Aldehydes and Ketones

Introduction
• Compounds containing carbon – oxygen double bond ( >C=O) as functional group, are
known as aldehydes and ketones.
• They have the general formula CnH2nO.
• The functional group ( >C=O) is called oxo or carbonyl group; so aldehydes and ketones
are called carbonyl compounds.
• The carbon atom is called carbonyl carbon while oxygen is called carbonyl oxygen.
Carbonyl oxygen
O

C
Carbonyl carbon
• In aldehydes, carbonyl carbon is bonded to at least one hydrogen atom.
• In ketones, carbonyl carbon is bonded to two other carbon atoms.

Aldehyde Ketone
O O

R C H R C R
 NOMENCLATURE
• Aldehydes and ketones can be named in following two systems:
1. Common System
2. IUPAC System

• FOR ALDEHYDES
• In common system, aldehydes are named by replacing “–ic acid” from the
common name of corresponding carboxylic acid with “aldehyde”.
• The substituent attached to the carbon chain is indicated by Greek letters α-,
β-, γ-, δ- and so on.
• The carbon which is directly bonded to –CHO group is called α- carbon.

• In IUPAC system, aldehydes are called “alkanals” by replacing “e” from

alkanes with “al”.
• The longest chain containing –CHO group is taken as parent chain.
• The position of substituent is indicated by suitable number where the
terminal carbon is always considered as number 1.
 NOMENCLATURE
Aldehydes Common Name IUPAC Name

HCHO Formaldehyde Methanal

CH3CHO Acetaldehyde Ethanal

CH3CH2CHO Propionaldehyde Propanal

CH3CH2CH2CHO n-Butyraldehyde Butanal

CH3CH2CH2CH2CHO n-Valeraldehyde Pentanal

CH3-CH2-CH-CH2-CHO β-Methylvaleraldehyde 3-Methylpentanal

CH3
 NOMENCLATURE
• FOR KETONES
• In common system, the names of unsymmetrical ketones are obtained by writing the names
of the two alkyl groups in alphabetical order followed by the term “ketone”.
• For symmetrical ketones, the term “dilalkyl” is used before “ketone”.

• In IUPAC system, ketones are called “alkanones”.

• The longest chain containing >C=O is taken as parent structure and “e” of alkane is replaced
with “one”.

Ketones Common Name IUPAC Name

CH3COCH3 Dimethyl ketone or Propanone

acetone
CH3CH2COCH3 Ethyl methyl ketone Butanone

CH3CH2COCH2CH3 Diethyl ketone Pentan-3-one

CH3CH2CH2COCH3 Methyl n-propyl ketone Pentan-2-one

CH3-CH—CO-CH3 Methyl isopropyl ketone 3-Methylbutan-2-one

CH3
 ISOMERISM
• Aldehydes and ketones show following types of isomerism:
1. Chain isomerism:
• These isomers differ in number of carbon atoms in the longest carbon chain.
• Both aldehydes and ketones show chain isomerism.
• Aldehydes with at least 4 carbon atoms whereas ketones with at least 5 carbon atoms give
chain isomerism.
O CH3 O
∥ ∥
CH3-CH2-CH2-C-H CH3-CH—C-H
Butanal 2-Methylpropanal

O CH3 O
∥ ∥
CH3-CH2-CH2—C-CH3 CH3-CH—C-CH3
Pentan-2-one 3-Methylbutan-2-one
 ISOMERISM
2. Functional isomerism:
• These isomers differ in functional groups.
• Aldehydes and ketones are functional isomers of one another.
O O
∥ ∥
CH3-CH2-C-H CH3—C—CH3
Propanal Propanone

3. Metamerism:
• These isomers differ in the nature of alkyl groups bonded to either side of functional group.
• Only ketones show this type of isomerism.
O O
∥ ∥
CH3-CH2-CH2—C-CH3 CH3-CH2—C-CH2-CH3
Pentan-2-one Pentan-3-one
 GENERAL METHODS OF PREPARATION

1. By catalytic dehydrogenation of alcohols:

When vapours of primary alcohols are heated with copper at 300℃, dehydrogenation
occurs and aldehydes are formed.

