1. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 1 of 83 Philip Dutton University of Windsor, Canada Prentice-Hall © 2007 CHEMISTRY Ninth Edition GENERAL Principles and Modern Applications Petrucci Harwood Herring Madura Chapter 26: Organic Chemistry

2. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 2 of 83 Contents 26-1Organic Compounds and Structures: An Overview 26-2Alkanes 26-3Alkenes and Alkynes 26-4Aromatic Hydrocarbons 26-5Alcohols, Phenols, and Ethers 26-6Aldehydes and Ketones 26-7Carboxylic Acids and Their Derivatives 26-8Amines 26-9Heterocyclic Compounds

3. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 3 of 83 Contents 26-10Nomenclature of Stereoisomers in Organic Compounds 26-11An Introduction to Substitution Reactions at sp 3 Hybridized Carbon Atoms 26-12Synthesis of Organic Compounds 26-13Polymerization Reactions  Focus On Green Chemistry and Ionic Liquids

4. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 4 of 83 26-1 Organic Compounds and Structures: An Overview  Hydrocarbons – the simplest organic compounds.  Simplest hydrocarbon is methane.

5. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 5 of 83 Ethane

6. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 6 of 83 Propane

7. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 7 of 83 Skeletal Isomerism

8. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 8 of 83 Simplified Drawings of Organic Structures

9. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 9 of 83 Nomenclature  Select the longest continuous carbon chain.  This determines the base name.  Consider each branch and name similarly except change the name from –ane to –yl.  Number the C atoms so that substituents have the lowest possible number.

10. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 10 of 83 Nomenclature  Name each substituent according to its identity and the number of the C atom to which it is attached.  Use di, tri, tetra as appropriate.  Separate numbers from one another by commas.  List substituents alphabetically by name.

11. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 11 of 83 Table 26.1. Some Common Alkyl Groups

12. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 12 of 83 Positional Isomerism

13. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 13 of 83

14. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 14 of 83

15. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 15 of 83

16. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 16 of 83 26-2 Alkanes  Saturated hydrocarbons:  Only single bonds.  Normal formula is C n H 2n+2  Branching of chains affects properties.

17. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 17 of 83 Conformations

18. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 18 of 83 Ring Structures C n H 2n

19. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 19 of 83 Ring Strain

20. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 20 of 83 Cyclohexane Conformations

21. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 21 of 83 Preparation of Alkanes CH 2 =CH 2 + H 2 → CH 3 -CH 3 cat Δ 2 CH 3 CH 2 Br + 2 Na → CH 3 CH 2 CH 2 CH 3 + 2 NaBr pressure Δ cat = Pt or Pd

22. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 22 of 83 Reactions of Alkanes Initiation:Cl-Cl → 2 Cl· Propagation:H 3 C-H + Cl· → H 3 C· + HCl H 3 C· + Cl 2 → H 3 C-Cl + Cl· Termination: H 3 C· + Cl· → H 3 C-Cl Cl· + Cl· → Cl-Cl H 3 C· + H 3 C· → H 3 C-CH 3 Δ or h

23. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 23 of 83 Combustion Reactions C 8 H 18 (l) + O 2 (g) → 8 CO 2 (g) + 9 H 2 O(l) 25 2 ΔH° = -5.48  10 3 J

24. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 24 of 83 Table 26.4 Principle Petroleum Fractions

25. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 25 of 83 Octane Number

26. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 26 of 83 26-3 Alkenes and Alkynes

27. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 27 of 83 Geometric Isomerism

28. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 28 of 83 Elimination Reaction

29. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 29 of 83 Addition Reactions Markovnikov rule

30. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 30 of 83 Hydration Reaction Addition is favored in dilute acid and elimination is favored in strong.

31. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 31 of 83 Reduction of C=C

32. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 32 of 83 26-4 Aromatic Hydrocarbons

33. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 33 of 83 Characteristics of Aromatic Hydrocarbons  Planar (flat) cyclic molecules.  Conjugated п systems (4n + 2)

34. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 34 of 83 Naming Aromatic Hydrocarbons

35. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 35 of 83 Aromatic Substitution Reactions

36. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 36 of 83 Aromatic Substitution Reactions

37. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 37 of 83 26-5 Alcohols, Phenols, and Ethers

38. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 38 of 83 Diols, Triols and Polyols

39. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 39 of 83 Preparation and Use of Alcohols  Methanol.  21 st amongst industrial chemicals.  Ethanol.  fermentation or by hydration of ethylene.  Ehylene glycol.  High boiling point, soluble in water.  Glycerin.

40. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 40 of 83 Ethers CH 3 CH 2 OH + HOCH 2 CH 3  CH 3 CH 2 OCH 2 CH 3 + H 2 O conc H 2 SO 4 140 C

41. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 41 of 83 The Carbonyl Group

42. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 42 of 83 Aldehydes and Ketones

43. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 43 of 83 Preparation and Use  Oxidation of alcohols.  Extract from natural sources

44. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 44 of 83 Addition Reactions of the Carbonyl Group

45. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 45 of 83 26-7 Carboxylic Acids and Their Derivatives Oh My Such Good Apple Pie, Sweet As Sugar oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic

46. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 46 of 83 Aromatic Acids

47. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 47 of 83 Acetyl Group

48. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 48 of 83 Esters General Chemistry: Chapter 25 CH 3 CO 2 CH 2 (CH 2 ) 6 CH 3

49. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 49 of 83 Amides

50. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 50 of 83 Resonance in Amides

51. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 51 of 83 Reduction Reactions

52. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 52 of 83 Amines

53. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 53 of 83 Preparation of Amines 2 NH 3 + CH 3 Br → CH 3 NH 3 + Br - + NH 3 → CH 3 NH 2 + NH 4 Br

54. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 54 of 83 Basicity of Amines

55. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 55 of 83 Ammonium Salts

56. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 56 of 83 26-9 Heterocyclic Compounds

57. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 57 of 83 26-10 Nomenclature of Stereoisomers in Organic Compounds

58. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 58 of 83 Chirality

59. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 59 of 83 The R,S System of Nomenclature Substituent of higher atomic number takes precedence over one of lower atomic number:

60. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 60 of 83 The R,S System of Nomenclature

61. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 61 of 83 The R,S System of Nomenclature If two substituents attached to the stereocenter have the same priority, proceed along the chains to the first point of difference:

62. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 62 of 83 The R,S System of Nomenclature Double and triple bonds count as if they were single and the atoms are duplicated or triplicated at the other end of the double or triple bond:

63. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 63 of 83 The E,Z System of Nomenclature zed iz on ze zame zide

64. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 64 of 83 The E,Z System of Nomenclature

65. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 65 of 83 26-11 An Introduction to Substitution Reactions at sp 3 Hybridized Carbon Charged nucleophiles Neutral nucleophiles

66. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 66 of 83 S N 2 Mechanism Rate = k[OH - ][CH 3 Cl] General Chemistry: Chapter 26Prentice-Hall © 2007

67. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 67 of 83 Inversion of Configuration

68. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 68 of 83 S N 1 Mechanism

69. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 69 of 83 S N 1 Mechanism Rate = k [(CH 3 ) 3 CCl] slow fast

70. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 70 of 83 Racemic Products From S N 1 Reactions

71. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 71 of 83 26-12 Synthesis of Organic Compounds

72. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 72 of 83 26-13 Polymerization Reactions

73. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 73 of 83 Polymerization

74. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 74 of 83 Table 26.5 Some Polymers Produced by Chain-Reaction Polymerization

75. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 75 of 83 Condensation Polymerization

76. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 76 of 83 Table 26.6 Some Polymers Produced by Step Reaction Polymerization

77. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 77 of 83 Stereospecific Polymers

78. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 78 of 83 Focus On Green Chemistry and Ionic Liquids Diels Alder Reaction CO 2 CH 3 EMIC (2S)-methylbicyclo[2.2.a]hept-5-ene-2-carboxylate

79. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 79 of 83 Effect of Ionic Liquids on DA Reaction

80. Prentice-Hall © 2007 General Chemistry: Chapter 26 Slide 80 of 83 End of Chapter Questions  Take your knowledge and skills with you.  Any area of expertise requires a base on which to build. Your first year courses are that base of knowledge.  Your first year problem solving skills are a base on which to build more advanced skills.