1. Reactions of aldehydes and ketones:
oxidation
reduction
nucleophilic addition
Aldehydes are easily oxidized, ketones are not.
Aldehydes are more reactive in nucleophilic additions than ketones.

2. alkane
alcohol
reduction
reduction
aldehyde
ketone
addition
product
nucleophilic
addition
oxidation
carboxylic acid

3. nucleophilic addition to carbonyl:

4. Mechanism: nucleophilic addition to carbonyl1) 2)

5. Mechanism: nucleophilic addition to carbonyl, acid catalyzed1) 2) 3)

6. Aldehydes & ketones, reactions:
Oxidation
Reduction
Addition of cyanide
Addition of derivatives of ammonia
Addition of alcohols
Cannizzaro reaction
Addition of Grignard reagents
8) (Alpha-halogenation of ketones)
9) (Addition of carbanions)

7. 1) Oxidation
Aldehydes (very easily oxidized!)
CH3CH2CH2CH=O KMnO4, etc.  CH3CH2CH2COOH
carboxylic acid
CH3CH2CH2CH=O Ag+  CH3CH2CH2COO Ag
Tollen’s test for easily oxidized compounds like aldehydes.
(AgNO3, NH4OH(aq))
Silver mirror

8. Ketones only oxidize under vigorous conditions via the enol.

9. b) Methyl ketones:
Yellow ppt
test for methyl ketones

10. 2) Reduction:
To alcohols

13. Then + H+  alcohol

14. Reduction
b) To hydrocarbons

16. 3) Addition of cyanide

17. 1) 2)

18. Cyanohydrins have two functional groups plus one additional carbon
Cyanohydrins have two functional groups plus one additional carbon. Nitriles can be hydrolyzed to carboxylic acids in acid or base:

19. 4) Addition of derivatives of ammonia

20. 1) 2) 3)

22. melting points of derivatives ketones bp semi- 2,4-dinitro- oxime
carbazone phenylhydrazone
2-nonanone
acetophenone
menthone
2-methylacetophenone
1-phenyl-2-propanone
propiophenone
3-methylacetophenone
isobutyrophenone

23. 5) Addition of alcohols

27. Cannizzaro reaction. (self oxidation/reduction)
a reaction of aldehydes without α-hydrogens

28. Formaldehyde is the most easily oxidized aldehyde
Formaldehyde is the most easily oxidized aldehyde. When mixed with another aldehyde that doesn’t have any alpha-hydrogens and conc. NaOH, all of the formaldehyde is oxidized and all of the other aldehyde is reduced.
Crossed Cannizzaro:

29. 7) Addition of Grignard reagents.

30. 1) 2)

31. #3 synthesis of alcohols
#3 synthesis of alcohols. Used to build larger molecules from smaller organic compounds.

33. Aldehydes & ketones, reactions:
Oxidation
Reduction
Addition of cyanide
Addition of derivatives of ammonia
Addition of alcohols
Cannizzaro reaction
Addition of Grignard reagents
8) (Alpha-halogenation of ketones)
9) (Addition of carbanions)

34. Planning a Grignard synthesis of an alcohol:
The alcohol carbon comes from the carbonyl compound.
The new carbon-carbon bond is to the alcohol carbon.
New carbon-carbon bond

35. “The Grignard Song” (sung to the tune of “America the Beautiful”)
Harry Wasserman
The carbonyl is polarized,
the carbon end is plus.
A nucleophile will thus attack
the carbon nucleus.
The Grignard yields an alcohol
of types there are but three.
It makes a bond that corresponds
from “C” to shining “C.”

36. or

37. HX Mg
ROH RX
RMgX
larger
alcohol
H2O
ox.
R´OH
-C=O

38. Stockroom:
alcohols of four-carbons or less:
(methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl-1-propanol.)
benzene
cyclohexanol
any needed inorganic reagents or solvents.

39. Grignard synthesis of 4-methyl-2-pentanol from alcohols of four-carbons or less:
Step one: determine the carbonyl compound and Grignard reagent that you would use:
H2O
CH3
CH3CHCH2MgBr CH3CH=O
CH3
CH3CHCH2CHCH3 OH
Step two: show the syntheses of the Grignard reagent and the carbonyl compound from alcohols…

40. CH3 HBr CH3 Mg CH3 4-methyl-2-pentanol
CH3CHCH2OH CH3CHCH2Br CH3CHCH2MgBr H+
K2Cr2O CH3
CH3CH2OH CH3CH=O CH3CHCH2CHCH3
special cond OH
4-methyl-2-pentanol

41. 2-phenyl-2-propanol

42. 1-methylcyclohexanol

43. cyclohexylmethanol

44. ketone
aldehyde
RCOOH
ROH
ROR
alkene RX
Alcohols are central to organic syntheses RH
alkyne

45. HX Mg
ROH RX
RMgX
larger
alcohol
H2O
ox.
R´OH
-C=O

46. Using the Grignard synthesis of alcohols we can make any alcohol that we need from a few simple alcohols. From those alcohols we can synthesize alkanes, alkenes, alkynes, alkyl halides, ethers, aldehydes, ketones, carboxylic acids…
eg. Outline all steps in a possible laboratory synthesis of methyl-1-butene from alcohols of four carbons or less.
CH3
CH3CHCH=CH2

47. Retrosynthesis:
alkenes, syntheses:
1. Dehydrohalogenation of an alkyl halide
2. Dehydration of an alcohol
3. Dehalogenation of a vicinal dihalide
4. Reduction of an alkyne
Methods 3 & 4 start with compounds that are in turn made from alkenes.

48. Dehydration of an alcohol?
CH H+
CH3CHCHCH yields a mixture of alkenes OH
CH H+
CH3CHCH2CH2-OH yields a mixture of alkenes
E1 mechanism via carbocation!

49. Dehydrohalogenation of an alkyl halide?
CH KOH(alc)
CH3CHCHCH yields a mixture of alkenes Br
CH KOH(alc) CH3
CH3CHCH2CH2-Br CH3CHCH=CH2
only product 
E2 mechanism, no carbocation, no rearrangement

50. CH HBr CH3
CH3CHCH2CH2-OH CH3CHCH2CH2-Br
1o alcohol, SN2 mechanism, no rearrangement!
CH KOH(alc) CH3
CH3CHCH2CH2-Br CH3CHCH=CH2
Use the Grignard synthesis to synthesize the intermediate alcohol from the starting materials.

51. CH3 PBr3 CH3 Mg CH3 CH3CHCH2-OH CH3CHCH2Br CH3CHCH2MgBr K2Cr2O7
CH3OH H2C=O
special cond H2O
CH3
CH3CHCH2CH2-OH
HBr
CH KOH(alco) CH3
CH3CHCH=CH2 CH3CHCH2CH2-Br

52. Notes on Exam I:
Given the structures, be able to name aldehydes/ketones using either common or IUPAC names.
Be able to outline all steps in the mechanisms: nucleophilic addition & acid catalyzed nucleophilic addition.
Be able to draw structures for the organic products of the reactions of aldehydes/ketones.
Be able to outline possible laboratory syntheses of aldehydes/ketones and Grignard syntheses of alcohols, etc.
Be able to match structures with their IR spectra.
Be able to predict the 1H-nmr spectrum, given the structure.
Given the 1H-nmr spectrum and formula, be able to draw the structure of the compound.