1. 13-1 Chemistry 121, Summer 2013, LA Tech Introduction to Organic Chemistry and Biochemistry Instructor Dr. Upali Siriwardane (Ph.D. Ohio State) E-mail: upali@chem.latech.edu Office: 311 Carson Taylor Hall ; Phone: 318-257-4941; Office Hours: MTWTF 8:00 am - 10:00 am; by e-mail June 14, 2013 Test 1 (Chapters 12-13) July 8, 2013 Test 2 (Chapters 14,15 & 16) July 19, 2013 Test 3(Chapters 17, 18 & 19) August 5, 2013 Test 4 (Chapters 20, 21 & 22) August 8, 2013 Comprehensive Make Up Exam: Chemistry 121(01) Summer 2013

2. 13-2 Chemistry 121, Summer 2013, LA Tech Chapter 13: Unsaturated Hydrocarbons Sections 4.1-4.5

3. 13-3 Chemistry 121, Summer 2013, LA Tech Chapter 13: Unsaturated Hydrocarbons 13.2 Characteristics of Alkenes and Cycloalkenes 13.3 Names for Alkenes and Cycloalkenes 13.4 Line-Angle Formulas for Alkenes 13.5 Isomerism in Alkenes 13.6 Naturally Occurring Alkenes 13.7 Physical Properties of Alkenes 13.8 Chemical Reactions of Alkenes 13.9 Polymerization of Alkenes: Addition Polymers 13.10 Alkynes 13.11 Aromatic Hydrocarbons 13.12 Names for Aromatic Hydrocarbons 13.13 Aromatic Hydrocarbons: Physical Properties and Sources 13.14 Chemical Reactions of Aromatic Hydrocarbons 13.15 Fused-Ring Aromatic Compounds Chemical Connections: Ethene: A Plant Hormone and High-Volume Industrial Chemical; Cis-Trans Isomerism and Vision; Carotenoids: A Source of Color; Fused-Ring Aromatic Hydrocarbons and Cancer

4. 13-4 Chemistry 121, Summer 2013, LA Tech IUPAC Nomenclature of Alkyne  CAG 13.2

5. 13-5 Chemistry 121, Summer 2013, LA Tech Copyright © Houghton Mifflin Company. All rights reserved.13 | 5 → Fig. 13.18 2-chlorotoluene molecule Unsaturated Hydrocarbons cont’d

6. 13-6 Chemistry 121, Summer 2013, LA Tech Unsaturated hydrocabons Hydrocarbons with carbon-carbon double bonds and triple bonds double bonds: alkenes triple bonds: alkynes three alternating double bond in 6 carbon ring: aromatics

7. 13-7 Chemistry 121, Summer 2013, LA Tech Unsaturated Hydrocarbons in Use Acetylene: Welding Beta-carotene is in carrots sex pheromones in insect control involves luring insect into a trap. involves luring insect into a trap. Ethene is the hormone that causes tomatoes to ripen.

8. 13-8 Chemistry 121, Summer 2013, LA Tech etheneethyne benzene C 2 H 4 C 2 H 2 C 6 H 6 C n H 2n C n H 2n  2 C n H n unsaturatedunsaturated Aromatic alkenealkyne Arene Chapters 13 Chapters 13 Chapter 13 Unsaturated Hydrocarbons: Unsaturated Hydrocarbons: Alkenes Alkynes Arenes

9. 13-9 Chemistry 121, Summer 2013, LA Tech Units of Unsaturation Cycloalkane ring Cycloalkane ring C n H 2n (one unit of unsat.) Unsaturated hydrocarbons: bond C n H 2n (one unit of unsat.) bond C n H 2n  2 (two units of unsat.) Compounds that have have fewer hydrogens than saturated hydrocarbons (C n H 2n+2 ). Two hydrogen are considered as unit of unstauration

10. 13-10 Chemistry 121, Summer 2013, LA Tech AlkeneAlkene: contains a carbon-carbon double bond and has the general formula C n H 2n The two carbon atoms of a double bond and the four atoms bonded to them lie in a plane, with bond angles of approximately 120° Structure of Alkenes