Cu 300℃
R-CH2-OH R-CHO + H2
I˚-alcohol aldehyde

O
∥
Cu
CH3-CH2 –OH CH3-C –H + H2
300℃
Ethanol Ethanal
Similarly, secondary alcohols on catalytic dehydrogenation produce ketones.
Cu
R-CH-OH R-CO-R + H2
300℃
R ketone
2˚-alcohol
 GENERAL METHODS OF PREPARATION
O
Cu ∥
• CH3-CH –OH CH3-C –CH3 + H2
300℃
CH3
Propan-2-ol Propanone

2. By oxidation of alcohols:
Primary alcohols on oxidation using pyridinium chlorochromate (PCC) produce
aldehydes.
O
PCC, CH2Cl2 ∥
R-CH2-OH R-C-H
I˚-alcohol aldehyde

O
CH3-CH2 –OH PCC, CH2Cl2 ∥
CH3-C –H
Ethanol Ethanal

• Use of other oxidising agents like KMnO4, acidified K2Cr2O7, glacial acetic acid, etc. may
further oxidise aldehydes into carboxylic acids.
 GENERAL METHODS OF PREPARATION

• When secondary alcohols are oxidised by using chromic anhydride in pyridine ( Sarett’s
reagent), ketones are obtained.
O
CrO3, Pyridine ∥
R-CH –OH R- C –R
R ketone
2˚-alcohol
O
CrO3, Pyridine ∥
CH3-CH –OH CH3-C –CH3
CH3 Propanone
Propan-2-ol

3. Ozonolysis of alkenes:
Alkenes react with ozone to produce ozonide which on heating with zinc dust and water
gives aldehydes or ketones or their mixture.
This reaction is used to locate the position of double bond in the alkenes.
 GENERAL METHODS OF PREPARATION

O
O O
C C Zn/H2O ∥ ∥
C=C + O3 -C – + -C –
-ZnO
Carbonyl compounds
alkene O O
ozonide

Straight chain alkenes produce aldehydes on ozonolysis.

O
H H O O
H H Zn/H2O ∥ ∥
C C
C=C + O3 H-C –H + H-C –H
H H
H H -ZnO
methanal methanal
ethene O O
ozonide
 GENERAL METHODS OF PREPARATION
O
CH3 H O O
C C Zn/H2O ∥ ∥
CH3-CH=CH2 + O3 H H CH3-C –H + H-C –H
-ZnO
propene ethanal methanal
0 O
ozonide

Ozonolysis of branched chain alkenes gives mixture of aldehydes and ketones or just ketones.

O
CH3 H O O
C C Zn/H2O ∥ ∥
CH3-C=CH2 + O3 H CH3-C –CH3 + H-C –H
CH3 -ZnO
CH3 propanone methanal
0 O
2-methylpropene
ozonide
 GENERAL METHODS OF PREPARATION
O CH3
CH3 CH3 O O
CH3 O3 C C Zn/H2O ∥ ∥
CH3 CH3 CH3-C –CH3 CH3-C –CH3
C=C -ZnO +
CH3 CH3 propanone propanone
2,3-dimethylbut-2-ene
0 O
ozonide

4. From acid chlorides:

Aldehydes can be prepared by reduction of acid chlorides with hydrogen in presence of palladium
suspended over barium sulphate ( Rosenmund’s reduction).

O O
∥ Pd/BaSO4 ∥
R- C –Cl + H2 R- C –H + HCl
Quinoline
Acid chloride Aldehyde
 GENERAL METHODS OF PREPARATION

O O
∥ Pd/BaSO4 ∥
CH3-C –Cl + H2 Quinoline
CH3-C –H + HCl
Acetyl chloride Ethanal
Ethanoyl chloride

Ketones can be prepared from acid chlorides by reacting with dialkyl cadmium.

