1. Chemistry 121(001) Winter 2015
Introduction to Organic Chemistry and Biochemistry
Instructor Dr. Upali Siriwardane (Ph.D. Ohio State)
Office: 311 Carson Taylor Hall ; Phone: ;
Office Hours: MTW 8: :00 am;
ThF 9: :00 am 1:00 - 2:00 pm.
December 19, 2014: Test 1 (Chapters 12-13)
January 26 , 2015: Test 2 (Chapters 14-16)
February 13, 2015: Test 3 (Chapters 17-19)
March 2, 2015: Test 4 (Chapters 20-22)
March 3 , 2015: Make Up Exam: Chapters 12-22)
Bring Scantron Sheet 882-E

2. Chapter 15: Aldehyde and Ketones
15.1 The Carbonyl Group, 469
15.2 Compounds Containing a Carbonyl Group, 470
15.3 The Aldehyde and Ketone Functional Groups, 471
15.4 Nomenclature for Aldehydes, 472
15.5 Nomenclature for Ketones, 474
15.6 Isomerism for Aldehydes and Ketones, 476
15.7 Selected Common Aldehydes and Ketones, 476
15.8 Physical Properties of Aldehydes and Ketones, 479
15.9 Preparation of Aldehydes and Ketones, 481
15.10 Oxidation and Reduction of Aldehydes and Ketones, 482
15.11 Reaction of Aldehydes and Ketones with Alcohols, 486
15.12 Formaldehyde-Based Polymers, 491
15.13 Sulfur-Containing Carbonyl Groups, 492

3. Carbonyl Group

4. Simplest Aldehyde

5. Common Names of Aldehyde and Ketones
Aldehydes:
Fomaldehyde: HCHO
Acetaldehyde: CH3CHO
Propionaldehyde: CH3CH2CHO
Butyraldehyde: CH3CH2CH2CHO
Valeraldehyde: CH3CH2CH2CH2CHO
Ketones:
Acetone: CH3COCH3
Methyl ethyl ketone CH3CH2COCH3
Butyl propyl ketone CH3CH2CH2CH2COCH2CH2CH3

6. 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.
aldehyde, -CHO use -al ending.
Ketones -RCOR’ use -one ending.

7. 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.
aldehyde, -CHO use -al ending.
Ketones -RCOR’ use -one ending.

8. Example C - C - C - C - CHO C - C - C - C - CO-C-C
Base contains 5 carbon
- aldehyde name is pentane
- remove -e and add -al
C - C - C - C - CO-C-C
Base contains 7 carbon
- aldehyde name is heptane
- remove -e and add -one
3-heptanone

9. 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. 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. Physical properties of aldehydes and ketones.

12. Nomenclature

13. Name the Aldehyde
2,4-dimethylpentanal

14. 1. Assign the type of organic compound with following general condensed (structural formula.

15. 2. Names (common/IUPAC)of following aldehydes and ketones.
a) ____________ b) _______________ c) __________________
d) ____________ e) _______________ f) __________________
g) ____________ h) __________________

16. Nomenclature

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

18. Addition reactions of als & ones
Hemiacetal or hemiketal formation

19. Hemiacetal form of cyclic sugars

20. 4. Identify each of the following compounds as a hemiacetal, hemiketal, acetal, or ketal:
a) ____________ b) _______________ c) __________________
d) ____________ e) _______________ f) __________________

21. 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:

22. Bakelite

23. Preparation of Aldehydes:
Partial oxidation of primary alcohols with H2CrO4:

24. Preapration of ketones:
Oxidation of secondary alcohols with KMnO4, or H2CrO4

25. Oxidation of alcohol

26. 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

27. Oxidation of alcohol

28. 5) Which alcohol would you oxidize to produce each of the following compounds?b) c) d)

29. 6) Preparation of adehydes and ketones
a) Control oxidation of 1ry alcohol
b) Complete oxidation of 1ry alcohol

30. 6) Preparation of adehydes and ketones c) Oxidation of 2ry alcohol
d) Oxidation of 3ry alcohol
No Reaction

31. 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 : 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.
O: both reactants (H-X (X= Cl, OH)) and the alkene need to be asymmetric
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.

32. Chemical Reactions of Aldehydes and Ketone
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 : 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.
O: both reactants (H-X (X= Cl, OH)) and the alkene need to be asymmetric

33. Reduction of als & ones compounds to alcohols:

34. Redox Reactions
Reduction Reactions: both aldehydes and ketones are reduced to alcohols by taking H from the reducing agents.
LiAlH4
NaBH4
H2/Ni or Pt catalysts
Oxidation Reactions: only aldehydes are oxidized to carboxylic acids.
Jone’s Reagent
AgNO3/NH4OH (silver mirror test)
CuSO4/Na2CO3/Citrate (Benedict’s reagent)

35. Aldehyde and Ketone Reduction: To alcohols

36. 7) Complete the following reductions of aldehyde and ketones and identify the type of alcohols (1ry, 2ry and 3ry) produced. d)

37. Reduction of als & ones compounds to alcohols:

38. Addition reactions of als & ones
Hemiacetal or hemiketal formation

39. Addition reactions of als & ones
Hemiacetal or hemiketal formation

40. Hemiacetal form of cyclic sugars

41. Formation of Acetals and Ketals.

42. 8) Complete the following formation reactions hemiacetal, hemiketal, acetal, or ketal:

43. Redox Reactions
Reduction Reactions: both aldehydes and ketones are reduced to alcohols by taking H from the reducing agents.
LiAlH4
NaBH4
H2/Ni or Pt catalysts
Oxidation Reactions: only aldehydes are oxidized to carboxylic acids.
Jone’s Reagent
AgNO3/NH4OH (silver mirror test)
CuSO4/Na2CO3/Citrate (Benedict’s reagent)

44. Chemical Reactions Oxidation of aldehyde.
Benedict's Test for aldehydes:

45. Test for Urine Glucose: Benedict’s Test

46. Tollen's Test: Oxidation of aldehyde.
The commercial manufacture of silver mirrors uses a similar process.

47. 9) Complete reactions of following aldehydes and ketones
Tollen’s Reagent: Silver mirror test:
Benedict's test:

48. 9) Complete reactions of following aldehydes c) Oxidation of aldehyde
and ketones
c) Oxidation of aldehyde
d) Cyclic hemi-acetal formation

49. Addition of HCN and H2O

50. Aldol Condensation
In biological systems this reaction is catalysed by an enzyme named aldolase.

51. Keto & Enol tautomers
keto form enol from

52. Keto & Enol tautomers in sugars
aldehyde enol ketone

53. Addition reactions of als & ones
Hemiacetal or hemiketal formation

54. Formation of Acetals and Ketals.

55. Hemiacetal form of cyclic sugars