1. Organic Chemistry The Chemistry of Carbon Compounds

2. Carbon

3. “Organic” Chemistry Historically, organic compounds are defined as compounds extracted or isolated from plants and animals. –VITALISM: Scientists believed that organic compounds contained a vital force that was only found in living systems Disproved by Friederich Wohler in 1828 by synthesizing urea using inorganic materials (silver cyanate and ammonium chloride)

4. Friederich Wohler

5. Organic Chemistry Study of carbon compounds –Composed of carbon, hydrogen, oxygen, nitrogen, sulfur, phosphorus, and the halogens More than 95% of known compounds are organic compounds (Carbon-containing) Recall –Carbons can have 4 bonds –Nitrogen can have 3 bonds –Oxygen can have 2 bonds –Hydrogen can have 1 bond

6. Common Elements in Organic Compounds C, H, O, (N, S)

7. The Secret to Organic Compounds: the unique carbon atom CATENATION –Ability of C-atoms to bond to each other so strongly, they can form long chains. Eg. Thousands of C-atoms bonded. –Each carbon can have four bonds, maximum

8. Common organic compound families HYDROCARBONS: Only C and H –Alkanes, alkenes, alkynes, arenes, aromatic compounds OXYGEN-CONTAINING –Alcohols, ethers, aldehydes, ketones, carboxylic acids, esters, acid anhydrides NITROGEN-CONTAINING –Amines, Amides

9. Examples

10. Classification of Hydrocarbons

11. Hydrocarbons

12. Hydrocarbons: Alkanes Simplest hydrocarbons Contains only C–C and C–H bonds Usually used as fuels Three types –Straight chain alkanes –Branched alkanes –Cyclic alkanes

13. Examples of Alkanes

14. Structures of Alkanes

15. Structural Isomers

17. Cycloalkanes Alkanes that form rings are called cycloalkanes

18. Haloalkanes Alkanes with halogens Freon 11 Freon 12 Freon 14

19. Chlorofluorocarbons Insoluble in water and are unreactive towards substances Unreactiveness lets them reach the stratosphere and react with the ozone layer

21. Alkenes

22. Alkynes Contains a C≡C bonds

23. August Kekule and the Dream C 6 H 6

24. "...I was sitting writing on my textbook, but the work did not progress; my thoughts were elsewhere. I turned my chair to the fire and dozed. Again the atoms were gamboling before my eyes. This time the smaller groups kept modestly in the background. My mental eye, rendered more acute by the repeated visions of the kind, could now distinguish larger structures of manifold conformation; long rows sometimes more closely fitted together all twining and twisting in snake-like motion. But look! What was that? One of the snakes had seized hold of its own tail, and the form whirled mockingly before my eyes. As if by a flash of lightning I awoke; and this time also I spent the rest of the night in working out the consequences of the hypothesis." "I fell into a reverie, and lo, the atoms were gamboling before my eyes! Whenever, hitherto, these diminutive beings had appeared to me, they had always been in motion; but up to that time, I had never been able to discern the nature of their motion. Now, however, I saw how, frequently, two smaller atoms united to form a pair; how a larger one embraced the two smaller ones; how still larger ones kept hold of three or even four of the smaller; whilst the whole kept whirling in a giddy dance. I saw how the larger ones formed a chain, dragging the smaller ones after them, but only at the ends of the chain... The cry of the conductor: “Clapham Road,” awakened me from my dreaming; but I spent part of the night in putting on paper at least sketches of these dream forms. This was the origin of the Structural Theory."

25. 24.3 Aromatic Hydrocarbons C C C CC C H H H H H H C C C CC C H H H H H H

26. Cyclic structures with alternating C–C and C=C bonds

27. 24.3 Polycyclic Aromatic Hydrocarbons

28. Functional Groups Determines the properties of the organic compound –Compounds with the same functional group will react similarly Alkenes: –C=C– bond Alkynes: –C≡C– bond Aromatic hydrocarbons: cyclic structure with alternating –C–C– and –C=C– bonds

29. Alcohols has the general structure R–OH –derived from hydrocarbons and contain -OH groups Polar molecules and are soluble in water (Why?)