11. 13-11 Chemistry 121, Summer 2013, LA Tech → Fig. 13.1 In ethene, the atoms are in a flat rather than a tetrahedral arrangement. Bonding in ethene (ethylene)

12. 13-12 Chemistry 121, Summer 2013, LA Tech Planar Structure of Alkenes According to the orbital overlap model, a double bond consists of a  bond formed by overlap of sp 2 hybrid orbitals a  bond formed by overlap of sp 2 hybrid orbitals a  bond formed by overlap of parallel 2p orbital a  bond formed by overlap of parallel 2p orbital Rotating by 90°breaks the pi bond

13. 13-13 Chemistry 121, Summer 2013, LA Tech Structure of Alkynes The functional group of an alkyne is a carbon-carbon triple bond A triple bond consists of one  bond formed by the overlap of sp hybrid orbitals two  bonds formed by the overlap of sets of parallel 2p orbitals

14. 13-14 Chemistry 121, Summer 2013, LA Tech Alkenes Second members of the hydrocarbon family. contain only hydrogen and carbon have single bonds and at least one C=C double bond All members have the general formula of C n H 2n C n H 2n Twice as many hydrogen as carbon Twice as many hydrogen as carbon

15. 13-15 Chemistry 121, Summer 2013, LA Tech Alkenes: Naming and Structures One simple class of compound is the alkene which has only C, H and single bonds. ethene propene 2- butene C 2 H 4 C3H6C3H6 C4H8C4H8 CH 2 CH 3 CH 2 CH 2 CH 3 CH 2 CHCH 3

16. 13-16 Chemistry 121, Summer 2013, LA Tech IUPAC Nomenclature of Alkenes and Alkynes name the longest continuous carbon chain containing the multiple bond(s) (parent chain). If cyclic, ring is the parent. name the longest continuous carbon chain containing the multiple bond(s) (parent chain). If cyclic, ring is the parent. use the infix -en- to show the presence of a carbon-carbon double bond use the infix -en- to show the presence of a carbon-carbon double bond use the infix -yn- to show the presence of a carbon-carbon triple bond use the infix -yn- to show the presence of a carbon-carbon triple bond number the parent chain to give the 1st carbon of the double/triple bond the lower number number the parent chain to give the 1st carbon of the double/triple bond the lower number If both double and triple are present and cannot have the same #, then double bonds take priority. If both double and triple are present and cannot have the same #, then double bonds take priority. follow IUPAC general rules for numbering and naming substituents follow IUPAC general rules for numbering and naming substituents for a cycloalkene, the double bond must be numbered 1,2 for a cycloalkene, the double bond must be numbered 1,2

17. 13-17 Chemistry 121, Summer 2013, LA Tech IUPAC Nomenclature of Alkynes ynuse the infix -yn- to show the presence of a carbon- carbon triple bond number the parent chain to give the 1st carbon of the triple bond the lower number follow IUPAC rules for numbering and naming substituents

18. 13-18 Chemistry 121, Summer 2013, LA Tech Example of IUPAC Nomenclature of Alkenes Cycloalkanes

19. 13-19 Chemistry 121, Summer 2013, LA Tech Nomenclature of Alkenes: Common Names Some alkenes, particularly low-molecular-weight ones, are known almost exclusively by their common names

20. 13-20 Chemistry 121, Summer 2013, LA Tech AlkenesFirst four members of the alkanes Name # of C Condensed formula Ethene2 CH 2 = CH 2 Propene3 CH 3 CH = CH 2 2-Butene4 CH 3 CH=CHCH 3 Called a homologous series “Members differ by number of CH 2 groups”

21. 13-21 Chemistry 121, Summer 2013, LA Tech Physical state summary for unbranched 1 alkynes at room temperature and pressure. Physical State of Alkynes

22. 13-22 Chemistry 121, Summer 2013, LA Tech Cis and trans Geometrical isomers of alkenes two groups are said to be located cis to each other if they lie on the same side of a plane with respect to the double bond. two groups are said to be located cis to each other if they lie on the same side of a plane with respect to the double bond. If they are on opposite sides, their relative position is described as trans.

