Oxidation of Primary Alcohols

• To aldehyde: pyridinium chlorochromate (PCC,

C5H6NCrO3Cl) in dichloromethane
• Other reagents produce carboxylic acids
 Oxidation of Secondary
Alcohols
• Effective with inexpensive reagents such as
Na2Cr2O7 in acetic acid
• PCC is used for sensitive alcohols at lower
temperatures
 Mechanism of Chromic Acid
Oxidation
• Alcohol forms a chromate ester followed by
elimination with electron transfer to give ketone
• The mechanism was determined by observing the
effects of isotopes on rates
 Dry Distillation of Metal salts of
carboxylic acids
• Calcium salt of carboxylic acid can undergo dry
distillation with calcium formate to form Aldehyde
• Dry distillation with calcium salt alone form
Ketone

O
(CH3COO)2Ca + (HCOO)2Ca Dry 2CH3C + CaCO3
distillation
H

H3C
2(CH3COO)2Ca Dry CaCO3
distillation C O +

H3C
 Reduction of Acid chlorides
• Acid chlorides can be reduced using Lithium
aluminium hydrogen tritertiary butoxide, acid
hydrolysis yield Aldehyde
• The reducing agent is mild as the carbonyl
functionality is preserved.
O O

Cl H
LiAlH[OC(CH3)3]3
H2O, H

O O
CH3CH2C CH3CH2C

Cl H
 Friedel-crafts Acylation -
Ketone formations
• Acid chloride reacts with aromatic hydrocarbons
• The reaction is catalysed by a Lewis acid e.g.
Aluminium chloride AlCl3, Iron bromide FeBr3
• The product is Ketone.
O

C
O
AlCl3 CH3
+ CH3C
Cl
O O

C C
Cl
AlCl3
+
Reactions of Aldehydes and
Ketones
• Nucleophilic addition reactions

• Condensation reaction with Derivatives of

Ammonia

• Haloform reaction

• Reduction reactions

• Oxidation reactions
 Nucleophilic Addition reactions
of Aldehydes and Ketones
• Treatment of an Aldehyde or Ketone with KCN
followed by H2SO4 acid yeilds Cyanohydrin
• Acid hydrolysis of Cyanohydrin yields
Hydroxycarboxylic acid
CH3 CH3
H3C H2O
KCN
C O H3C C OH H3C C OH
dil H2SO4 H
H3C CN COOH
Condensation (Addition-Elimination)
reactions of Aldehydes and Ketones
• Ammonia derivatives add to aldehyde and
ketone to form derivatives that are important
for identification of aldehydes and ketones
• The product contains a carbon-nitrogen double
bond resulting from elimination of a molecule
of water from the initial addition product
CH3 CH3
H3C -H2O
NH2-R1
C O H3C C OH H3C C

R N-R1
NH-R1
Condensation (Addition-Elimination)
reactions of Aldehydes and Ketones
• Hydroxyamine Oxime
H3C H3C
NH2-OH
C O C N-OH
-H2O
H H

• Hydrazine Hydrazone
H3C H3C
NH2-NH2
C O C N-NH2
-H2O
H3C H3C
Condensation (Addition-Elimination)
reactions of Aldehydes and Ketones
• Phenylhydrazine Phenylhydrazone
H3C H3C
PhNH-NH2
C O C N-NHPh
-H2O
H3C H3C
• 2,4-dinitro 2,4-dinitro
phenylhydrazine Phenylhydrazone
(Brady’s reagent) (Yellow crystal) H
H
N C
NH-NH2
H CH3
-H2O
C O +
Yellow crystal
H3C O2N NO2
O2N NO2
Condensation (Addition-Elimination)
reactions of Aldehydes and Ketones
• Phenylhydrazine Phenylhydrazone
H3C H3C
PhNH-NH2
C O C N-NHPh
-H2O
H3C H3C
• 2,4-dinitro 2,4-dinitro
phenylhydrazine Phenylhydrazone
(Brady’s reagent) (Yellow crystal)
H3C H3C
NH2-NH2
C O C N-NH2
-H2O
H3C H3C
 Haloform reactions of Aldehydes
and Ketones
• Aldehydes and ketones containing a methyl
carbonyl fraction react with warm solution of
sodium hypoiodate to form yellow crystals with
distinctive smell

R R
I2 C O + 3HI
C O
NaOH
H3C I3C CHI3 + RCOONa
yellow crystal
Reduction reactions of Aldehydes
and Ketones
• Reduction of a carbonyl compound in general gives
an alcohol

• Note that organic reduction reactions add the

equivalent of H2 to a molecule
Reduction reactions of Aldehydes
and Ketones
• Aldehydes gives primary alcohols

• Ketones gives secondary alcohols

Reduction reactions of Aldehydes
and Ketones
O
Pt, Pd or Ni
RCH + H2 RCH2OH
aldehyde primary alcohol

O Pt, Pd or Ni
OH
RCR' + H2 RCHR'
ketone secondary alcohol
Reduction reactions of Aldehydes
and Ketones
Oxidation reactions of Aldehydes
and Ketones
• Oxidation reaction is used to differentiate
between the aldehydes and ketones.
• Aldehydes are easily oxidised while ketones
are not
• Aldehydes are easily oxidised using mild
oxidising agents which cannot oxidise the
Ketones
• Aldehydes are easily oxidised to the
corresponding carboxylic acids
Oxidation reactions of Aldehydes

• Oxidation using Tollens reagent (Silver mirror test)

• Tollen’s reagent is ammoniacal solution of silver (I)
nitrate (v) containing the complex ion (AgNH3)+
• Warming an aldehyde with the reagent, the
complex is reduced to metallic silver
• Forms a mirror on the walls of the test tube.

H HO
C O Ag(NH3)2 C O + 2Ag

H3C mirror
H3C
 Oxidation reactions of Aldehydes
• Oxidation using Fehlings reagent (Fehlings test)
• Fehlings reagent is a complex ion of copper (II) ion
and 2,3-dihydroxybutanedioic acid (tartaric acid)
• Warming an aldehyde with the reagent, the
complex is reduced to copper (I)oxide (red/brown
precipitate)

H HO
C O
2Cu2 C O + 4H + Cu2O
NaOH/H20 Red/
H3C H3C Brown
ppt