1. Chapter 13 Alcohols, Phenols, Ethers; Thiols and Sulfides

2. Fig. 13-1, p. 505 Alcohol introduction: Hydrogen Bonding

3. Alcohol introduction: Types of Alcohols

4. Alcohol introduction: reaction of sp3 oxygen with strong acids

5. Table 13-1, p. 506

6. Fig. 13-2, p. 508

7. [elim] [sub]

8. Reactions I.Substitution Reactions of Alcohols (review) A. Conversion to alkyl halides 1. 1° & 3° with strong acid

9. Reactions I.Substitution Reactions of Alcohols (review) A. Conversion to alkyl halides 1. 1° & 3° with strong acid

10. Reactions I.Substitution Reactions of Alcohols (review) A. Conversion to alkyl halides 1. 1° & 3° with strong acid 2. 1° & 2° with SOCl 2, pyridine 3. 1° & 2° with PBr 3.

11. p. 516 Substitution Reactions of alcohols : review

12. Reactions I.Substitution Reactions of Alcohols (review) A. Conversion to alkyl halides 1. 1° & 3° with strong acid 2. 1° & 2° with SOCl 2, pyridine 3. 1° & 2° with PBr 3 4. 1° & 2° with TsCl

13. Reactions I.Substitution Reactions of Alcohols (review) A. Conversion to alkyl halides 1. 1° & 3° with strong acid 2. 1° & 2° with SOCl 2, pyridine 3. 1° & 2° with PBr 3 4. 1° & 2° with TsCl Problem: Enantiomeric products from same starting material.

14. I.Substitution Reactions of Alcohols (cont.) B. Formation of alkoxide ions pKa’s of alcohols Reactions

15. Table 13-1, p. 506

16. I.Substitution Reactions of Alcohols (cont.) B. Formation of alkoxide ions pKa’s of alcohols 1. Strong Bases (NaH, NaNH 2 ) 2. Metals (Na 0 ) Reactions

17. I.Substitution Reactions of Alcohols (cont.) B. Ether formation 1. Williamson Ether Synthesis a. Formation of alkoxides b. acyclic ethers c. cyclic ethers (including oxiranes) 2. Acid catalyzed ether formation Reactions

18. I.Substitution Reactions of Alcohols (cont.) C. Protection 1. introduction to protection a. TMS ether Reactions

19. II.Reactions of ethers. A. Unstrained B. Oxiranes (epoxides) 1. basic / nucleophilic conditions epoxy resins (what is in those two tubes) Reactions

20. Epoxy Resins

21. Two substances Substance #1. diepoxy prepolymer.

22. Epoxy Resins Two substances Substance #1. diepoxy prepolymer.

23. Epoxy Resins Two tubes Substance #1. diepoxy prepolymer. Substance #2. A polyamine (hardener, curing agent)

24. II.Reactions of ethers. A. Unstrained B. Oxiranes (epoxides) 1. basic / nucleophilic conditions epoxy resins (what is in those two tubes) 2. acidic conditions a. 1° & 2° b. 3° Reactions

25. II.Reactions of ethers. A. Unstrained B. Oxiranes (epoxides) 1. basic / nucleophilic conditions epoxy resins (what is in those two tubes) 2. acidic conditions a. 1° & 2° b. 3° C. Allyl Aryl Ethers (The Claisen Rearrangement) Reactions

26. Professor Rainer Ludwig Claisen (January 14, 1851 – January 5, 1930) was a famous German chemist best known for his work with condensations of carbonyls and sigmatropic rearrangements. He was born in Cologne as the son of a jurist and studied chemistry at the university of Bonn under August Kekulé, where he became a member of K.St.V. Arminia. He served in the army as a nurse in 1870-1871 and continued his studies at Göttingen University until he returned to the University of Bonn in 1872. He started his academic career at the same university in 1874. During his career he worked with other notable chemists, including the Noble Laureates Adolf von Baeyer and Emil Fischer. He died in 1930 in Godesberg am Rhein. In addition to the Claisen (1887) and Claisen-Schmidt (1881) condensations, the Claisen rearrangement (1912) and the Claisen isatin synthesis (1879), his name is associated with the Claisen flask and Claisen's rule which relates acidity to enolisation. http://www.chem.qmul.ac.uk/rschg/biog.html

27. Reactions III.Preparation of alcohols From Alkenes (review) 1. Hydration (section 8.4) a. H 2 O + HX (Markovnikov) b. Oxymercuration (Markovnikov) c. Hydroboration & oxidation (anti-Markovnikov)

28. p. 509 Synthesis of alcohols : review

29. IV. Reduction and Oxidation reactions oxidation statesoxidation states Reactions

30. Fig. 13-2, p. 508

31. [elim] [sub]

32. Fig. 13-2, p. 508 [red]

33. Fig. 13-2, p. 508 [ox]

34. V. Reduction and Oxidation reactions oxidation states A. Alcohols From Carbonyl Compounds (reduction) 1. Hydride Reducing Agents 2. Grignard Reagents i. TMS protection Reactions

35. p. 557

36. Fig. 1, p. 557

37. V. Reduction and Oxidation reactions oxidation states A. Alcohols From Carbonyl Compounds (reduction) 1. Hydride Reducing Agents 2. Grignard Reagents B.Alcohols To Carbonyl Compounds (oxidation) 1. CrO 3, H 2 SO 4 2. K 2 Cr 2 O 7 3. PCC 4. Dess – Martin Periodinane Reactions

38. A better way to oxidize alcohol? Cr(VI) reagents: 3–10 mg acutely poisonous for a 150-lb adult. An investigation into an illegal release of Cr(VI) into drinking water was the basis of the film Erin Brockovich.

39. Chemical Reaction 2 K 2 Cr 2 O 7 + 3 CH 3 CH 2 OH + 8 H 2 SO 4 2 Cr 2 (SO 4 ) 3 + 2 K 2 SO 4 + 3 CH 3 COOH + 11 H 2 O AgNO 3

40. Fig. 13-9, p. 536 Spectroscopy of alcohols : Infrared

41. Fig. 13-10, p. 536 Spectroscopy of alcohols : Infrared

42. Fig. 13-11, p. 537 Spectroscopy of alcohols : NMR

43. p. 552 C 5 H 10 O

44. Fig. 13-12, p. 538 Spectroscopy of alcohols : Mass Spec