1. 17.10 Reaction with Primary Amines: Imines2

2. Compounds related to imines Enamines The Wittig reaction
Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage
Acetal formation
Imine formation
Compounds related to imines
Enamines
The Wittig reaction 22

3. Compounds related to imines Enamines The Wittig reaction
Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage
Acetal formation
Imine formation
Compounds related to imines
Enamines
The Wittig reaction 22

4. Imine (Schiff's Base) Formation•• •• +
H2N R C O HN C O H
• •
• • •• •• R
a carbinolamine •• N C
(imine)
+ H2O R 3

5. N-Benzylidenemethylamine (70%)
Example CH O +
CH3NH2
CH=NCH3
+ H2O
N-Benzylidenemethylamine (70%) 4

6. N-Benzylidenemethylamine (70%)
Example CH O +
CH3NH2 OH CH
NHCH3
CH=NCH3
+ H2O
N-Benzylidenemethylamine (70%) 4

7. N-Cyclohexylideneisobutylamine (79%)
Example O +
(CH3)2CHCH2NH2
NCH2CH(CH3)2
+ H2O
N-Cyclohexylideneisobutylamine (79%) 5

8. N-Cyclohexylideneisobutylamine (79%)
Example O +
(CH3)2CHCH2NH2 OH
NHCH2CH(CH3)2
NCH2CH(CH3)2
+ H2O
N-Cyclohexylideneisobutylamine (79%) 5

9. Compounds related to imines Enamines The Wittig reaction
Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage
Acetal formation
Imine formation
Compounds related to imines
Enamines
The Wittig reaction 22

10. Compounds related to imines Enamines The Wittig reaction
Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage
Acetal formation
Imine formation
Compounds related to imines
Enamines
The Wittig reaction 22

11. Reaction with Derivatives of Ammonia
H2N G +
R2C O NG
H2O 14

12. Reaction with Derivatives of Ammonia
H2N G +
R2C O NG
H2O
H2N OH
R2C
NOH
hydroxylamine
oxime 14

13. Example
CH3(CH2)5CH
+ H2NOH O
CH3(CH2)5CH
+ H2O
NOH
(81-93%) 15

14. Reaction with Derivatives of Ammonia
H2N G +
R2C O NG
H2O
H2N OH
R2C
NOH
hydroxylamine
oxime
H2N
NH2
R2C
NNH2
hydrazine
hydrazone
etc. 14

15. Example O C
+ H2NNH2
NNH2 C
+ H2O
(73%) 16

16. a phenylhydrazone (87-91%)
Example O
CCH3
+ H2NNH
phenylhydrazine
CCH3
NNH
+ H2O
a phenylhydrazone (87-91%) 17

17. Example O H2NNHCNH2 O + CH3(CH2)9CCH3 semicarbazide CH3(CH2)9CCH3
a semicarbazone (93%) 18

18. 17.11 Reaction with Secondary Amines: Enamines20

19. Compounds related to imines Enamines The Wittig reaction
Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage
Acetal formation
Imine formation
Compounds related to imines
Enamines
The Wittig reaction 22

20. Compounds related to imines Enamines The Wittig reaction
Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage
Acetal formation
Imine formation
Compounds related to imines
Enamines
The Wittig reaction 22

21. Enamine Formation C O R2N H C O H R2NH C R2N + H2O (enamine) •• • • ••21

22. Example O
(heat in benzene) N +
N H
(80-90%) 22

23. Example O
(heat in benzene) N +
N H OH N
via 22