2. WWU -- Chemistry Nucleophilic Substitution Reactions: Reactions and Synthetic Applications

3. WWU -- Chemistry Assignment for Chapter 12 l Read Sections 12.0 through 12.4 l SKIP Pages 1108 (bottom) through 1112 (Sect. 12.4) l New material on N-bromosuccinimide reactions l SKIP Sections 12.5 through 12.6 l Read Sections 12.7 through 12.8 l SKIP Section 12.9 l Read Sections 12.10 through 12.11 l SKIP Section 12.12 l Read Sections 12.13 through end of chapter l ORGANIC NOMENCLATURE: Alcohols and Ethers

4. WWU -- Chemistry Problem Assignment l In-Text Problems –12-1 through 12-8 –12-12 through 12-24 –12-27 through 12-32 –12-34 through 12-39 l End-of-Chapter Problems –40 through 42 –46 through 54 –57 through 61 –63 through 75

5. WWU -- Chemistry General Rules for Nomenclature l Choose the longest continuous chain of carbon atoms which includes the carbon atom bearing the functional group. This chain will identify the parent hydrocarbon. l Number the parent carbon chain from the end nearest the functional group, irrespective of other substitution. l Indicate the substituents by name and number. Assign a number to the carbon atom bearing the functional group. l Combine all parts into one word, using correct punctuation.

6. WWU -- Chemistry General Rules for Nomenclature (continued) l Show the presence of the functional group by replacing the -e of the alkane ending (sometimes the -ane) with the appropriate ending for the functional group. Show the position of the functional group by inserting a number into the name immediately before the name of the parent chain.

7. WWU -- Chemistry Block Diagram for Nomenclature

8. WWU -- Chemistry Nucleophilic Substitution

9. WWU -- Chemistry Nucleophilic Substitution

10. WWU -- Chemistry Assisted Nucleophilic Substitution

11. WWU -- Chemistry Assisted S N 2: Mechanism

12. WWU -- Chemistry Assisted S N 1: Mechanism

13. WWU -- Chemistry Alcohol + Hydrogen Halide l This method is best with tertiary alcohols l This reaction works very slowly with primary and secondary alcohols. l Rearrangements are possible!

14. WWU -- Chemistry Neopentyl Alcohol + Lucas Reagent

15. WWU -- Chemistry Alcohols + Phosphorus Halides

16. WWU -- Chemistry Alcohol + Phosphorus Halide l This method is best for primary and secondary alcohols. l This method is generally unsuccessful with tertiary alcohols l Rearrangements do not happen with this method.

17. WWU -- Chemistry Preparation of Tosylates TsCl R-OTs

18. WWU -- Chemistry Which Alkyl Halide Should I Use? l If the halide is a better leaving group, the reaction will go in higher yield. I - > Br - > Cl - l If the halide is cheaper, the reaction will be more economical. Cl - > Br - > I -

19. WWU -- Chemistry Which Alkyl Halide Should I Use? (Part Two) l Best compromise… Alkyl bromides! l Exception: For CH 3 —X, use Methyl iodide

20. WWU -- Chemistry Addition of Hydrogen Halides to Double Bonds This reaction follows Markovnikov’s Rule Chapter 8, Section 8.4

21. WWU -- Chemistry Free Radical Halogenation of Alkanes Chapter 3, Section 3.17

22. WWU -- Chemistry Allylic Halogenation with N-Bromosuccinimide

23. WWU -- Chemistry Mechanism – Step 1

24. WWU -- Chemistry Mechanism – Step 2

25. WWU -- Chemistry Mechanism – Step 3

26. WWU -- Chemistry Mechanism – Step 4

27. WWU -- Chemistry Halogenation at a Benzylic Position

28. WWU -- Chemistry Benzylic Substitution – Mechanism Step 2

29. WWU -- Chemistry Conversion of Alkyl Halides to Alcohols SN1SN1 SN2SN2

30. WWU -- Chemistry Synthesis of Ethers

31. WWU -- Chemistry Williamson Ether Synthesis SN2SN2

32. WWU -- Chemistry General Reaction of Epoxides

33. WWU -- Chemistry Under Acidic Conditions…

34. WWU -- Chemistry Reactions of Epoxides

35. WWU -- Chemistry More Reactions of Epoxides

36. WWU -- Chemistry Reactions of Epoxides in Basic Medium

37. WWU -- Chemistry Reactions of Epoxides in Acidic Medium

38. WWU -- Chemistry Synthesis of Heliannuol E Hydrolyze to remove methyl group.

39. WWU -- Chemistry Synthesis of Heliannuol C Hydrolyze to remove methyl group.

40. WWU -- Chemistry Synthesis Problem #1

41. WWU -- Chemistry Outline the Mechanism

42. WWU -- Chemistry HBr or PBr 3 ???

43. WWU -- Chemistry Synthesis Problem #2

44. WWU -- Chemistry Synthesis of MTBE (Methyl tert-Butyl Ether)

45. WWU -- Chemistry Synthesis Problem #3

46. WWU -- Chemistry Reactions of Epoxides

47. WWU -- Chemistry More Reactions of Epoxides

48. WWU -- Chemistry What are the Products?

49. WWU -- Chemistry Synthesis Problem #4

50. WWU -- Chemistry The Synthesis Problem from Hell!

51. WWU -- Chemistry Try this! Plus any additional needed reagents and solvents

52. WWU -- Chemistry

54. Change in Assignment (August 11, 2004) l Include the following sections: –12.9 –12.10 –12.11 –12.14 –12.15