O O
∥ Dry ether ∥
R- C –Cl + R2Cd R- C –R + CdCl2
Acid chloride Dialkyl cadmium ketone

O O
∥ Dry ether ∥
+ (CH3)2Cd + CdCl2
CH3-C –Cl CH3-C –CH3
Acetyl chloride Dimethyl Propanone
cadmium
 GENERAL METHODS OF PREPARATION

5. From Gem-dihalides:
Aldehydes and ketones are obtained from alkaline hydrolysis of gem-dihalides ( two halogen
atoms bonded to the same carbon atom).
Aldehydes can be prepared using terminal dihalides.

O
X OH ∥
R-CH + 2 NaOH R-CH R- C –H
-2NaX -H2O
X OH Aldehyde
1,1-Dihaloalkane unstable

Cl OH O
∥
CH3-CH + 2NaOH CH3-CH CH3-C –H
Cl -2NaCl OH -H2O
Ethanal
1,1-Dichloroethane unstable
 GENERAL METHODS OF PREPARATION

Ketones are obtained by alkaline hydrolysis of non-terminal dihalides.

X OH O
∥
R-C-R + 2KOH R-C-R R- C –R
-2KX -H2O
ketone
X OH
2,2-Dihaloalkane unstable

Cl OH O
∥
CH3-C-CH3 + 2KOH CH3-C-CH3 CH3-C –CH3
-2KCl -H2O
Propanone
Cl OH
2,2-Dichloropropane unstable
 GENERAL METHODS OF PREPARATION

6. From alkynes:
When alkynes are catalytically hydrated, i.e. heated with water in presence of dil. H2SO4 and
HgSO4 as catalyst at 60℃, aldehydes and ketones are produced.
Catalytic hydration of ethyne gives ethanal.
O
Dil.H2SO4 tautomerism ∥
CH≡CH + H2O CH2=CH-OH CH3-C –H
HgSO4, 60℃
ethyne ethenol ethanal

All other alkynes except ethyne give ketones on catalytic hydration.

OH O
Dil.H2SO4 tautomerism ∥
CH3-C≡CH + H2O CH3-C=CH2 CH3-C –CH3
HgSO4, 60℃ Propanone
Propyne Propen-2-ol
 PHYSICAL PROPERTIES
• State: Formaldehyde is gas at a room temperature. Other lower aldehydes and ketones are
colourless volatile liquid. Higher aldehydes and ketones are solid at ordinary temperature.
• Odour: Lower members of aldehydes have unpleasant, irritating smell while lower ketones
have pleasant odour. Higher aldehydes and ketones possess sweet, pleasant smell.
• Density: Aldehydes and ketones are lighter than water.
• Solubility: Lower members of aldehydes and ketones are soluble in water due to their ability
to form intermolecular hydrogen bond with water molecules.

C=O-------- H-O-H-------O=C

Intermolecular H-bond

• Higher members are insoluble in water due to increase in number of carbon atoms
(hydrophobic part). They are soluble in organic solvents like ether and alcohol.
 PHYSICAL PROPERTIES
• Boiling point: Aldehydes and ketones have higher boiling point than corresponding alkanes
having comparable mass. This is due the presence of strong dipole-dipole interaction
between the >C=O dipoles. However, they cannot form hydrogen bond among themselves. So
their boiling point is lower than those of alcohols and carboxylic acids.
 CHEMICAL PROPERTIES
• Structure and nature of carbonyl group

δ+ δ-
1200 C=O

In carbonyl group, the carbonyl carbon is doubly bonded to carbon containing one sigma
and one pi bond. Both the carbonyl carbon and oxygen are sp2 hybridised. The bond angle
between each angle is 1200 and it has trigonal planar geometry.
The oxygen atom being more electronegative in nature, attracts the bonded pair of
electron with carbon, more towards itself. As a result, the carbon-oxygen bond in carbonyl
group gets polarised. The carbon atom acquires slightly positive charge whereas oxygen
acquires slightly negative charge. Hence, the partially positively charged carbon is easily
attacked by nucleophile.
O- OH
- H+
>C=O + Nu C C
Carbonyl
group Nucleophile Nu Nu
Addition
compound
 CHEMICAL PROPERTIES
• Therefore, the typical reaction of aldehydes and ketones is nucleophilic addition reaction.
• The fundamental reason of reactivity of carbonyl compounds towards nucleophile is the
ability of oxygen to carry negative charge.
• Aldehydes are more reactive than ketones towards nucleophilic addition reaction. This can be
explained as follows:
Inductive effect: Ketones contain two electron releasing alkyl groups ( only one in aldehydes). So,
in ketones, the positive charge in carbonyl carbon is more reduced which makes it less susceptible
for attack by nucleophile.
R
R δ +
δ - δ+ δ-
C=O C=O

