ALDEHYDES AND KETONES

METHODS OF PREPARATION
Preparation of aliphatic aldehydes and ketones
Aldehydes
10Alcohols are oxidized using K 2Cr2O7 to carboxylic acids but
0
from 1
the reaction can be stopped to aldehyde stage by distilling
alcohols
the aldehyde as it is formed.
Direct
conversion
can
be
done
using
pyridinium
chlorochromate(PCC- Collin reagent.)
Ketones
Ketones are obtained by the oxidation of secondary alcohols
0
from 2
using acidified K2Cr2O7 or alkaline KMnO4 or Jones reagent
alcohols
(Solution of chromic anhydride (CrO3) in water, acetone and
sulphuric acid)
From
Alcohol vapours are passed over heavy metal catalysts (Ag or
dehydrogen Cu). Primary and secondary alcohols give aldehydes and
ation of
ketones respectively.
alcohols
From
Reductive ozonolysis of alkenes gives corresponding carbonyl
alkenes
compounds.
From
Hydration of alkynes yields carbonyl compounds.
alkynes
Borohydration using Sia2BH followed by oxidation using
H2O2/OH_ yields aldehydes.
Acid catalysed hydrolysis of alkynes using H2SO4/HgSO 4gives
ketones.
From partial Acid chlorides when reacted with Lindlar catalyst (Pd on
reduction of BaSO4
partly
poisoned
with
quinoline)
give
acid
aldehydes.Similarly nitriles can be partially reduced to
chlorides,nit aldehydes using Stephens reaction using SnCl2 and HCl.
riles and
Esters can be reduced to aldehydes using DIBAL-H(which
esters
also reduces nitriles and acid chlorides to aldehydes). Acyl
chloride can be converted into aldehyde using Alkyl
cadmium(R2Cd) and ketones can be made from nitriles and
Grignard reagents.
Preparation of aromatic aldehydes and ketones.
Etard
Chromyl chloride(CrO2Cl2) followed by hydrolysis converts
formylation
toluene to benzaldehyde
Gattermann When benzene is treated with CO and HCl in the presence of
AlCl3 or CuCl, it gives benzaldehyde.
formylation
From side
Toluene is converted into benzyl choride and subsequent
chain
hydrolysis of chloride gives benzaldehyde.
oxidation
FriedelBenzene when reacted with acid chloride in presence of
AlCl3 gives aromatic ketones.
crafts
acylation

REACTIONS OF ALDEHYDES AND KETONES

REACTIONS
Addition of HCN

Addition of
NaHSO3
Addition of
Grignard
reagents
Addition of
alcohols

Addition of
ammonia and its
derivatives

Reductions

Oxidations

Iodoform

PRODUCTS
Aldehydes and ketones react with HCN in the presence of
catalytic amount of base to form cyanohydrins.Cyano group of
cyanohydrins can be further hydrolysed to carboxylic acids
and reduced to amines.
Aldehydes and ketones react with sodium bisulphate to form
addition products.Formation of addition product is reversible
so the reaction can be used as a method to purify aldehydes.
Formaldehyde gives 10 alcohol any other aldehyde gives 20
alcohol and ketones give 30 alcohol with Grignard reagents.
Aldehydes in the presence of dry HCl add one molecule of
alcohol to give hemiacetals,with two molecules of alcohol they
form acetals.The corresponding products with ketones are
called hemiketals and ketals respectively.These products are
hydrolysed to corresponding carbonyl compounds using aq
HCl.
Aldehydes and ketones react with ammonia to give imines
Amines giveSchiff base
Hydrazines give hydrazones
Hydroxyl amine give oximes
Carbazides give carbazones
Aldehydes and ketones are reduced using NaBH4 and LiAlH4
and catalytic hydrogenation using H2/Pd to corresponding
alcohols.
They can be reduced to hydrocarbons using Clemmensen
reduction and Wolf-Kishner reduction.
Aldehydes and ketones are oxidized using strong reagents like
nitric acid, potassium permanganate, potassium dichromate
and also by mild oxidizing agents like Tollens and Fehlings
reagents to carboxylic acids.
Aldehydes and ketones having at least one methyl group (methyl

reaction
Reactions due to
-hydrogens
Aldol reaction

Cannizarro
reaction

ketones)are oxidised by sodium hypohalite(NaOX) to sodium

salts of corresponding carboxylic acids.
Aldehydes and ketones containing at least one -hydrogen
when reacted with acids or bases to give -hydroxy aldehydes
and -hydroxy ketones.The above compounds can be
dehydrated to give corresponding ,-unsaturated aldehydes
and ketones.In crossed aldol reaction reaction takes place
between two different carbonyl compounds.
Aldehydes which do not have an -hydrogen atom, undergo self
oxidation and reduction(disproportionation) reaction on treatment
with concentrated alkali. In this reaction, one molecule of the
aldehyde is reduced to alcohol while another is oxidised to
carboxylic acid salt.

