1. 1-1 Chemistry 121, Winter 2016, LA Tech Introduction to Organic Chemistry and Biochemistry Instructor Dr. Upali Siriwardane (Ph.D. Ohio State) E-mail: upali@latech.edu Office: 311 Carson Taylor Hall ; Phone: 318-257-4941; Office Hours: MTW 8:00 - 10:00 am; ThF 9:00 - 10:00 am 1:00 - 2:00 pm. December 18, 2015: Test 1 (Chapters 12-13) January 25, 2016: Test 2 (Chapters 14-16) February 17, 2016: Test 3 (Chapters 17-19) February 29, 2016: Test 4 (Chapters 20-22) March 1, 2016: Make Up Exam: Chapters 12-22) Bring Scantron Sheet 882-E Chemistry 121 Winter 2016 1

2. 1-2 Chemistry 121, Winter 2016, LA Tech Chapter 15: Aldehyde and Ketones 15-1 The Carbonyl Group 15-2 Compounds Containing a Carbonyl Group 15-3 The Aldehyde and Ketone Functional Groups 15-4 Nomenclature for Aldehydes 15-5 Nomenclature for Ketones 15-6 Isomerism for Aldehydes and Ketones 15-7 Selected Common Aldehydes and Ketones 15-8 Physical Properties of Aldehydes and Ketones 15-9 Preparation of Aldehydes and Ketones 15-10Oxidation and Reduction of Aldehydes and Ketones 15-11Reaction of Aldehydes and Ketones with Alcohols 15-12Sulfur-Containing Carbonyl Groups

3. 1-3 Chemistry 121, Winter 2016, LA Tech Carbonyl Group

4. 1-4 Chemistry 121, Winter 2016, LA Tech Simplest Aldehyde

5. 1-5 Chemistry 121, Winter 2016, LA Tech Common Names of Aldehyde and Ketones Aldehydes: Fomaldehyde: HCHO Acetaldehyde: CH 3 CHO Propionaldehyde: CH 3 CH 2 CHO Butyraldehyde: CH 3 CH 2 CH 2 CHO Valeraldehyde: CH 3 CH 2 CH 2 CH 2 CHOKetones: Acetone: CH 3 COCH 3 Methyl ethyl ketone CH 3 CH 2 COCH 3 Butyl propyl ketone CH 3 CH 2 CH 2 CH 2 COCH 2 CH 2 CH 3

6. 1-6 Chemistry 121, Winter 2016, LA Tech IUPAC Nomenclature of Aldehyde and Ketones The IUPAC system deals with functional groups two different ways. Modification of the hydrocarbon name to indicate the presence of a functional group. al aldehyde, -CHO use -al ending. one Ketones -RCOR’ use -one ending.

7. 1-7 Chemistry 121, Winter 2016, LA Tech IUPAC Nomenclature of Aldehyde and Ketones The IUPAC system deals with functional groups two different ways. Modification of the hydrocarbon name to indicate the presence of a functional group. al aldehyde, -CHOuse -al ending. one Ketones -RCOR’ use -one ending.

8. 1-8 Chemistry 121, Winter 2016, LA Tech Example C - C - C - C - CHO Base contains 5 carbon -aldehyde name is pentane -e -al -remove -e and add -al C - C - C - C - CO-C-C Base contains 7 carbon -aldehyde name is heptane -e -one -remove -e and add -one 3-heptanone

9. 1-9 Chemistry 121, Winter 2016, LA Tech Physical Properties of Aldehydes and ketones Aldehyde and ketones can only make dipole-dipole attraction. BP and MP are lower than alcohols, higher than hydrocarbons and ether with comparable carbon numbers

10. 1-10 Chemistry 121, Winter 2016, LA Tech Bonding Characteristics of Aldehydes Ketones Both aldehydes and ketones contain a carbonyl functional group. A carbonyl group is an carbon atom double-bonded to an oxygen atom. The structural representation for a carbonyl group is Carbon-oxygen (C=O) and carbon-carbon (C=C) double bonds differ in a major way. A carbon oxygen double bond is more polar

11. 1-11 Chemistry 121, Winter 2016, LA Tech Physical properties of aldehydes and ketones.

