1. Chemistry of Aromatic Compounds
Electrophilic Aromatic Substitution
Directing Effects
Side-chain Reactions
Synthesis
Nucleophilic Aromatic Substitution

2. Electrophilic Aromatic Substitution

3. EAS Reactions of Benzene

4. Bromination / Chlorination

5. Bromination Mechanism

6. Reaction Profile

7. Nitration

8. Nitration Mechanism

9. Nitration of Toluene

10. Sulfonation is Reversible

11. Desulfonation

12. Friedel-Crafts Acylation

14. 1st, Formaton of Electrophile

15. Acylation Mechanism

16. Intermediate is Resonance-Stabilized

17. An Acylation

18. Friedel-Crafts Alkylation many more limitations

20. Mechanism

21. Carbocation Generated From Alkene

22. Unexpected Product?

23. Carbocations Rearrange…

24. 1o RX Typically Undergoes Shift

25. Side Chain Reactions
1) Reduction of Aromatic Ketones

26. Straight-chain Alkylation can be Accomplished in 2 steps: Acylation, then Reduction

27. 2) Oxidation of Alkyl Substituents

28. 3) Benzylic Bromination with NBS

29. 4) Alkali Fusion of Sulfonic Acids

30. 5) Reduction of Nitro Groups

31. Directing Effects

32. ortho/para-Directing Activating Groups

33. Nitration of Anisole

34. Nitration Affords ortho and para Products

35. Activating ortho/para directors

36. Nitration of Toluene

37. meta-Directing Deactivating Groups

38. Electron-Withdrawing Nitro Group Directs meta

40. meta Directors

41. Comparison

42. More Limitations with Friedel Crafts Reactions

43. Substituent Summary

44. Halogens are the Anomoly Deactivators and o,p-Directors

45. Reactions of Rings With Two or More Substituents

46. The (More) Activated Ring Reacts

47. Mixtures with Conflicting Directing Effects

48. Provide the Reagents

49. Must Acylate First

50. Sulfonic Acid Blocks para Position

51. Give the Reagents

52. Provide the Reagents

54. Provide the Reagents

56. Nucleophlic Aromatic Substitution

57. Not an SN1

58. Not an SN2

61. “SNA” criteria: Strongly deactivated ring Leaving group
Deactivating group(s) ortho &/or para to leaving group (preferably)
Strong base (nucleophile) such as RO-, NH2-

62. Methoxide as a nucleophile

63. Mechanism

64. With no EWG, reaction conditions are more extreme Elimination/Addition Mechanism

65. “Benzyne” Intermediate

66. Carbons are sp2 (not a second p bond)

67. Benzyne can be trapped by a Diene: Undergoes a Diels-Alder rxn

68. Benzyne intermediate has 2 reactive sites

69. Mixture of Regioisomers