H R
ketone
aldehyde
Steric effect: The effect due to size is more prominent in ketones than in aldehydes. This is
because ketones contain two alkyl groups with large size. They create more crowding around
carbonyl carbon and make it difficult for nucleophile to attack.
 Distinction of aldehydes and ketones
(from other functional groups)
2,4-DNP test:
Aldehydes and ketones (carbonyl compounds) can be distinguished from other compounds by
using 2,4-DNP reagent. With 2,4-dinitrophenylhydrazine, aldehydes and ketones produce
yellow-orange or orange-red ppt. of 2,4-dinitrophenylhydrazones. The hydrazones obtained have sharp
melting point and are crystalline in nature.
NO2 NO2
OH

C=O + NH2-NH NO2 C-N-NH NO2

H
Carbonyl 2,4-dinitrophenylhydrazine -H2O
compound
NO2

C=N-NH NO2

2,4-dinitrophenylhydrazone
CH3 NO2 CH3 NO2

C=O + NH2-NH NO2 C=N-NH NO 2 + H2O

H H
Ethanal-2,4-dinitrophenylhydrazone
2,4-dinitrophenylhydrazine
Ethanal

NO2 CH3 NO2

CH3

C=O + NH2-NH NO2 C=N-NH NO 2 + H2O

CH3 CH3
propanone 2,4-dinitrophenylhydrazine Propanone-2,4-dinitrophenylhydrazone
 Distinction between aldehydes and ketones

1. Using Tollen’s reagent:

Tollen’s reagent is an ammoniacal solution of silver nitrate. It is prepared by adding NH4OH
solution AgNO3 solution till the ppt. of Ag2O initially formed, redissolves.

2AgNO3 + 2NH4OH Ag2O + 2NH4NO3 + H2O

Grey ppt.
Ag2O + 4NH4OH 2[Ag(NH3)2]+ OH- + 3H2O
Tollen’s reagent
Aldehydes show reducing properties. They reduce Tollen’s reagent into metallic silver upon
warming. This reaction is also known as silver mirror test or Tollen’s test.
O O
∥ ∥
R- C –H + 2[Ag(NH3)2]+ OH - R- C –O-NH4+ + 2Ag + H2O + 3NH3
Silver
Aldehyde Tollen’s reagent mirror
O O
∥ ∥
CH3-C –H
+
+ 2[Ag(NH3)2] OH -
CH3- C –O-NH4+ + 2Ag + H2O + 3NH3
Silver mirror
ethanal Tollen’s reagent
Distinction between aldehydes and ketones
• Both aliphatic and aromatic aldehydes reduce Tollen’s reagent.
• Ketones do not reduce Tollen’s reagent because they lack oxidisable
hydrogen atom. Hence, this reaction can be used to distinguish aldehydes
from ketones.
O O
∥ ∥
C-H C- O-NH4+

+ 2[Ag(NH3)2]+ OH- + 2Ag + H2O + 3NH3

Silver
mirror
benzaldehyde

2. Using Fehling’s solution:

Alkaline solution of CuSO4 containing some Rochelle salt i.e. sodium potassium
tartarate is called Fehling’s solution. It can be prepared by adding alkaline solution of
Rochelle salt (Fehling’s solution A) to an aqueous solution of CuSO4 (Fehling’s solution B).

• Aliphatic aldehydes reduce Fehling’s solution to red ppt. of cuprous oxide.

 Distinction between aldehydes and
ketones
O O
∥ ∥
R- C –H + 2Cu++ + 5OH- R- C –O- + Cu2O + 3H2O
Aldehyde Red ppt.
From Fehling’s
solution(deep cuprous oxide
blue colour)

O O
∥ ∥
CH3-C –H ++
+ 2Cu + 5OH - CH3- C –O- + Cu2O + 2H2O
From Fehling’s cuprous oxide
ethanal
solution(deep Red ppt.
blue colour)

● Aromatic aldehydes do not reduce Fehling’s solution.