12. 1-12 Chemistry 121, Winter 2016, LA Tech Nomenclature

13. 1-13 Chemistry 121, Winter 2016, LA Tech Name the Aldehyde 2,4-dimethylpentanal

14. 1-14 Chemistry 121, Winter 2016, LA Tech 1. Assign the type of organic compound with following general condensed (structural formula.

15. 1-15 Chemistry 121, Winter 2016, LA Tech 2. Names (common/IUPAC)of following aldehydes and ketones. a) ____________ b) _______________ c) __________________ d) ____________ e) _______________ f) __________________ g) ____________ h) __________________

16. 1-16 Chemistry 121, Winter 2016, LA Tech Nomenclature

17. 1-17 Chemistry 121, Winter 2016, LA Tech 3. Draw the condensed formula of following aldehydes and ketones : a)acetaldehyde/ ethanal b) ethyl methyl ketone c) 3-methyl-2- pentanone d) isopropyl methyl ketone e) 2- methylbutanal f) 5-methyl-3- hexanone g) benzophenone h) acetophenone

18. 1-18 Chemistry 121, Winter 2016, LA Tech Important Aldehydes Methanal or formaldehyde Ethanal or acetaldehyde 2-Propanone or acetone 2-Butanone or methyl ethyl ketone Oil of almonds or benzaldehyde Oil of Cinnamon or cinnamaldehyde Oil of vanilla beans or vanillin Mushroom flavoring or 2-octanone Oil of lemongrass or citral:

19. 1-19 Chemistry 121, Winter 2016, LA Tech Preparation of Aldehydes: Partial oxidation of primary alcohols with H 2 CrO 4 : PCC >

20. 1-20 Chemistry 121, Winter 2016, LA Tech Preapration of ketones: Oxidation of secondary alcohols with KMnO 4, or H 2 CrO 4 (Oxidizing agents)

21. 1-21 Chemistry 121, Winter 2016, LA Tech Bakelite (Polymers)

22. 1-22 Chemistry 121, Winter 2016, LA Tech Chemical Reactions of Aldehydes and Ketone 1) Combustion: Alkenes are very flammable and the combustion products are carbon dioxide and water. 2) Addition Reactions: Atoms or group of atoms are added to each a carbon oxygen double bond. Two different reactants are involved. a) hemi-acetal or hemi-ketal formation: Addition of Alcohols: - OR group of the R-OH is added to the C atom and H of the ROH is added to O atom. b) Aacetal or ketal formation : Substiution of hemi-acetal or -ketal Another or second ROH is reacted in a substitution reaction to replace the H atom of the -OH group of the hemi-acetal or hemi-ketal and water molecule is produced. 3) Oxidation Reactions : only aldehydes are oxidized to carboxylic acids. 4) Reduction Reactions : both aldehydes and ketones are reduced to alcohols by taking H from the reducing agents.

23. 1-23 Chemistry 121, Winter 2016, LA Tech Addition reactions of als & ones Hemiacetal or hemiketal formation

24. 1-24 Chemistry 121, Winter 2016, LA Tech Substitution reactions of hem-acetals/ketals Acetal or Ketal formation

25. 1-25 Chemistry 121, Winter 2016, LA Tech Hemiacetal form of cyclic sugars

26. 1-26 Chemistry 121, Winter 2016, LA Tech 4. Identify each of the following compounds as a hemiacetal, hemiketal, acetal, or ketal: a) ____________ b) _______________ c) __________________ d) ____________ e) _______________ f) __________________

27. 1-27 Chemistry 121, Winter 2016, LA Tech Oxidation of alcohol PCC

28. 1-28 Chemistry 121, Winter 2016, LA Tech Oxidation of alcohol

29. 1-29 Chemistry 121, Winter 2016, LA Tech 5) Which alcohol would you oxidize to produce each of the following compounds? a) b) c) d)

30. 1-30 Chemistry 121, Winter 2016, LA Tech Oxidation of Alcohols to oxidize a 1° alcohol to an aldehyde, use PCC PCC oxidation of geraniol gives geranial Tertiary alcohols are not oxidized by either of these reagents; they are resistant to oxidation

31. 1-31 Chemistry 121, Winter 2016, LA Tech 6) Preparation of aldehydes and ketones a) Control oxidation of 1ry alcohol b) Complete oxidation of 1 ry alcohol

