Chapter 8: Aldehyde-Ketone

The content includes:

8.1. Carbonyl compounds

8.2. Nomenclature

8.3. Preparation of Aldehyde, Ketone

8.3.1. Oxidation of Alcohol

04/28/2016 602035- Aldehyde-Ketone 1

 Chapter 8: Aldehyde-Ketone

8.3.2. Ozonolysis of Alkene

8.3.3. Friedel–Crafts acylation

8.3.4. Hydration of Alkyne

8.3.5. Reactions of Grignard reagents

04/28/2016 602035- Aldehyde-Ketone 2

 Chapter 8: Aldehyde-Ketone

8.3.6. The Gatterman–Koch formylation

8.4. Physical Properties

8.5. Reactions of Aldehyde, Ketones

8.5.1. Nucleophilic Addition

8.5.1.1. Addition of HCN

04/28/2016 602035- Aldehyde-Ketone 3

 Chapter 8: Aldehyde-Ketone

8.5.1.2. Hydration of Ketone, Aldehydes

8.5.1.3. Addition of Alcohol

8.5.1.4. Addition of NH3 and deriatives of amonia

8.5.1.5. Addition of NaHSO3

04/28/2016 602035- Aldehyde-Ketone 4

 Chapter 8: Aldehyde-Ketone

8.5.2. Aldol Condensations

8.5.3. Cannizzaro reaction.

8.5.4. α-halogenation reactions

8.5.5. Oxidation reactions

8.5.6. Reduction of carbonyl compounds

04/28/2016 602035- Aldehyde-Ketone 5

 Chapter 8: Aldehyde-Ketone

8.1. Carbonyl compounds

Compounds containing the carbonyl group

04/28/2016 602035- Aldehyde-Ketone 6

 Chapter 8: Aldehyde-Ketone

8.2. Nomenclature

Ketones: replacing the final -e in the alkane name with -

one

Aldehydes : replacing the final -e of the alkane name with -

al

04/28/2016 602035- Aldehyde-Ketone 7

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 8

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 9

 Chapter 8: Aldehyde-Ketone

8.3. Preparation of Aldehyde, Ketone

8.3.1. Oxidation of Alcohol

04/28/2016 602035- Aldehyde-Ketone 10

 Chapter 8: Aldehyde-Ketone

8.3.2. Ozonolysis of Alkene

04/28/2016 602035- Aldehyde-Ketone 11

 Chapter 8: Aldehyde-Ketone

8.3.3. Friedel–Crafts acylation

04/28/2016 602035- Aldehyde-Ketone 12

 Chapter 8: Aldehyde-Ketone

8.3.4. Hydration of Alkynes

04/28/2016 602035- Aldehyde-Ketone 13

 Chapter 8: Aldehyde-Ketone

8.3.5. Reaction of Grignard reagents

04/28/2016 602035- Aldehyde-Ketone 14

 Chapter 8: Aldehyde-Ketone

8.3.6. The Gatterman–Koch formylation

04/28/2016 602035- Aldehyde-Ketone 15

 Chapter 8: Aldehyde-Ketone

8.4. Physical Properties

Ketones and aldehydes have higher boiling points than

hydrocarbons, ethers with similar molecular weights

04/28/2016 602035- Aldehyde-Ketone 16

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 17

 Chapter 8: Aldehyde-Ketone

8.5. Reaction of Aldehyde, Ketone

8.5.1. Nucleophilic Addition

8.5.1.1. Addition of HCN

O HCN NC OH

KCN

04/28/2016 602035- Aldehyde-Ketone 18

 Chapter 8: Aldehyde-Ketone

Step 1: Cyanide adds to the carbonyl.

04/28/2016 602035- Aldehyde-Ketone 19

 Chapter 8: Aldehyde-Ketone

Step 2: Protonation gives the cyanohydrin.

04/28/2016 602035- Aldehyde-Ketone 20

 Chapter 8: Aldehyde-Ketone

8.5.1.2. Hydration of Ketone, Aldehyde

04/28/2016 602035- Aldehyde-Ketone 21

 Chapter 8: Aldehyde-Ketone

In acid:

04/28/2016 602035- Aldehyde-Ketone 22

 Chapter 8: Aldehyde-Ketone

8.5.1.3. Addition of Alcohol

In Base OR
-
OH
C + H2O
+ ROH
du
O
OH

04/28/2016 602035- Aldehyde-Ketone 23

 Chapter 8: Aldehyde-Ketone

In acid

+ OR
H
C + H2O
+ ROH du
O
OR

04/28/2016 602035- Aldehyde-Ketone 24

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 25

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 26

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 27

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 28

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 29

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 30

 Chapter 8: Aldehyde-Ketone

Acetals as Protecting Groups

04/28/2016 602035- Aldehyde-Ketone 31

 Chapter 8: Aldehyde-Ketone

Propose an efficient synthesis for each of the following

transformations:

04/28/2016 602035- Aldehyde-Ketone 32

 Chapter 8: Aldehyde-Ketone

8.5.1.4. Addition of NH3 and deriatives of amonia

04/28/2016 602035- Aldehyde-Ketone 33

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 34

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 35

 Chapter 8: Aldehyde-Ketone

8.5.2. Aldol addition

-hydroxy aldehyde

04/28/2016 602035- Aldehyde-Ketone 36

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 37

 Chapter 8: Aldehyde-Ketone

Crossed Aldol addition

04/28/2016 602035- Aldehyde-Ketone 38

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 39

 Chapter 8: Aldehyde-Ketone

Aldol condensation

04/28/2016 602035- Aldehyde-Ketone 40

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 41

 Chapter 8: Aldehyde-Ketone

Predict the product of the aldol addition reaction that occurs

when the following compound is treated with aqueous
sodium hydroxide

04/28/2016 602035- Aldehyde-Ketone 42

 Chapter 8: Aldehyde-Ketone

8.5.3. Cannizzaro reaction

04/28/2016 602035- Aldehyde-Ketone 43

 Chapter 8: Aldehyde-Ketone

8.5.3. -halogenation reaction

04/28/2016 602035- Aldehyde-Ketone 44

 Chapter 8: Aldehyde-Ketone

8.5.5. Oxidation reactions

Oxidation of Aldehydes: Easily oxidized to carboxylic acids.

04/28/2016 602035- Aldehyde-Ketone 45

 Chapter 8: Aldehyde-Ketone

Predict the major products of the following reactions

04/28/2016 602035- Aldehyde-Ketone 46

 Chapter 8: Aldehyde-Ketone

Tollens Test : oxidize Aldehydes to forms a silver mirror.

O
+
_ H2O
R C H+ 2 Ag(NH3)2 + 3 OH 2

O O
+
_ H2O _
C H+ 2 Ag(NH3)2 + 3 OH 2 Ag + R C O + 4 NH3 + 2 H2O
=>

04/28/2016 602035- Aldehyde-Ketone 47

 Chapter 8: Aldehyde-Ketone

8.5.6. Reduction of carbonyl compounds

04/28/2016 602035- Aldehyde-Ketone 48

 Chapter 8: Aldehyde-Ketone

Exercises: Draw the major product for each of the

following reactions

04/28/2016 602035- Aldehyde-Ketone 49

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 50

 Chapter 8: Aldehyde-Ketone

04/28/2016 602035- Aldehyde-Ketone 51