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Chapter 13 Alcohols, Phenols, Ethers; Thiols and Sulfides

Chapter 13 Alcohols, Phenols, Ethers; Thiols and Sulfides. Alcohol introduction: Hydrogen Bonding. Fig. 13-1, p. 505. Alcohol introduction: Types of Alcohols. Alcohol introduction: reaction of sp3 oxygen with strong acids. Table 13-1, p. 506. Fig. 13-2, p. 508. [elim]. [sub]. [sub].

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Chapter 13 Alcohols, Phenols, Ethers; Thiols and Sulfides

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

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

  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] [sub] Fig. 13-2, p. 508

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

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

  10. Reactions • Substitution Reactions of Alcohols (review)A. Conversion to alkyl halides 1. 1° & 3° with strong acid 2. 1° & 2° with SOCl2, pyridine 3. 1° & 2° with PBr3.

  11. Substitution Reactions of alcohols : review p. 516

  12. Reactions • Substitution Reactions of Alcohols (review)A. Conversion to alkyl halides 1. 1° & 3° with strong acid 2. 1° & 2° with SOCl2, pyridine 3. 1° & 2° with PBr3 4. 1° & 2° with TsCl

  13. Reactions • Substitution Reactions of Alcohols (review)A. Conversion to alkyl halides 1. 1° & 3° with strong acid 2. 1° & 2° with SOCl2, pyridine 3. 1° & 2° with PBr3 4. 1° & 2° with TsClProblem: Enantiomeric products from same starting material.

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

  15. Table 13-1, p. 506

  16. Reactions • Substitution Reactions of Alcohols (cont.)B. Formation of alkoxide ions • pKa’s of alcohols 1. Strong Bases (NaH, NaNH2) 2. Metals (Na0)

  17. Reactions • 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

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

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

  20. Epoxy Resins

  21. Epoxy Resins Two substancesSubstance #1. diepoxy prepolymer.

  22. Epoxy Resins Two substancesSubstance #1. diepoxy prepolymer.

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

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

  25. Reactions • Reactions of ethers.A. UnstrainedB. 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)

  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 • Preparation of alcohols From Alkenes (review) 1. Hydration (section 8.4) a. H2O + HX (Markovnikov) b. Oxymercuration (Markovnikov) c. Hydroboration & oxidation (anti-Markovnikov)

  28. Synthesis of alcohols : review p. 509

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

  30. Fig. 13-2, p. 508

  31. [elim] [sub] [sub] Fig. 13-2, p. 508

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

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

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

  35. p. 557

  36. Fig. 1, p. 557

  37. Reactions V. Reduction and Oxidation reactions • oxidation states A. Alcohols From Carbonyl Compounds (reduction) 1. Hydride Reducing Agents 2. Grignard Reagents • Alcohols To Carbonyl Compounds (oxidation) 1. CrO3, H2SO4 2. K2Cr2O7 3. PCC4. Dess – Martin Periodinane

  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 K2Cr2O7 + 3 CH3CH2OH + 8 H2SO4 2 Cr2 (SO4)3 + 2 K2SO4 + 3 CH3COOH + 11 H2O AgNO3

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

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

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

  43. C5H10O p. 552

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

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