 NUCLEOPHILIC ADDITION REACTIONS
1. Addition of hydrogen:
Aldehydes and ketones are easily reduced into corresponding alcohols by heating with hydrogen in
presence of nickel as catalyst ( catalytic hydrogenation).
Aldehydes are reduced into corresponding primary alcohols.

O
∥ Ni
R- C –H + H2 R-CH2-OH

Aldehyde 1˚- alcohol

O
∥ Ni
CH3-C –H + H2 CH3-CH2-OH

ethanal ethanol

O
∥ Ni
R- C –R + H2 R-CH –OH
ketone R
2˚- alcohol
 NUCLEOPHILIC ADDITION REACTIONS

O
∥
+ H2 Ni CH3-CH –OH
CH3-C –CH3
propanone CH3
Propan-2-ol
2. Addition of HCN:
Aldehydes and ketones react with hydrogen cyanide to give cyanohydrins.

C=O + HCN H+
C –OH
CN
cyanohydrin
CH3
C=O + HCN H+
CH3-CH –OH
H CN
acetaldehyde cyanohydrin
acetaldehyde (2-hydroxypropanenitrile)
CH3 CH3
H+
C=O + HCN C –OH + NH3

CH3 CN
CH3
acetone
acetone
cyanohydrin

These cyanohydrins like other cyanides, are easily hydrolysed in presence of acid to get α-hydroxy
carboxylic acids.

H+
CH3-CH –OH CH3-CH –COOH
CN OH
2-hydroxy 2-hydroxy Propanoic
propanenitrile acid(Lactic Acid)
(acetaldehyde
Cyanohydrin)

Q1. How would you convert ethanal into 2-hydroxypropanoic acid?

Q2. What happens when ethanal is treated with HCN followed by hydrolysis?
CH3 CH3
H+ C–COOH + NH3
C –OH
CH3 CN CH3 OH

2-hydroxy-2-methyl 2-hydroxy-2-methyl
propanenitrile Propanoic acid
(acetone
Cyanohydrin)
Dehydration of α-hydroxy carboxylic acids produce α,β-unsaturated acids.

-H2O
CH3-CH –COOH CH2=CH –COOH
OH Propenoic acid
Lactic acid
3. Addition of NaHSO3:
Aldehydes and ketones react with saturated solution of sodium bisulphite in presence of
ethanol to give bisulfite adducts.
OH

C=O + NaHSO3 ethanol C

SO-3Na+
adduct
CH3 CH3 OH
C=O + NaHSO3 ethanol C

H H SO-3Na+
acetaldehyde Acetaldehyde
Sodium bisulphite
(adduct)
 CH3 OH
CH3
ethanol
C=O + NaHSO3 C

CH3 CH3 SO-3Na+

acetone Acetone
Sodium bisulphite
(adduct)
The solid adduct can be decomposed by acid or base to regenerate the original aldehyde or
ketone. Hence, this reaction can be used for purification and separation of carbonyl compounds.

CH3 OH
O
C
+
H or OH - ∥ + SO + Na +
+ H2O
CH3-C –H 2

H SO-3Na+ acetaldehyde

Acetaldehyde
Sodium bisulphite
 ADDITION FOLLOWED BY ELIMINATION
Action with ammonia derivatives:
• Ammonia derivatives are the organic compounds that are obtained by replacing one H-atom
from ammonia and are represented as NH2-G.
• Aldehydes and ketones react with ammonia derivatives to form compounds containing
carbon-nitrogen double bond (C=N) called imines. It occurs in two stages:
a) Addition of NH3 catalyzed by acid
..
NH2-G
C=O C –OH Carbinol
+
H amine
NH-G

b) Elimination of water to form imine

C –OH -H2O C =N-G

NH-G
imine
ADDITION FOLLOWED BY ELIMINATION
1. Addition of hydroxyl amine (NH2-OH):
Aldehydes and ketones react with hydroxyl amines to form oximes.

