1. Chapter 10 Structure and Synthesis of Alcohols Jo Blackburn Richland College, Dallas, TX Dallas County Community College District  2003,  Prentice Hall Organic Chemistry, 5 th Edition L. G. Wade, Jr.

2. Chapter 102 Structure of Alcohols Hydroxyl (OH) functional group Oxygen is sp 3 hybridized. =>

3. Chapter 103 Classification Primary: carbon with –OH is bonded to one other carbon. Secondary: carbon with –OH is bonded to two other carbons. Tertiary: carbon with –OH is bonded to three other carbons. Aromatic (phenol): -OH is bonded to a benzene ring. =>

4. Chapter 104 Classify these: =>

5. Chapter 105 IUPAC Nomenclature Find the longest carbon chain containing the carbon with the -OH group. Drop the -e from the alkane name, add - ol. Number the chain, starting from the end closest to the -OH group. Number and name all substituents. =>

6. Chapter 106 Name these: 2-methyl-1-propanol 2-methyl-2-propanol 2-butanol 3-bromo-3-methylcyclohexanol =>

7. Chapter 107 Unsaturated Alcohols Hydroxyl group takes precedence. Assign that carbon the lowest number. Use alkene or alkyne name. 4-penten-2-ol (old) pent-4-ene-2-ol (1997 revision of IUPAC rules) =>

8. Chapter 108 Naming Priority Acids Esters Aldehydes Ketones Alcohols Amines Alkenes Alkynes Alkanes Ethers Halides =>

9. Chapter 109 Hydroxy Substituent When -OH is part of a higher priority class of compound, it is named as hydroxy. Example: 4-hydroxybutanoic acid also known as GHB =>

10. Chapter 1010 Common Names Alcohol can be named as alkyl alcohol. Useful only for small alkyl groups. Examples: isobutyl alcohol sec-butyl alcohol =>

11. Chapter 1011 Naming Diols Two numbers are needed to locate the two -OH groups. Use -diol as suffix instead of -ol. 1,6-hexanediol =>

12. Chapter 1012 Glycols 1, 2 diols (vicinal diols) are called glycols. Common names for glycols use the name of the alkene from which they were made. 1,2-ethanediol ethylene glycol 1,2-propanediol propylene glycol =>

13. Chapter 1013 Naming Phenols -OH group is assumed to be on carbon 1. For common names of disubstituted phenols, use ortho- for 1,2; meta- for 1,3; and para- for 1,4. Methyl phenols are cresols. 3-chlorophenol meta-chlorophenol 4-methylphenol para-cresol =>

14. Chapter 1014 Physical Properties Unusually high boiling points due to hydrogen bonding between molecules. Small alcohols are miscible in water, but solubility decreases as the size of the alkyl group increases. =>

15. Chapter 1015 Boiling Points =>

16. Chapter 1016 Solubility in Water Solubility decreases as the size of the alkyl group increases. =>

17. Chapter 1017 Methanol “Wood alcohol” Industrial production from synthesis gas Common industrial solvent Fuel at Indianapolis 500  Fire can be extinguished with water  High octane rating  Low emissions  But, lower energy content  Invisible flame =>

18. Chapter 1018 Ethanol Fermentation of sugar and starches in grains 12-15% alcohol, then yeast cells die. Distillation produces “hard” liquors Azeotrope: 95% ethanol, constant boiling Denatured alcohol used as solvent Gasahol: 10% ethanol in gasoline Toxic dose: 200 mL ethanol, 100 mL methanol =>

19. Chapter 1019 2-Propanol “Rubbing alcohol” Catalytic hydration of propene =>

20. Chapter 1020 Acidity of Alcohols pK a range: 15.5-18.0 (water: 15.7) Acidity decreases as alkyl group increases. Halogens increase the acidity. Phenol is 100 million times more acidic than cyclohexanol! =>

21. Chapter 1021 Table of K a Values =>

22. Chapter 1022 Formation of Alkoxide Ions React methanol and ethanol with sodium metal (redox reaction). React less acidic alcohols with more reactive potassium. =>

23. Chapter 1023 Formation of Phenoxide Ion Phenol reacts with hydroxide ions to form phenoxide ions - no redox is necessary. OH + OH O + HOH pK a = 10 pK a = 15.7 =>

24. Chapter 1024 Synthesis (Review) Nucleophilic substitution of OH - on alkyl halide Hydration of alkenes  water in acid solution (not very effective)  oxymercuration - demercuration  hydroboration - oxidation =>

25. Chapter 1025 Glycols (Review) Syn hydroxylation of alkenes  osmium tetroxide, hydrogen peroxide  cold, dilute, basic potassium permanganate Anti hydroxylation of alkenes  peroxyacids, hydrolysis =>

