Chapter 17 - Aldehydes and Ketones

The dominant functional group is the carbonyl, C=O

Aldehydes have a carbonyl flanked by one carbon group and 1 H
Ketones have a carbonyl flanked by two carbon groups
Nomenclature:
O O
aldehyde, -al ketone, -one
R H R R

Me
H
Cl
O CHO CHO
butanal 2-methylcyclopentanecarboxaldehyde
4-chloro-2,4-dimethylpentanal

O
2-methyl-3-phenylcyclopentanone
O O
Cl
O
Ph
3-hexanone Cl
4-ethyl-3,3-dimethylhex-5-en-2-one O2N
3,3-dichloro-5-nitrocycloctanone
 Preparation of Aldehydes and Ketones
Oxidation of alcohols
OH PCC , CH2Cl2 O
CrO3Cl
H N
H
Cr2O7–2 PDC
N
H 2 CHO
OH CH2Cl2

Jones oxidation
OH CrO3 , H2SO4 O

aq acetone
 Oxidation of Alkenes
Ozonolysis Me2S is a a reducing agent
HCOOH is an oxidizing agent

O
1. O3 , –78°C

2. Me2S O H

O
1. O3 , –78°C
2. HCOOH O OH

O
1. O3 , –78°C

2. Me2S O

1. O3 , –78°C O

2. Me2S
O
H

1. O3 , –78°C
O
2. HCOOH
O
HO
 Oxidation of Alkenes
Ozonolysis Me2S is a a reducing agent
HCOOH is an oxidizing agent

O
1. O3 , –78°C

2. Me2S O H

O
1. O3 , –78°C
2. HCOOH O OH

O
1. O3 , –78°C

2. Me2S O

1. O3 , –78°C O

2. Me2S
O
H

1. O3 , –78°C
O
2. HCOOH
O
HO
 Friedel-Crafts Acylation

O An acid chloride
O 1-phenyl-1-pentanone
Cl
AlCl3

O
CH3 O
CH3
O FeCl3

Cl CH3

para- + ortho-

Deactivated aromatic compounds do not undergo

Friedel-Crafts reactions. Therefore, acid chlorides +
a Lewis acid give no reaction with nitrobenzene, benzoic acid,
acetophenone, etc.
 From Alkynes
oxymercuration
HgSO4 , Hg(OAc)2 OH O
H2O , H3PO4

enol
Tautomerizes to the ketone
Via 2° vinyl carbocation

Hydroboration
BH3 NaOH

BH2 H2 O2 O
ether OH
H
Via 4-center transition state
to put B on less substituted carbon Oxidation gives the enol, which in
this case tautomerizes to the
aldehyde
 Reactions.
Oxidation of Aldehydes

O CrO3 , H2SO4 O

H aq acetone OH

Jones oxidation
O O
KMnO4 , H2O
OH
H

Silver(II) oxide
O O
Ag2O , NH4OH

H H2O OH
 Oxidative Cleavage

Vigorous oxidation of cyclic ketones leads to oxidative cleavage

O CrO3 , 100°C CO2H Breaks adjacent C-C

or KMnO4 , H2O , >100°C CO2H bond and both carbon
atoms converted to
carboxylic acids

1,2-Diols are cleaved with periodic acid, HIO4

OsO4 , t-BuOOH OH HIO4 CHO

OH CHO

Remember that alkenes react with osmium tetroxide

O O
To give the cis-1,2-diol (dihydroxylation) via I
O O
Gives dialdehyde
 Acyl Addition

R R R R
C O C O 
C C
R R
+ R R
1 2 3

The
-bond of the carbonyl is an electron donor, but

the bond polarization leads to a + dipole on carbon,
so it is susceptible to nucleophilic attack
X
R
X: + C O 
C O
R R
+
R
4

Nucleophile donates 2 electrons to carbon, forming a new C-X

Bond. The
-bond breaks, transferring electrons to the more
Electronegative atom, oxygen, forming an alkoxide
 Angle of Attack

X– X
R C O –
R C O
R
R
Bond angle = 120° Bond angle = 109°28'
Assume a late transition state (Hammond postulate), so the
Angle of attack in the transition state should be closer to
The angles in the product, or about 110°
Nucleophiles attack C=O at an angle of about 110°, which is
called the Bürgi-Dunitz trajectory. George S. Hammond, 1921-2005

X– Jack David Dunitz Hans-Beat Bürgi

110°
R C O
R
Bürgi, H. B.; Dunitz, J. D.; Shefter, E., "Geometrical Reaction Coordinates. II.
Nucleophilic Addition to a Carbonyl Group". J. Am. Chem. Soc. 1973, 95, 5065-5067
 Nucleophilic Attack

Nucleophile X
R C O –
R C O
R
R

Nucleophile = RMgX , RLi , RC
C–Na , Na+–CN

Mg , ether
Br MgBr

Grignard reagent

+
MgBr

– H3O+
O
O– MgBr+ OH
ether
 Reactions
O 1. PhMgCl , THF OH
Ph
2. H3O+

1. Mg , ether

Br OH
2 O
3. H3 O+

Other carbon nucleophiles: alkyne anions; cyanide

C
CCH3 H3O+ C
CCH3
CH3 C
C:–Na+ , ether

O–Na+ OH
O
C
N H3O+ C
N
THF , Na+–C
N

O O–Na+ OH
more reversible since cyanide is
a weaker nucleophile - can cause
the yield to be diminished