetals

• Cyclic hemiacetals with 5- or 6-membered

rings are usually much more stable than open-
chain hemiacetals.
28

14
 12/5/2017

The Addition of Alcohols: Hemiacetals

• Most simple sugars exist primarily in a cyclic

hemiacetal form (e.g. glucose).

29

The Addition of Alcohols: Hemiacetals Formation

• The formation of hemiacetals is catalyzed by

acids and bases!

30

15
 12/5/2017

Assignment

• Draw a full mechanism for:

 Acid-catalyzed hemiacetal formation.
 Base-catalyzed hemiacetals formation.

31

Oxidation of Aldehydes

• Aldehydes are much more easily oxidized than

ketones.
• Aldehydes are readily oxidized by strong
oxidizing agent (e.g. KMnO4).
• Aldehydes are also oxidized by such mild
oxidizing agent such as Ag2O.

32

16
 12/5/2017

Oxidation of Aldehydes

• In these oxidations aldehydes lose the

hydrogen that is attached to the carbonyl
carbon. Because ketones lack this hydrogen,
they are more resistant to oxidation.
33

17