30. Some Common Alcohols CH 3 OH (methanol) –Used as an industrial solvent –Possible replacement for gasoline in automobiles CH 3 CH 2 OH (ethanol) –Made from fermentation of grain or other sugar materials –Made by reaction of ethylene with water (denatured alcohol) –Used for beverages and fuels

31. Some Common Alcohols Isopropyl Alcohol –Also known as rubbing alcohol –Used as a disinfectant Ethylene glycol –Also known as antifreeze –Has multiple –OH groups

32. Alcohols Sterols, ethylene glycol

33. C 6 H 12 O 6 (aq) 2CH 3 CH 2 OH (aq) + 2CO 2 (g) enzyme CH 2 CH 2 (g) + H 2 O (g) CH 3 CH 2 OH (g) H 2 SO 4 Biological production of ethanol Commercial production of ethanol Metabolic oxidation of ethanol CH 3 CH 2 OH CH 3 CHO + H 2 alcohol dehydrogenase DRINKABLE vs. DENATURED Alcohol

34. Ethers Has the R-O-R’ general structure Compounds in which two hydrocarbons linked by an oxygen are called ethers. Used as general anesthetic Used as solvents Less soluble in water than alcohols

35. Ethers

36. Compounds with a Carbonyl Group Carbonyl functional group is C=O Types of different carbonyl compounds –Aldehydes –Ketones –Carboxylic Acids –Esters –Amides

37. Aldehydes and Ketones Aldehydes must have at least one H atom attached to the carbonyl group: Ketones must have two C atoms attached to the carbonyl group:

38. Functional Group Chemistry H C H O H C O CH 3 C O H3CH3C formaldehydeacetaldehydeacetone ALMONDS, FORMALIN

39. Carboxylic Acids Carboxylic acids contain a carbonyl group with an -OH attached. The carboxyl functional group is -COOH Carboxylic acids are weak acids. VINEGAR, ASPIRIN, FACIAL WASH, ANTS, CITRUS FRUITS, PROTEINS, PRESERVATIVES

40. Common Carboxylic Acids

41. Esters Esters contain -COOR groups: Usually have fruity odors and tastes

42. Ester Flavors and Fragrances

43. Functional Group Chemistry Esters have the general formula R’COOR, where R is a hydrocarbon group. CH 3 COOH + HOCH 2 CH 3 CH 3 C O CH 2 CH 3 + H 2 O O ethyl acetate Banana: isopentyl acetate Pineapple: ethyl butanoate Apple: methyl butanoate Pear: propyl ethanoate Orange: Octyl ethanoate Raspberry: 2-Methylpropyl ethanoate Oil of Wintergreen: methyl salycilate

44. Esters Galore! allyl caproate pineapple amyl acetate apple, banana amyl butyrate apricot, pear, pineapple amyl caproate apple, pineapple amyl valerate apple benzyl acetate pear, strawberry bornyl acetate pine tree flavor iso-butyl acetate cherry, raspberry, strawberry ethyl acetate peach, pineapple, raspberry ethyl butyrate banana, pineapple, strawberry ethyl caproate strawberry ethyl cinnamate cinnamon ethyl formate lemon, strawberry ethyl heptoate grape, pineapple ethyl isovalerate apple ethyl heptanoate apricot, cherry, grape, raspberry ethyl lactate grape ethyl pelargonate grape geranyl acetate geranium geranyl butyrate cherry geranyl valerate apple linalyl acetate lavender,sage linalyl butyrate peach linalyl formate apple, peach menthyl acetate peppermint methyl benzyl acetate cherry methyl cinnamate strawberry methyl phenyl acetate honey methyl salicylate wintergreen methyl anthranilate grape,jasmine nonyl caprylate orange octyl butyrate parsnip terpenyl butyrate cherry

45. HOW TO MIMIC NATURE: Making synthetic flavoring A good cherry is supposed to be tough to formulate. Here is an example of a *minimum* synthetic cherry flavoring: ethyl methyl p-tolyl glycidate 16.0 % iso-amyl acetate 12.0 % iso-butyl acetate 12.0 % p-methyl benzyl acetate 11.0 % benzaldehyde 8.0 % vanillin 7.0 % benzyl alkcohol 5.5 % piperonal 5.0 % ethyl caprate 4.0 % cinnamic aldehyde dimethyl acetal 3.0 % p-tolyl aldehyde 3.0 % cinnamyl anthranilate 3.0 % ethyl caproate 2.0 % geranyl butyrate 2.0 % terpenyl butyrate 0.5 %