23. 13-23 Chemistry 121, Summer 2013, LA Tech Fig. 13.2 A comparison of structural isomerism possibilities for four and five-carbon alkane and alkene systems. Isomerism in Alkanes & Alkenes

24. 13-24 Chemistry 121, Summer 2013, LA Tech ← Fig. 13.3 Cis-trans isomers: Different representatives of the cis and trans isomers of 2-butene. Cis-trans isomerism in 2-butene

25. 13-25 Chemistry 121, Summer 2013, LA Tech Unsaturated Aromatic Hydrocarbons  CC 13.2

26. 13-26 Chemistry 121, Summer 2013, LA Tech Geometrical Stereoisomerism Because of restricted rotation about a C-C double bond, groups on adjacent carbons are either cis or trans to each other

27. 13-27 Chemistry 121, Summer 2013, LA Tech Physical Properties Alkenes and alkynes are nonpolar compounds the only attractive forces between their molecules are dispersion forces Their physical properties are similar to those of alkanes of similar carbon skeletons those that are liquid at room temperature are less dense than water (1.0 g/m L) they dissolve in each other and in nonpolar organic solvents they are insoluble in water

28. 13-28 Chemistry 121, Summer 2013, LA Tech Cis-Trans Isomerism trans alkenes are more stable than cis alkenes because of nonbonded interaction strain between alkyl substituents of the same side of the double bond

29. 13-29 Chemistry 121, Summer 2013, LA Tech Summary of Physical State of Unsaturated Hydrocarbons

30. 13-30 Chemistry 121, Summer 2013, LA Tech Geometric isomers There are two possible arrangements. Example 2-butene C=C H CH 3 H3CH3C H C=C CH 3 HH H3CH3C cis Largest groups are on the same side.trans Largest groups are on opposite sides.

31. 13-31 Chemistry 121, Summer 2013, LA Tech Cis-Trans Isomerism in Cycloalkenes the configuration of the double bond in cyclopropene through cycloheptene must be cis; these rings are not large enough to accommodate a trans double bond cyclooctene is the smallest cycloalkene that can accommodate a trans double bond

32. 13-32 Chemistry 121, Summer 2013, LA Tech Cis-Trans Isomerism Dienes, trienes, and polyenes n 2 nfor an alkene with n carbon-carbon double bonds, each of which can show cis-trans isomerism, 2 n cis-trans isomers are possible consider 2,4-heptadiene; it has four cis-trans isomers, two of which are drawn here

33. 13-33 Chemistry 121, Summer 2013, LA Tech Naturally Occurring AlkenesCis-Trans Isomerism vitamin A has five double bonds four of the five can show cis-trans isomerism vitamin A is the all-trans isomer

34. 13-34 Chemistry 121, Summer 2013, LA Tech Naturally Occurring Alkenes: The Terpenes Terpene: a compound whose carbon skeleton can be divided into two or more units identical with the carbon skeleton of isoprene

35. 13-35 Chemistry 121, Summer 2013, LA Tech Terpenes with isoprene units

36. 13-36 Chemistry 121, Summer 2013, LA Tech Terpenes: Polymers of Isoprene myrcene, C 10 H 16, a component of bayberry wax and oils of bay and verbena menthol, from peppermint

37. 13-37 Chemistry 121, Summer 2013, LA Tech Terpenes Vitamin A (retinol) the four isoprene units in vitamin A are shown in red they are linked head to tail, and cross linked at one point (the blue bond) to give the six-membered ring

38. 13-38 Chemistry 121, Summer 2013, LA Tech Reactions of Unsaturated Hydrocarbons CAG 13.1

39. 13-39 Chemistry 121, Summer 2013, LA Tech Reactions of alkenes Combustion C 2 H 4 + 4 O 2 2 CO 2 + 2 H 2 O + heat C 2 H 4 + 4 O 2 2 CO 2 + 2 H 2 O + heat Alkynes also under go combustion reactions similarly

40. 13-40 Chemistry 121, Summer 2013, LA Tech Addition Reactions The exposed electrons of double bonds make alkenes more reactive than alkanes and show addition reactions.