(i) O3
(ii) H2O/Zn

(i) O3

(ii) H2O/Zn

(i) O3

(ii) H2O/Zn

R
R

Sia2BH

H2O2/HO

CH + H2O

RCH2OH +

[O]

RCHOHR + [O]

CH3CH2OH

Hg(SO4) / dil. H2SO4

70o C
(K2Cr2O7 + dil H2SO4)
heat/-H2O
(K2Cr2O7 + H2SO4)
heat

Cu / 570 K

C6H5CHOHCH3
O
R

(iBu)2AlH

H3O

(i) (iBu)2AlH

CN
O
Cl
O
R

Cl

+ H2

(ii) H2O

(i) (iBu)2AlH
(ii) H2O

Pd-BaSO4
heat

[O]

R
R

C
C

N +

heat
(i) ether

R MgX

Et

(SnCl2 + HCl)

N + 2[H]

(ii) H3O +

(i) ether/heat

R MgX

(ii) H3O +

O
2R

Cl +
CH3

ether

R2Cd

CrO2Cl2/CCl4
heat

CH3COCl

anhy.ZnCl2

[CO + HCl]

heat

AlCl3

ether/heat

O
+
OH

Cl

AlCl3

ether/heat

PCC

O
H

HO

O
O
H +

H HO
H2O
O

R
C

O + H2O

R
R

ROH/H

O + ROH

ROH/H

R
R
C

O+

HO

CH2

H+

HO

CH2

H 2O

R
R

O + HCN
H3O+/boil

(i) NaCN(aq)/ether
(ii) dil HCl

A
[H]

2-butanone

LiAlH4 / H2O

O
R

H +

NaHSO3

O +

H2N

O + H2N

R
R

NH2

R
R

NHPh
O

R
C

O +

H2N

NH

O
R

CH3 + 4NaOH + 3I2

O
R

NH2

heat

R + 4[H]

H2N-NH2/HO
heat

..

HO

CARBOXYLIC ACIDS
METHODS OF PREPARATION
Preparation of carboxylic acids

From 10
alcohols

10Alcohols are oxidized using K 2Cr2O7,KMnO4 or CrO3 in acid

medium to carboxylic acids

From alkyl
benzenes

Vigorous oxidation of alkyl benzenes with acidic or alkaline

potassium permanganate give carboxylic acids. The entire
side chain is oxidised to the carboxyl group irrespective of
length of the side chain.At least one hydrogen must be
present in benzylic position.
Hydrolysis of amides and nitriles in the presence of acid or
base give carboxylic acids.

From
nitriles and
amides
From
Grignard
reagents
From
hydrolysis

When Grignard reagents are reacted with CO2 followed by

acidification.
Acid chlorides,anhydrides give carboxylic acids when reacted
with water.
Esters can be hydrolysed to acids using acid or base.The
hydrolysis reaction with acids is reversible and with base
irreversible.

REACTIONS OF CARBOXYLIC ACIDS

Acidic
properties
Dehydration
Esterification
Formation of
acid
chlorides
Reaction
with
ammonia
Reduction
Decarboxylat
ion
halogenation

Carboxylic acids react with Na,NaOH,and NaHCO3 to form

corresponding sodium salts
Carboxylic acids when heated with H2SO4 or P2O5 undergo
dehydration to form anhydrides
Carboxylic acids react with alcohols in the presence of catalytic
amount of acid to form esters
Carboxylic acids react with PCl5,POCl3 and SOCl2 to form acid
chlorides.
Carboxylic acids react with ammonia to form ammonium salts
which after heating form amides
Carboxylic acids react with LiAlH4 or diborane to give alcohols
Carboxylic acids lose carbon dioxide to form hydrocarbons when
their sodium salts are heated with sodalime (NaOH and CaO in the
ratio of3 : 1).
Carboxylic acids are halogenated in the position by reacting with
chlorine or bromine in the presence of red P

+ 2Na

2RCOOH
RCOOH +

NaOH

2RCOOH +

Na2CO3

RCOOH +

NaHCO3

O
R

OH +

C
O

H+

R OH
O

OH +

HO

H2O

O
O
R

NH3

OH +
O

heat
H 2O

heat

OH + PCl5

O
3 R

heat

OH + PCl3

O
R

OH

O
R

OH +
OH

O
RCOONa +

heat

SOCl2

4[H]

Br2

LiAlH4/ether

red P
heat

NaOH

CaO
heat

or

H2SO4

H+

OH

HO

P2O5