加州大学伯克利分校有机化学课件.ppt

? University of California ? Univesity of California Chapter 17: Aldehydes and Ketones Nomenclature Systematic Naming (IUPAC) Structure 1H NMR: Carbonyl group is deshielding 13C NMR UV Synthesis (A review of Chapter 8) Reactions Catalyzed Ionic Additions 1. Hydration: Geminal Diols (Carbonyl Hydrates) 2. Addition of Alcohols 3. Amine Additions 4. Addition of Non-organometallic Carbon Nucleophiles 5. Addition of Hydroxy Groups Revisited: Baeyer-Villiger Oxidation Cyclic Acetals: Protecting Groups CH3OH Intramolecular variant (important for sugars, Chapter 24). Best for 5- and 6-membered rings. H+, H2O Hydrolysis = Deprotection 1. 2. Mg 3. 4. H+, H2O This is also a method to protect diols: Thioacetals: Stable to acid! Application of thioacetals: Desulfurization Deprotection: Thioacetalization uses Lewis acid catalysis, e.g., ZnCl2. Again, cyclic version particularly favorable. More applications: Chapter 23. Example: Ammonia and primary amines add to the carbonyl function and then dehydrate: A “condensation” reaction. Mechanism: Hemiaminal Dehydration Imine Formation A condensation product (-H2O) Lipshutz BBoys Intramolecular reaction: Best for 5- and 6-membered rings. Cat. H+ Teaser: An 1H NMR spectrum of an imine (downfield region) Special Imines + H2N-OH (as H3N+-OH Cl-) An oxime + Semicarbazide Semicarbazone -H2O -H2O + -H2O Hydrazone Hydroxylamine Reaction of the carbonyl function with secondary amines gives hemiaminals in which normal condensation is not possible: No H left on N. Therefore, water loss occurs to the “carbon side” to form an enamine. Enamine Formation Mechanism: Enamines are useful, can be alkylated (Chapter 18-4). Wolff-Kishner Reduction An Application of Hydrazones Synthesis of a Hydrazone Wolff-Kishner Reduction Mechanism: Nitrogen elimination In practice, the reaction is carried out without isolating the intermediate hydrazone. A diazaallylic anion Use in alkylbenzene synthesis: The Wolff-Kishner reduction is an alternativ