26. Chapter 1026 Organometallic Reagents Carbon is bonded to a metal (Mg or Li). Carbon is nucleophilic (partially negative). It will attack a partially positive carbon.  C - X  C = O A new carbon-carbon bond forms. =>

27. Chapter 1027 Grignard Reagents Formula R-Mg-X (reacts like R: - + MgX) Stabilized by anhydrous ether Iodides most reactive May be formed from any halide  primary  secondary  tertiary  vinyl  aryl =>

28. Chapter 1028 Some Grignard Reagents =>

29. Chapter 1029 Organolithium Reagents Formula R-Li (reacts like R: - + Li) Can be produced from alkyl, vinyl, or aryl halides, just like Grignard reagents. Ether not necessary, wide variety of solvents can be used. =>

30. Chapter 1030 Reaction with Carbonyl R: - attacks the partially positive carbon in the carbonyl. The intermediate is an alkoxide ion. Addition of water or dilute acid protonates the alkoxide to produce an alcohol. =>

31. Chapter 1031 Synthesis of 1° Alcohols Grignard + formaldehyde yields a primary alcohol with one additional carbon. =>

32. Chapter 1032 Synthesis of 2º Alcohols Grignard + aldehyde yields a secondary alcohol. =>

33. Chapter 1033 Synthesis of 3º Alcohols Grignard + ketone yields a tertiary alcohol. =>

34. Chapter 1034 How would you synthesize… =>

35. Chapter 1035 Grignard Reactions with Acid Chlorides and Esters Use two moles of Grignard reagent. The product is a tertiary alcohol with two identical alkyl groups. Reaction with one mole of Grignard reagent produces a ketone intermediate, which reacts with the second mole of Grignard reagent. =>

36. Chapter 1036 Grignard + Acid Chloride (1) Ketone intermediate => Grignard attacks the carbonyl. Chloride ion leaves.

37. Chapter 1037 Grignard and Ester (1) Grignard attacks the carbonyl. Alkoxide ion leaves! ? ! Ketone intermediate =>

38. Chapter 1038 Second step of reaction Second mole of Grignard reacts with the ketone intermediate to form an alkoxide ion. Alkoxide ion is protonated with dilute acid. =>

39. Chapter 1039 How would you synthesize... Using an acid chloride or ester. =>

40. Chapter 1040 Grignard Reagent + Ethylene Oxide Epoxides are unusually reactive ethers. Product is a 1º alcohol with 2 additional carbons. =>

41. Chapter 1041 Limitations of Grignard No water or other acidic protons like O-H, N-H, S-H, or -C—C-H. Grignard reagent is destroyed, becomes an alkane. No other electrophilic multiple bonds, like C=N, C—N, S=O, or N=O. =>

42. Chapter 1042 Reduction of Carbonyl Reduction of aldehyde yields 1º alcohol. Reduction of ketone yields 2º alcohol. Reagents:  Sodium borohydride, NaBH 4  Lithium aluminum hydride, LiAlH 4  Raney nickel =>

43. Chapter 1043 Sodium Borohydride Hydride ion, H -, attacks the carbonyl carbon, forming an alkoxide ion. Then the alkoxide ion is protonated by dilute acid. Only reacts with carbonyl of aldehyde or ketone, not with carbonyls of esters or carboxylic acids. =>

44. Chapter 1044 Lithium Aluminum Hydride Stronger reducing agent than sodium borohydride, but dangerous to work with. Converts esters and acids to 1º alcohols. =>

45. Chapter 1045 Comparison of Reducing Agents LiAlH 4 is stronger. LiAlH 4 reduces more stable compounds which are resistant to reduction. =>

46. Chapter 1046 Catalytic Hydrogenation Add H 2 with Raney nickel catalyst. Also reduces any C=C bonds. =>

47. Chapter 1047 Thiols (Mercaptans) Sulfur analogues of alcohols, -SH. Named by adding -thiol to alkane name. The -SH group is called mercapto. Complex with heavy metals: Hg, As, Au. More acidic than alcohols, react with NaOH to form thiolate ion. Stinks! =>

48. Chapter 1048 Thiol Synthesis Use a large excess of sodium hydrosulfide with unhindered alkyl halide to prevent dialkylation to R-S-R. =>

49. Chapter 1049 Thiol Oxidation Easily oxidized to disulfides, an important feature of protein structure. Vigorous oxidation with KMnO 4, HNO 3, or NaOCl, produces sulfonic acids. =>

50. Chapter 1050 End of Chapter 10