1. 10-1 Alcohols & Thiols & Ethers Sources Structure, Nomenclature, Properties Acidity and Basicity Rx with active metals Conversion to R-X, inorganic acid halides Rxs with HX S N 1/S N 2, sulfonates Dehydration of alcohols Oxidation of 1 o and 2 o alcohols Oxidation of glycols [Pinacol & Thiols/Sulfur chemistry - skip] 6, 31, ss34 Chapter 10 Chapter 11

2. 10-2 Chapter 10 reactions acid base active metal substitution oxidation sources nomenclature (alcohol & ethers) properties

3. 10-3 Preparation of alcohols - (review)

4. 10-4 Chapter 10 sources nomenclature (alcohol & ethers) properties reactions acid base active metal substitution oxidation

5. 10-5 Nomenclature alcohols & ethers IUPAC names – alcohol sp 3 C-OH -longest chain that contains the -OH = root -OH gp lowest number - suffix -e to -ol ether R-O-R’ sp 3 C, sp 2 C, spC in R & R’ bonded to O -always subsituent - #-prefix, alkoxy (special ethers #,#-epoxy) 1-ethoxy-2-butanol

6. 10-6 Epoxides - 11 - special ethers Nomenclature - #,#-epoxy (substituent) or oxirane #,#-epoxy-#-pentyn-#-ol (4S)-4,5-epoxy-2-pentyn-1-ol ether acetylene alcohol

7. 10-7 Nomenclature-Alcohols IUPAC names Longest chain that contains the -OH = root Give -OH group lowest number Change suffix -e to -ol (S)-2-methyl-1-butanol

8. 10-8 oxygen sp 3 Structure - Alcohols Alcohol functional group: -OH group bonded to an sp 3 hybridized carbon bond angles ~ 109.5° CO H H H 3 C H

9. 10-9 Physical Properties Hydrogen bonding: H bonded to an electronegative atom (F, O, or N) etc. R O H O H R O H R O H R Hydrogen bond weak (~ 5 kcal/mol)

10. 10-10 Physical Properties ethanol & dimethyl ether - constitutional isomers but weak hydrogen bonds have dramatic effects: hydrogen bonds no hydrogen bonds

11. 10-11 Quiz Name:___________________________ seat:_____ Write a reaction equation that represents one of the source of alcohols.

12. 10-12 Reactions alcohols: acid base indirect substitution indirect  -elimination active metals oxidation ethers: base indirect substitution indirect  -elimination epoxides: substitution, indirect & direct

13. 10-13 Acidity of Alcohols weak acids conjugate bases strong

14. 10-14 Acidity of Alcohols RSH 8.5

15. 10-15 Acidity of Alcohols Acidity  on: stabilization and solvation electron donation destabilize alkoxides decreases solvation

16. 10-16 Alcohols + Li, Na, K (active metals) form metal alkoxides metal alkoxide sodium methoxide alcohols rx with metals

17. 10-17 rx with metals sodium cyclohexoxide

18. 10-18 basicity of alcohols/ethers weak Lewis base (water-like) R = H or alkyl oxonium ion

19. 10-19 3° alcohols (ethers) react very rapidly with HCl, HBr, HI. Alcohols/Ethers indirect Substitution ( with HX) 1°alcohols/ethers are unreactive under these conditions R = H or alkyl

20. 10-20 2° alcohols + HBr (or HI ) racemization, rearrangement, olefins indirect Substitution ( with HX)

21. 10-21 2 o or 3 o ROH/ROR’ with HX - S N 1 -H + +X - [-HOR] good leaving group racemization, rearrangement, olefins R = H or alkyl

22. 10-22 1 o ROH/ROR’ with HI or HBr - S N 2 X (-) displace R’ = H or alkyl

23. 10-23 indirect Substitution (with SOCl 2 )

24. 10-24 indirect Substitution (with PBr 3 ) 2 nd ROH to RBr 3 rd ROH to RBr

25. 10-25 indirect Substitution R= H, alkyl R’= H, alkyl; X= Br, I

26. 10-26 alcohols - alkyl sulfonates, good Lgp

27. 10-27 alkyl sulfonates (sulfonate ester) S S S R good leaving group for Sn2 rx DMF

28. 10-28 rx: alkyl sulfonates prep:

29. 10-29 rx: alkyl sulfonates prep:

30. 10-30 1° alcohols (ethers) with H 2 SO 4 or H 3 PO 4 dehydration of ROH/[-HOR’] of ROR’ 2° alcohols (ethers) 3° alcohols (ethers) R = H or alkyl

31. 10-31 Dehydration of ROH (-OR of ethers) Mechanism - same forward or reverse. alkene addition and  -elimination compete

32. 10-32 Pinacol Rearrangement This section out [rearrangement under dehydration conditions]

33. 10-33 Chapter 10 sources nomenclature properties reactions acid base active metal substitution oxidation

34. 10-34 Oxidation

35. 10-35 Oxidation: 1° ROH Pyridinium chlorochromate (PCC): pyridine + CrO 3 [Cr(VI)] + HCl PCC converts 1° alcohols to aldehydes and 2 o alcohols to ketones

36. 10-36 Oxidation aldehyde acid ketone NR (no reaction)

37. 10-37  -elimination of H and chromate +

38. 10-38 Oxidation: 1° ROH hydrate

39. 10-39 Oxidation 1 o and 2 o ROH K 2 Cr 2 O 7 and many other reagents

40. 10-40 Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O) acyclic or cis-1,2 cyclic diols

41. 10-41 Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O) 11

42. 10-42 OsO 4 / HIO 4 equivalent to O 3 /red. source of diols

43. 10-43 mechanism Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O)

44. 10-44 Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O) 10

45. 10-45 Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O) 10

46. 10-46 How does one make butanal from 1-bromobutane?

47. 10-47 What else can be made using the chemistry of chapters 3, 6, 7, 8, 9, 10, 11 & “15”?

48. 10-48 Chapter 15 future chapter chemistry

49. 10-49 Chapter 10 sources nomenclature properties reactions acid base active metal substitution oxidation Chapter 11/15