REACTIONS OF ALDEHYDES AND

KETONES

BY
HARJEET GUJRAL
ASSOCIATE PROFESSOR
GOVT. COLLEGE ROPAR
Reactions of aldehydes and ketones:
oxidation
reduction
nucleophilic addition

1) Aldehydes are easily oxidized, ketones are not.

2) Aldehydes are more reactive in nucleophilic additions than
ketones.
alkane alcohol

reduction reduction

aldehyde addition
ketone product
nucleophilic
oxidation addition

carboxylic acid
nucleophilic addition to carbonyl:


O OY
C + Y Z C
 Z
 Mechanism: nucleophilic addition to carbonyl

O RDS O
1) C + Z C
Z

O OY
2) C + Y C
Z Z
Mechanism: nucleophilic addition to carbonyl, acid
catalyzed

O OH
1) C + H C

OH RDS OH
2) C + HZ C
ZH

OH OH
3) C C + H
ZH Z
Aldehydes & ketones, reactions:
1) Oxidation
2) Reduction
3) Addition of cyanide
4) Addition of derivatives of ammonia
5) Addition of alcohols
6) Cannizzaro reaction
7) Addition of Grignard reagents
8) (Alpha-halogenation of ketones)
9) (Addition of carbanions)
1) Oxidation
a) Aldehydes (very easily oxidized!)

CH3CH2CH2CH=O + KMnO4, etc.  CH3CH2CH2COOH

carboxylic acid

CH3CH2CH2CH=O + Ag+  CH3CH2CH2COO- + Ag

Silver mirror

Tollen’s test for easily oxidized compounds like aldehydes.

(AgNO3, NH4OH(aq))
Ketones only oxidize under vigorous conditions via the enol.

+ KMnO4 NR

Cyclohexanone

+ KMnO4, heat HOOCCH2CH2CH2CH2COOH

adipic acid

OH

enol
 b) Methyl ketones:

O O
C + OI- C + CHI3
R CH3 R O-
iodoform
Yellow ppt
test for methyl ketones

O
CH3CH2CH2CCH3 + (xs) NaOI CH3CH2CH2CO2- + CHI3
2-pentanone
2) Reduction:
a) To alcohols

O H2, Ni OH
C C
H

NaBH4 or LiAlH4
then H+
 H2, Pt H
O
OH
cyclopentanol
cyclopentanone

O 1. NaBH4 OH
C CH3 CHCH3
2. H+
acetophenone 1-phenylethanol
 O H2, Pt
C CH2OH
H

benzaldehyde benzyl alcohol

CH3 LiAlH4 CH3

H+
CH3CHCH=O CH3CHCH2OH

isobutyraldehyde isobutyl alcohol

 hydride reduction
mechanism: nucleophilic addition; nucleophile = hydride

O RDS O
1) C + H: Al C + Al
H

O
2) C + Al H C O Al
H

Then + H+  alcohol
Reduction
b) To hydrocarbons

O NH2NH2, OH-
CH2
C
Wolff-Kishner

O Zn(Hg), HCl
C CH2
Clemmensen
O O
AlCl3
Cl +

Zn(Hg), HCl

n-pentylbenzene

cannot be made by Friedel-Crafts alkylation

due to rearrangement of carbocation
3) Addition of cyanide

O 1. CN- OH
C C
2. H+ CN
cyanohydrin

OH
O + NaCN; then H+
CN
 mechanism for addition of cyanide
nucleophilic addition

RDS O
O
1) + C N C
C
C
N

O ONa
2) C + Na+ C then + H+
C C
N N
Cyanohydrins have two functional groups plus one
additional carbon. Nitriles can be hydrolyzed to carboxylic
acids in acid or base:

OH OH
H2O, OH-
CH2CH C N CH2CH COO-
heat

OH
H2O, H+
CH2CH C N C C COOH
heat H H
4) Addition of derivatives of ammonia

O (H+)
+ H2N G + H2O
N G

O
H2N NH2 H2N OH
H2N N NH2
hydrazine hydroxylamine H
semicarbazide

O2N

H2N HN H2N HN NO2

phenylhydrazine

2,4-dinitrophenylhydrazine
 acid catalyzed nucleophilic addition mechanism followed by dehydration

1) O OH
C + H+ C

OH
OH
+ H2N G C RDS
2) C
NH2 G

OH
C + H2O + H+
C
3) N
NH2 G G
 CH2 CHO + H2NOH CH2 CH NOH
hydroxylamine
phenylacetaldehyde an oxime

O H+ O
O + H2NHNCNH2 NHNCNH2
semicarbazide
cyclohexanone a semicarbazone

CH3CH2CH2CH2CHO + NH2 NH CH3CH2CH2CH2CH N NH

pentanal a phenylhydrazone
phenylhydrazine
5) Addition of alcohols

O OR
+ ROH, H+ C
C
OR acetal

OH
C
OR hemiacetal
Mechanism = nucleophilic addition, acid catalyzed

O OH
1) + H C
C

RDS OH
OH2 ROH C
2) +
C HOR

OH OH
3) C C + H
HOR OR
 (xs) EtOH, H+ OEt
CH2CHO CH2 CH
OEt
acetal

OCH3
O (xs) CH3OH, dry HCl
OCH3

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

CHO CH2OH COO-

conc. NaOH
+
Br Br Br

conc. NaOH
H2C=O CH3OH + HCOO-
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:

CH=O CH2OH
conc. NaOH
+ H2C=O + HCOO-
OCH3 OCH3
OH OH
vanillin
7) Addition of Grignard reagents.

O O MgBr
C + RMgX C
R

O MgBr OH
C + H2O C + Mg(OH)Br
R R
larger alcohol
 mechanism = nucleophilic addition

O RDS O
1)
C + RMgBr C + MgBr
R

O OMgBr
2) C + MgBr C
R R
#3 synthesis of alcohols. Used to build larger molecules
from smaller organic compounds.

O
H+
RMgX + C RCH2OMgX RCH2OH
H H
1o alcohol + 1 C
formaldehyde

O H+
RMgX + R'CHOMgX R'CHOH
C
R' H R
R
other aldehydes 2o alcohol + X C's
 R' R'
O H+
R-MgX + C R-COMgX R-COH
R' R" R"
R"
ketone
3o alcohol + X C's

O H+
RMgX + RCH2CH2OMgX RCH2CH2OH
H2C CH2
ethylene oxide 1o alcohol + 2 C's
Planning a Grignard synthesis of an alcohol:
a) The alcohol carbon comes from the carbonyl
compound.
b) The new carbon-carbon bond is to the alcohol carbon.

O OH
H+
C + RMgX C
R

New carbon-carbon bond

“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.”