哥伦比亚大年夜学无机化学

  22 22 14 14 15 14 16 17 18 20 22 22 21 22 22 17.10 Reaction with Primary Amines: Imines Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage Acetal formation Imine formation 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 C O H2N R HN H R a carbinolamine N R C + H2O (imine) C O + ? ? ? ? Imine (Schiff's Base) Formation CH3NH2 CH O + CH=NCH3 + H2O N-Benzylidenemethylamine (70%) Example CH3NH2 CH O + CH=NCH3 + H2O N-Benzylidenemethylamine (70%) CH OH NHCH3 Example (CH3)2CHCH2NH2 O + + H2O N-Cyclohexylideneisobutylamine (79%) NCH2CH(CH3)2 Example (CH3)2CHCH2NH2 O + + H2O N-Cyclohexylideneisobutylamine (79%) NCH2CH(CH3)2 OH NHCH2CH(CH3)2 Example Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage Acetal formation Imine formation 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 Reaction with Derivatives of Ammonia H2N G + R2C O R2C NG + H2O Reaction with Derivatives of Ammonia H2N G + R2C O R2C NG + H2O H2N OH R2C NOH hydroxylamine oxime CH3(CH2)5CH + H2NOH O CH3(CH2)5CH + H2O NOH (81-93%) Example Reaction with Derivatives of Ammonia H2N G + R2C O R2C NG + H2O H2N OH R2C NOH hydroxylamine oxime H2N NH2 R2C NNH2 hydrazine hydrazone etc. + H2NNH2 + H2O (73%) Example O C NNH2 C CCH3 + H2NNH + H2O Example O CCH3 NNH phenylhydrazine a phenylhydrazone (87-91%) CH3(CH2)9CCH3 O H2NNHCNH2 O H2O CH3(CH2)9CCH3 NNHCNH2 O + + Example semicarbazide a semicarbazone (93%) 17.11 Reaction with Secondary Amines: Enamines Some reactions of aldehydes and ketones progress beyond the nucleophilic addition stage Acetal formation I