1. Chapter 15 Organic Chemistry

2. “Organic chemistry …is enough to drive one mad. It gives me the impression of a primeval forest, full of the most remarkable things, a monstrous and boundless thicket, with no way of escape, into which one may well dread to enter.” -Friedrich Wöhler

3. Which of these are “organic”? CH 3 CH 2 CH 2 OH NaCN CH 3 COOH CH 3 (CH 2 ) 16 COOH HC  CH CaCO 3 CH 3 CH=CH 2 What is special about carbon?

4. Carbon 1. Electron configuration, electonegativity, and covalent bonding 2. Bond properties, catenation, and molecular shape 3. Molecular stability

7. Hydrocarbons “Aliphatic” Alkanes Alkenes Alkynes “Aromatic” C H H HHC H H C H C H H H CC HH

9. Single, double, and triple bonds CHH H H CH H CH H CHCH CH 4 C2H4C2H4 C2H2C2H2

10. Alkanes, C n H 2n+2 “Saturated” C 9 H 20

11. Single Bonds - sp 3 (tetrahedral) 109.5°

12. Staggered Conformations

13. Single bonds - unrestricted rotation

14. Structures & Rotation Ethane C 2 H 6 CH 3 Staggered Eclipsed

15. Conformations Different spatial arrangements generated by rotation around a single bond

16. Constitutional (structural) isomers

18. Naming 1.Longest C-C chain:root name 2.Suffix:compound type 3.Prefix for rings: “cyclo” 4.Branches:root + “yl” alphabeticalnumbered

19. Alkane examples © Mc-Graw-Hill Companies, Inc. All rights reserved.

21. Physical Properties Straight:lower melting points, higher boiling points Branched:higher melting points, lower boiling points

23. Ring strain - cyclopropane

24. Conformations of cyclohexane

26. Enantiomers

30. Alkenes, C n H 2n - sp 2 “Unsaturated”

31. Geometric Isomers

32. Light energy temporarily excites  bond electrons Bond breaks - allows rotation

34. Alkynes, C n H 2n-2 - sp “Unsaturated”

35. Aromatic - Benzene derivatives Delocalized (conjugated)  electron cloud

38. Free-Radical Substitution Reactions Alkanes:

39. Functional Groups - Reactive Sites

41. Important Reactions 1 - Substitution C bonded to same number of atoms | R— C — X | :Y:Y R— C — Y | :X:X

42. Important Reactions 2 - Addition Two  bonds from one  bond and one  bond R— C — C — RX—Y X Y | | R— C — C — R | |

43. Important Reactions 3 - Elimination Elimination of small, stable molecule + entropy R— C — C — RX—Y X Y | | R— C — C — R | |

44. Oxidation-reduction Oxidation: – More bonds to O – Less bonds to H Reduction: – Less bonds to O – More bonds to H O R— C H | R— C — OH | O R— C OH | R— C —H |

45. Functional Groups with Single Bonds Alcohols & Ethers HaloalkanesAmines R—O —H  R—X: X = halogen  R— N — |  R—O —R 

47. Alcohol Reactions Elimination – Elimination of H 2 O in acid Dehydration to C=C – Elimination of 2 H w/ strong ox.agent Oxidation to C=O Substitution – Single bonded products – “Reactive” C bonded to electronegative atom

48. Haloalkane Reactions Elimination of HX in very strong base C=C product Substitution in base – Single bonded products —OH, —OR, —CN, —SH, —NH 2, … – “Reactive” C bonded to electronegative atom

51. Amine Reactions Substitution – Single bonded products – Lone pair on N attacks  + on another molecule | 2R— C — NH 2 | R’—C H 2 — Y  | R— C — NHR’ | | + R— C — NH 3 Cl |

52. Functional Groups with Double Bonds AlkenesAldehydesKetones Carboxylic Acids     e - rich R— C — C — R O R— C H O R— C OH  e - rich

53. Alkenes Addition reactions R— C — C — RH3O+H3O+ OH H | | R— C — C — R | | R— C — C — RHX X H | | R— C — C — R | |

55. Aromatic - Substitution Reactions Delocalized  electrons stabilize ring

56. Charge Distribution & Reactivity Can undergo substitution or oxidation-reduction

58. Oxidation of aldehydes to acids

59. Substitution Z—Y O—Z | R— C — OH | Y O R— C OH O R— C Y Z—OH 1. Addition 2. Elimination

61. Substitution dehydration

63. Substitution of —OH by N in amines

65. Functional Groups with Triple Bonds AlkynesNitriles  e - rich R— C — C — R R— C — N: e - rich Reactions:addition Formation increases C chain by 1 Reactions:subsitution/hydrolysis, reduction, …

68. Types of polymers Addition Polymerization: monomers “add together” to form the polymer, with no other products. (Teflon) Condensation Polymerization: A small molecule, such as water, is formed for each extension of the polymer chain. (Nylon)

71. Biological Polymers Carbohydrates, saccharides, polysaccharides Amino acids, peptides, proteins Fatty acids, lipids, fats, oils, waxes, steroids, phospholipids Nucleotides, nucleic acids

72. Saccharides/Carbohydrates

74. C C C C C CH 2 OH OH HO OH OH H H H H C C C C C CH 2 OH O OH HO OH H H H H H C C C C C CH 2 OH O OH HO OH H H H H H O H H H H H CH 2 OH OH O H H H H H CH 2 OH OH D-glucose  -D-glucopyranose  -D-glucopyranose

75. O H H H H H OH CH 2 OH OH O H H H H H CH 2 OH O O H H H H H OH CH 2 OH OH O H H H H H CH 2 OH O  -1-4-glycosidic bond  -1-4-glycosidic bond Glycosidic linkages (dehydration)

76. Disaccharides

77. Polysaccharides AmyloseAmylopectinStarchGlycogenCellulose

80. Amino acids H H | O N—C—C H | OH R  Amine  Acid  -carbon

82. Amide Linkage (“peptide bond”) H O H H H | || | | O N—C— C — N — C — C +H 2 O H | | OH R  R’ peptide bond (dehydration)

84. Levels of Structure 1

85. Levels of Structure 2

87. Levels of Structure 3