32. 1-32 Chemistry 121, Winter 2016, LA Tech 6) Preparation of adehydes and ketones c) Oxidation of 2 ry alcohol d) Oxidation of 3 ry alcohol No Reaction

33. 1-33 Chemistry 121, Winter 2016, LA Tech Chemical Reactions of Aldehydes and Ketone 1) Combustion: Alkenes are very flammable and the combustion products are carbon dioxide and water. 2) Addition Reactions: Atoms or group of atoms are added to each a carbon oxygen double bond. Two different reactants are involved. a) hemi-acetal or hemi-ketal formation: Addition of Alcohols: - OR group of the R-OH is added to the C atom and H of the ROH is added to O atom. b) Aacetal or ketal formation : Substiution of hemi-acetal or -ketal Another or second ROH is reacted in a substitution reaction to replace the H atom of the -OH group of the hemi-acetal or hemi-ketal and water molecule is produced. 3) Oxidation Reactions : only aldehydes are oxidized to carboxylic acids. 4) Reduction Reactions : both aldehydes and ketones are reduced to alcohols by taking H from the reducing agents.

34. 1-34 Chemistry 121, Winter 2016, LA Tech Reduction Reactions : Both aldehydes and ketones are reduced to alcohols by taking H from the reducing agents. Reducing Agents 1) 2) 3)

35. 1-35 Chemistry 121, Winter 2016, LA Tech Reduction of als & ones compounds to alcohols:

36. 1-36 Chemistry 121, Winter 2016, LA Tech Reduction of als & ones compounds to alcohols:

37. 1-37 Chemistry 121, Winter 2016, LA Tech Aldehyde and Ketone Reduction: To alcohols

38. 1-38 Chemistry 121, Winter 2016, LA Tech 7) Complete the following reductions of aldehyde and ketones and identify the type of alcohols (1ry, 2ry and 3ry) produced. d)

39. 1-39 Chemistry 121, Winter 2016, LA Tech Reduction of als & ones compounds to alcohols:

40. 1-40 Chemistry 121, Winter 2016, LA Tech Addition reactions of als & ones Hemiacetal or hemiketal formation

41. 1-41 Chemistry 121, Winter 2016, LA Tech Addition reactions of als & ones Hemiacetal or hemiketal formation

42. 1-42 Chemistry 121, Winter 2016, LA Tech Hemiacetal form of cyclic sugars

43. 1-43 Chemistry 121, Winter 2016, LA Tech Formation of Acetals and Ketals.

44. 1-44 Chemistry 121, Winter 2016, LA Tech 8) Complete the following formation reactions hemiacetal, hemiketal, acetal, or ketal:

45. 1-45 Chemistry 121, Winter 2016, LA Tech Chemical Reactions Oxidation of aldehyde. Benedict's Test for aldehydes:

46. 1-46 Chemistry 121, Winter 2016, LA Tech Test for Urine Glucose: Benedict’s Test

47. 1-47 Chemistry 121, Winter 2016, LA Tech Oxidation of aldehyde. The commercial manufacture of silver mirrors uses a similar process. Tollen's Test:

48. 1-48 Chemistry 121, Winter 2016, LA Tech 9) Complete reactions of following aldehydes and ketones a) Tollen’s Reagent: Silver mirror test: b) Benedict's test:

49. 1-49 Chemistry 121, Winter 2016, LA Tech 9) Complete reactions of following aldehydes and ketones c) Oxidation of aldehyde d) Cyclic hemi-acetal formation

50. 1-50 Chemistry 121, Winter 2016, LA Tech Addition of HCN and H 2 O

51. 1-51 Chemistry 121, Winter 2016, LA Tech Aldol Condensation In biological systems this reaction is catalysed by an enzyme named aldolase.

52. 1-52 Chemistry 121, Winter 2016, LA Tech Keto & Enol tautomers keto form enol from

53. 1-53 Chemistry 121, Winter 2016, LA Tech Keto & Enol tautomers in sugars aldehyde enol ketone

54. 1-54 Chemistry 121, Winter 2016, LA Tech Addition reactions of als & ones Hemiacetal or hemiketal formation

55. 1-55 Chemistry 121, Winter 2016, LA Tech Formation of Acetals and Ketals.

56. 1-56 Chemistry 121, Winter 2016, LA Tech Hemiacetal form of cyclic sugars