17.10%20Reaction%20with%20Primary%20Amines:%20Imines

1
17.10Reaction with Primary AminesImines
2
Some reactions of aldehydes and ketones
progressbeyond the nucleophilic addition stage

• Acetal formation
• Imine formation
• Compounds related to imines
• Enamines
• The Wittig reaction

3
Some reactions of aldehydes and ketones
progressbeyond the nucleophilic addition stage

• Acetal formation
• Imine formation
• Compounds related to imines
• Enamines
• The Wittig reaction

4
Imine (Schiff's Base) Formation



H
C
O
HN
C
O




R
a carbinolamine

N
H2O
C
(imine)
R
5
Example

CH3NH2
CHNCH3
H2O
N-Benzylidenemethylamine (70)
6
Example

CH3NH2
OH
CH
NHCH3
CHNCH3
H2O
N-Benzylidenemethylamine (70)
7
Example
(CH3)2CHCH2NH2

O
NCH2CH(CH3)2
H2O
N-Cyclohexylideneisobutylamine (79)
8
Example
(CH3)2CHCH2NH2

O
OH
NHCH2CH(CH3)2
NCH2CH(CH3)2
H2O
N-Cyclohexylideneisobutylamine (79)
9
Some reactions of aldehydes and ketones
progressbeyond the nucleophilic addition stage

• Acetal formation
• Imine formation
• Compounds related to imines
• Enamines
• The Wittig reaction

10
Some reactions of aldehydes and ketones
progressbeyond the nucleophilic addition stage

• Acetal formation
• Imine formation
• Compounds related to imines
• Enamines
• The Wittig reaction

11
Reaction with Derivatives of Ammonia
12
Reaction with Derivatives of Ammonia
hydroxylamine
oxime
13
Example
(81-93)
14
Reaction with Derivatives of Ammonia
hydroxylamine
oxime
hydrazine
hydrazone
etc.
15
Example
H2NNH2
H2O
(73)
16
Example
CCH3
H2NNH
phenylhydrazine
H2O
a phenylhydrazone (87-91)
17
Example

CH3(CH2)9CCH3
semicarbazide

H2O
a semicarbazone (93)
18
17.11Reaction with Secondary AminesEnamines
19
Some reactions of aldehydes and ketones
progressbeyond the nucleophilic addition stage

• Acetal formation
• Imine formation
• Compounds related to imines
• Enamines
• The Wittig reaction

20
Some reactions of aldehydes and ketones
progressbeyond the nucleophilic addition stage

• Acetal formation
• Imine formation
• Compounds related to imines
• Enamines
• The Wittig reaction

21
Enamine Formation
H2O
(enamine)
22
Example


(heat in benzene)
N

NH

(80-90)
23
Example


(heat in benzene)
N

NH

via