17.10 Reaction with Primary Amines: Imines 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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

17.11 Reaction with Secondary Amines: Enamines 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

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

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

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

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