1. Aldehydes/Ketones: Nucleophilic Addition Reactions

2. Carbonyls and Aldehyde/Ketone  Aldehydes/Ketones = Poor Leaving Group  Acid, Ester, Acid chloride, Amide, Anhydride = Can act as leaving group

3. Chemistry of Carbonyls Nucleophilic O: React with acids and electrophiles Electrophilic C: React with bases and nucleophiles

4. Nomenclature of aldehydes and ketones ending –e with –al  Simple aldehyde: replace the parent ending –e with –al carboxaldehyde  Complex (ring attached): carboxaldehyde  Ketone: Find the longest chain with C=O Replace –e with -one

5. Examples

6. Synthesis of Aldehydes and Ketones  Refer to alcohol chapter Oxidation of primary alcohol with PCC Oxidation of secondary alcohol Hydration of terminal alkynes Friedel-Crafts acylation

7. Oxidation of aldehydes  Tollen’s reagent for aldehyde testing

8. Nucleophilic Addition Reaction  Common nucleophilic addition reaction  To the carbonyl carbon Reduction Hydration Acetal formation Grignard addition Imine formation

9.  Guidelines Under basic (in presence of –OH, -OR) Negatively charged intermediates Under acidic (H+): positively charged intermediate Nucleophilic Addition Reaction

11. Reduction in Org. Chem. And Biochemistry Reducing reagent in Org. Chem. LiAlH4 >> NaBH4

13. Nucleophilic Addition of Water: Hydration  H to O rule: When ROH adds to C=O, H goes to oxygen of C=O (while) RO goes to carbon of C=O To form gem-diol or acetal

14. Nucleophilic Addition of Water: Hydration

15.  Sequential reaction of hemiacetal and acetal through oxonium ion Nucleophilic Addition of Alcohol

16. Hemiacetal formation in nature

17. Acetal as Protecting Group in Org. Syn.

18. Addition of Amines to Imines Imine formation as fundamentals of nitrogen assimilation in biosystems

19. Nucleophilic addition of Grignard reagents Alcohol formation Grignard reagent Formaldehyde:Primary alcohol Grignard reagent +Formaldehyde:Primary alcohol Aldehyde:Secondary alcohol Ketone:Tertiary alcohol Limitation:React with: -CHO, -COR, -CONR 2, -CN, -NO 2, -SO 2 R Decomp. by: -OH, -NH, -SH, -COOH

20. Conjugate addition of ,  -unsaturated ketone/aldehyde