41. 13-41 Chemistry 121, Summer 2013, LA Tech In an alkene addition, reaction, the atoms provided by an incoming molecule are attached to the carbon atoms originally joined by a double bond. In the process, the double bond becomes a single bond. Addition Reaction of Alkenes

42. 13-42 Chemistry 121, Summer 2013, LA Tech → Fig. 13.9 A bromine in water solution is reddish brown. When a small amount of such a solution is added to an unsaturated hydrocarbon, the added solution is decolorized. Addition of Bromines

43. 13-43 Chemistry 121, Summer 2013, LA Tech Vladimir Markovnikov synthesized rings containing four carbon atoms and seven carbon atoms. Markovnikov’s Rule

44. 13-44 Chemistry 121, Summer 2013, LA Tech Markovnikov Rule Non symmetric alkene In hydrohalogenation and hydration reations hydrogen adds to the double-bonded carbon with the most hydrogens

45. 13-45 Chemistry 121, Summer 2013, LA Tech Preparation of polystyrene. Addition Polymerizations

46. 13-46 Chemistry 121, Summer 2013, LA Tech (a) polyethylene (b) polypropylene (c) poly (vinyl chloride) Polymers of Unsaturated Hydrocarbons

47. 13-47 Chemistry 121, Summer 2013, LA Tech

48. 13-48 Chemistry 121, Summer 2013, LA Tech Halogenation Halogenation - Addition of halogen to the double bond. Textbook page xx.

49. 13-49 Chemistry 121, Summer 2013, LA Tech

50. 13-50 Chemistry 121, Summer 2013, LA Tech Hydrogenation Addition of hydrogen to the double bond. Textbook page 84

51. 13-51 Chemistry 121, Summer 2013, LA Tech

52. 13-52 Chemistry 121, Summer 2013, LA Tech Hydration Addition of water to the double bond. Textbook page86.

53. 13-53 Chemistry 121, Summer 2013, LA Tech

54. 13-54 Chemistry 121, Summer 2013, LA Tech

55. 13-55 Chemistry 121, Summer 2013, LA Tech

56. 13-56 Chemistry 121, Summer 2013, LA Tech

57. 13-57 Chemistry 121, Summer 2013, LA Tech Naming alkenes and alkynes Find the longest carbon chain. Use as base name with an ene or yne ending. Number the chain to give lowest number for the carbons of the double or triple bond. Locate any branches on chain.Use base names with a yl ending. For multiple branch of the same type, modify name with di, tri,... Show the location of each branch with numbers. List multiple branches alphabetically - the di, tri,... don’t count..

58. 13-58 Chemistry 121, Summer 2013, LA Tech Ethyne, is the simplest alkyne. Alkyne Bonding

59. 13-59 Chemistry 121, Summer 2013, LA Tech Reactions of alkynes Alkynes undergo hydration, halogenation, and hydrohalogenation just like alkenes. A special application is the carbide lamp (oxidation of alkyne). 2 C (coke) + CaO (lime) + heat ---> CaC 2 (calcium carbide) + CO ---> CaC 2 (calcium carbide) + CO CaC 2 + H 2 O ---> H-C  C-H (acetylene) + Ca(OH) 2 ---> H-C  C-H (acetylene) + Ca(OH) 2 Acetylene serves as combustion fuel for the carbide lamp.

