1. Keto-enol tautomerization • enolization • “normal” aldehydes and ketones • Keq = ~ 10-8

2. Stabilized aldehydes and ketones • -diketones • Keq = ~ 10

3. Mechanism for acid-catalyzed enolization

4. Mechanism for acid-catalyzed enolization

5. Reactions of enols: -halogenation

6. An example

7. An example

8. Mechanism of -halogenation

9. -Bromination of Acids: the HVZ Reaction

10. The HVZ Reaction

11. Acidity of carbonyl compounds • enolate ion formation • pKa = ~ 16-20

12. Base-catalyzed enolization

13. Ester Enolates • pKa = ~22

14. Alkylation of ester enolates

15. Alkylation of ester enolates

16. Alkylation of ester enolates

17. Alkylation of ester enolates

18. Alkylation of ester enolates

19. Reactions of enolates: • The Aldol Condensation

20. Aldol Condensation

21. More Aldol Condensation

22. Formation of -unsaturated carbonyls

23. An example

24. An example

25. Claisen-Schmidt condensation

26. Claisen-Schmidt condensation

27. Examples

28. Nucleophilic Addition to -Unsaturated Carbonyls

29. Michael Addition

30. Michael Addition

31. Robinson Annulation

32. Robinson Annulation

33. Michael Addition

34. Michael Addition

35. Robinson Annulation

36. Robinson Annulation

37. The Claisen condensation

38. The Claisen condensation

39. An example

40. The product

41. Another example

42. Another product

43. The Dieckmann condensation

44. The Dieckmann condensation

45. Decarboxylation of Malonic Acids and b-Ketoacids • Malonic acid Acetoacetic acid

46. Decarboxylation of Malonic Acids and b-Ketoacids

47. Ketone acylation using esters

48. Ketone acylation using esters

49. Ketone acylation using esters

50. Acetoacetic ester synthesis of ketones • ethyl acetoacetate