1. Organic Chemistry 4 th Edition Paula Yurkanis Bruice Chapter 18 Carbonyl Compounds II Radicals Irene Lee Case Western Reserve University Cleveland, OH ©2004, Prentice Hall

2. Nomenclature of Aldehydes

3. If the aldehyde group is attached to a ring,

4. If a compound has two functional groups, the one with the lowest priority is indicated by its prefix

5. Nomenclature of Ketones

7. If a ketone has a second functional group of higher priority,

8. An aldehyde has a greater partial positive charge on its carbonyl carbon than does a ketone

10. The carbonyl carbon of an aldehyde is more accessible to the nucleophile Ketones have greater steric crowding in their transition states, so they have less stable transition states Steric factors contribute to the reactivity of an aldehyde

11. Aldehydes and ketones react with nucleophiles to form addition products: nucleophile addition reactions

13. If the nucleophile that adds to the aldehyde or ketone is an O or an N, a nucleophilic addition–elimination reaction will occur

14. Formation of a New Carbon–Carbon Bond Using Grignard Reagents Grignard reagents react with aldehydes, ketones, and carboxylic acid derivatives

17. Reaction with Acetylide Ions

19. In basic solution, a cyanohydrin is converted back to the carbonyl compound

20. Synthesis Using Cyanohydrin

21. Reduction by Hydride Ion

24. Utilization of DIBAL to Control the Reduction Reaction

25. The reduction of a carboxylic acid with LiAlH 4 forms a single primary alcohol Acyl chloride is also reduced by LiAlH 4 to yield an alcohol

26. An amide is reduced by LiAlH 4 to an amine

27. Aldehydes and ketones react with a primary amine to form an imine This is a nucleophilic addition–elimination reaction The pH of the reaction must be controlled

28. Dependence of the rate of the reaction of acetone with hydroxylamine on the pH of the reaction: a pH rate profile

29. Aldehydes and ketones react with secondary amines to form enamines

30. Formation of Imine Derivatives

31. Deoxygenation of the Carbonyl Group

32. Water adds to an aldehyde or ketone to form a hydrate

34. Why is there such a difference in the K eq values?

35. The equilibrium constant for the reaction depends on the relative stabilities of the reactants and products

36. Addition of an Alcohol to an Aldehyde or a Ketone

37. Utilization of Protecting Groups in Synthesis LiAlH 4 will reduce the ester to yield an alcohol, but the keto group will also be reduced

38. The keto group is protected as a ketal in this synthesis

39. The more reactive aldehyde is protected with the diol before reaction with the Grignard reagent

40. The OH group in an alcohol can be protected as a trimethylsilyl ether The OH group in a carboxylic acid can be protected as an ester An amino group can be protected with an acetyl group

41. Addition of Sulfur Nucleophiles

42. Desulfurization replaces the C–S bonds with C–H bonds

43. Formation of Alkenes The Wittig Reaction

45. Preparation of the Phosphonium Ylide If two sets of reagents are available for the synthesis of an alkene, it is better to use the one that requires the less sterically hindered alkyl halides

46. The Wittig reaction is completely regioselective This reaction is the best way to make a terminal alkene Stable ylides form primarily E isomers, and unstabilized ylides form primarily Z isomers Stable ylides have a group (C=O) that can share the carbanion’s negative charge

47. Stereochemistry of Nucleophilic Addition Reaction

55. Nucleophiles that form unstable addition products form conjugated addition products, because the conjugate addition is not reversible Nucleophiles that form stable addition products can form direct addition products or conjugate addition products If the rate of direct addition is slowed down by steric hindrance, a Grignard reagent will form the conjugate addition product

56. Nucleophilic Addition to ,  -Unsaturated Carboxylic Acid Derivatives

57. Enzyme-Catalyzed Additions to ,  - Unsaturated Carbonyl Compounds