60. 13-60 Chemistry 121, Summer 2013, LA Tech Aromatic hydrocarbons Aromatic hydrocarbons - organic compounds that had aromas and had different chemical properties from alkane Benzene is the parent compound for the aromatic hydrocarbons. Textbook, page90. Consider benzene. C 6 H 6

61. 13-61 Chemistry 121, Summer 2013, LA Tech Copyright © Houghton Mifflin Company. All rights reserved.13 | 61 → Fig. 13.17 Space-filling and ball-and-stick models for the structure of benzene. Unsaturated Hydrocarbons cont’d

62. 13-62 Chemistry 121, Summer 2013, LA Tech → CC 13. 4 Unsaturated Hydrocarbons cont’d

63. 13-63 Chemistry 121, Summer 2013, LA Tech Resonance Structures of Benzene Resonance structures or contributing structures = when two or more structure can be drawn for a compound. In thiscase, the real structure is something between the proposed structures. Textbook, page 90-91.

64. 13-64 Chemistry 121, Summer 2013, LA Tech Naming Aromatic Hydroarbons. Monosubstituted benzenes: Ar-CH 2 CH 3 ethylbenzene Ar-CH 2 -CH 2 -CH 2 -CH 3 butylbenzene Ar-CH 2 -CH 2 -CH 2 -CH 3 butylbenzene Ar-CH 3 (methylbenzene) toluene Ar-CH 3 (methylbenzene) toluene Ar-X (halobenzene) bromobenzene, Ar-NO 2 nitrobenzene Ar-NO 2 nitrobenzene Ar-SO 3 H benzenesulfonic acid Ar-SO 3 H benzenesulfonic acid Ar-NH 2 a nitrile substituent Ar-NH 2 a nitrile substituent X

65. 13-65 Chemistry 121, Summer 2013, LA Tech Nomenclature Disubstituted benzenes locate substituents by numbering or use the locators ortho (1,2-), meta (1,3-), and para (1,4-) Where one group imparts a special name, name the compound as a derivative of that molecule

66. 13-66 Chemistry 121, Summer 2013, LA Tech Nomenclature Polysubstituted benzenes with three or more substituents, number the atoms of the ring if one group imparts a special name, it becomes the parent name if no group imparts a special name, number to give the smallest set of numbers, and then list alphabetically

67. 13-67 Chemistry 121, Summer 2013, LA Tech

68. 13-68 Chemistry 121, Summer 2013, LA Tech Disubstituted benzenes: Textbook, page 352. 2,6-dibromotoluenep-diethylbenzene3,5-dinitrotoluene p-cholonitrobenzene p-cholonitrobenzene o-nitrobenzenesulfonic acid o-nitrobenzenesulfonic acid 4-benzyl-1-octene 4-benzyl-1-octene m-cyanotoluene m-cyanotoluene

69. 13-69 Chemistry 121, Summer 2013, LA Tech Reactions of Benzene The most characteristic reaction of aromatic compounds is substitution at a ring carbon

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72. 13-72 Chemistry 121, Summer 2013, LA Tech

73. 13-73 Chemistry 121, Summer 2013, LA Tech Benzylic Oxidation Benzene is unaffected by strong oxidizing agents such as H 2 CrO 4 and KMnO 4 halogen and nitro substituents are unaffected by these reagents an alkyl group with at least one hydrogen on the benzylic carbon is oxidized to a carboxyl group

74. 13-74 Chemistry 121, Summer 2013, LA Tech Benzylic Oxidation if there is more than one alkyl group, each is oxidized to a -COOH group terephthalic acid is one of the two monomers required for the synthesis of poly(ethylene terephthalate), a polymer that can be fabricated into Dacron polyester fibers and into Mylar films

75. 13-75 Chemistry 121, Summer 2013, LA Tech Reactions of Benzene

76. 13-76 Chemistry 121, Summer 2013, LA Tech Nitration The electrophile is NO 2 +, generated in this way

77. 13-77 Chemistry 121, Summer 2013, LA Tech Friedel-Crafts Alkylation Friedel-Crafts alkylation forms a new C-C bond between an aromatic ring and an alkyl group

78. 13-78 Chemistry 121, Summer 2013, LA Tech Friedel-Crafts Acylations Treating an aromatic ring with an acid chloride in the presence of AlCl 3 acid (acyl) chloride:acid (acyl) chloride: a derivative of a carboxylic acid in which the -OH is replaced by a chlorine