46. Amines Organic bases Contain carbon, hydrogen, and nitrogen

47. Amides composites of carbonyl and amine functionalities proteins

49. Name the functional group

50. Compounds with multiple functional groups

51. Mango

52. Would you eat this?  -Terpinolene, Ethyl butanoate, 3-Carene, Ethyl acetate, Ethyl 2-butenoate,  -Terpinene,  -Thujene, Dimethyl sulfide, Limonene,  -Phellandrene, Myrcene, p- Cymen-8-ol,  -Caryophyllene, cis-3-Hexene-1-ol, hexadecyl acetate, 5-Butyldihydro-3H-2-furanone, trans-2-hexenal, Ethyl tetradeconaoate,  -Humulene, sabinene, 2-Carene, Camphene, Ethyl octanoate, 4- Isopropenyl-1-methylbenzene 1-Hexanol,  -terpinene, hexanal, Ethyl hexadecanoate,  -Copaene, Hexadecanal, Ethanol, Ethyl propionate, Dihydro-5- hexyl-3H-2-furanone, Carveol, Geranial, Ethyl decanoate, Furfural, Butyl acetate, Methyl butanoate, 2,3, Pentanedione, 1,1, diethoxyethane, pentadecanal, Butyl formate, 1-Butanol, 5-Methylfurfural, Ethyl dodecanoate, 2-Acetylfuran, 2 Methyl-1-butanol, 4- Methylacetophenoen, Acetaldehyde, Cyclohexane

53. FOSSIL FUELS Coal, Petroleum, Natural Gas From decayed organic matter Makes up 90% of energy used

54. Coal Main element is carbon, but contains small% of other elements Complete combustion: –C(s) + O 2 (g)  CO 2 (g) Limited supply, strip mining

55. Natural Gas Principally methane Formed ages ago probably by heat, pressure, and action of bacteria on organic matter.

56. Chemistry In Action: The Petroleum Industry Crude Oil

57. The Guimaras Oil Spill

58. Gasoline: C5-C12 alkanes C5-C12 alkanes, some sulfur and nitrogen-containing hydrocarbons >C15, difficult to combust, causes knock OCTANE Rating: Isooctane (CH 3 ) 3 CCH 2 CH(CH 3 ) 2 = 100 Heptane = 0 Some cpds improving octane rating: tetraethyllead Diesel Runs on engine designed by Engineer Rudolf Diesel Petrodiesel: It is a hydrocarbon mixture, (C10-C15) obtained in the fractional distillation of crude oil between 250 °C and 350 °C. Biodiesel: Methyl esters of fats from natural oils

59. POLYMERS Poly: Many Meros: Parts Made up of repeating monomers Copolymer is a polymer made up of two or more monomers Common biopolymers: Proteins, DNA, RNA, starch, cellulose ( CH CH 2 CH 2 CH CH CH 2 ) n

60. Some commercial polymers

61. PET: Polyethylene terephthalate –Plastic bottles Polytetrafluoroethylene –Teflon™ Polypropylene Polystyrene Polyvinyl chloride Nylon (synthetic polyamide, similar to bonds in proteins) http://www.nationalgeographic.com/education/plastics/index.html

62. References:  Hill, JW and Kolb DK. Chemistry for the Changing Times, 7th ed. Prentice Hall International. 1992.  Brown, TL. Le May, Jr., HE, and Bursten, BE. Chemistry: The Central Science. 1997.  Schmid, G. Organic Chemistry. Mosby-Year Book, Inc. 1996.  http://chemed.chem.purdue.edu/genchem/ (accessed on July 28, 2003) http://chemed.chem.purdue.edu/genchem/  Partial list of ingredients for the mango from Snyder, C.H. “The Extraordinary Chemistry of Ordinary Things”, J. Wiley & Sons, 1998. p. 54  Picture of Mango from http://www.globalgourmet.com/ggt/ggt0598/art/mango.jpg (accessed on June 6, 2003) http://www.globalgourmet.com/ggt/ggt0598/art/mango.jpg