CH3
C=O + NH2-OH H+ + H2O
CH3-CH =N-OH

H acetaldoxime
acetaldehyde

CH3
C=O + NH2-OH H+ CH3-C=N-OH + H2O

CH3 CH3

acetone acetoxime
ADDITION FOLLOWED BY ELIMINATION
2. Addition of hydrazine (NH2-NH2):
With hydrazine aldehydes and ketones give corresponding hydrazones.

CH3
C=O + NH2-NH2 H+ + H2O
CH3-CH =N-NH2
Acetaldehyde
H
hydrazone
acetaldehyde

CH3
C=O + NH2-NH2 H+ + H2O
CH3-C =N-NH2
CH3 CH3
Acetone
acetone
hydrazone
ADDITION FOLLOWED BY ELIMINATION
3. Addition of phenylhydrazine (C6H5NH-NH2):
On reacting with phenylhydrazine, aldehydes and ketones produce corresponding
phenylhydrazones.

CH3
H+
C=O + NH2-NH CH3-CH =N-NH + H2 O

H phenylhydrazine Acetaldehyde
acetaldehyde phenylhydrazone

CH3
C=O + NH2-NH H+ + H2 O
CH3-C =N-NH
CH3 CH3
phenylhydrazine
Acetone
acetone phenylhydrazone
ADDITION FOLLOWED BY ELIMINATION
4. Addition of semicarbazide ( NH2-NHCONH2):
Aldehydes and ketones react with semicarbazide to form corresponding semicarbazones.

CH3
C=O + NH2-NHCONH2 H+ CH3-CH =N-NHCONH2 + H2O
H Acetaldehyde
semicarbazone

acetaldehyde

CH3
C=O + NH2-NHCONH2 H+ CH3-C =N-NHCONH2 + H O
2
CH3
CH3
Acetone
acetone semicarbazone
 SOME SPECIAL REACTIONS OF
ALDEHYDES AND KETONES
1. Aldol condensation:

• Aldols are the compounds containing both aldehyde (or ketone) and alcohol functional group.
• Aldehydes and ketones having at least one α-hydrogen atom give this reaction.
When aldehydes and ketones that contain at least one α-hydrogen atom react with dilute
base like NaOH, they are condensed to form β-hydroxy aldehydes or β-hydroxy ketones i.e. aldols.

O O OH O
∥ + ∥ ∥
Dil.NaOH
CH3-C –H CH3-C –H CH3-CH-CH
β α 2
-C-H
2-molecules of ethanal 3-hydroxybutanal
β-hydroxy butyraldehyde
(Aldol)
 SOME SPECIAL REACTIONS OF
ALDEHYDES AND KETONES
O O O
∥
OH ∥
∥ Dil.NaOH
CH3-C –CH3 + CH3-C –CH3 CH3-C-CH2-C-CH3
CH3
2-molecules of propanone
4-hydroxy-4-methyl pentan-2-one
Crossed-Aldol condensation:
In this reaction, two different carbonyl compounds ( different aldehydes, different ketones or
mixture of aldehydes and ketones) one of them having at least one α-hydrogen atom undergo
condensation to give aldols.

O O
O
∥
∥ ∥ Dil.NaOH
H-C –H + CH3-C –H
OH-CH2-CH2-C-H

methanal ethanal 3-hydroxypropanal

 SOME SPECIAL REACTIONS OF
ALDEHYDES AND KETONES
O O OH O
∥ ∥ Dil.NaOH ∥
CH3-C –H + CH3-C –CH3 CH3-CH-CH2-C-CH3
ethanal propanone 4-hydroxypentan-2-one

2. Cannizzaro reaction:
Aldehydes that do not contain any α-hydrogen atom when treated with conc. alkali (aq. or
alc.), undergo self oxidation-reduction to give a mixture of alcohol and salt of carboxylic acid. This
is called Cannizzaro reaction.
This reaction is also called disproportionation reaction. One aldehyde molecule is oxidized into
salt of salt of carboxylic acid where another molecule is reduced into corresponding primary
alcohol.

O O O
∥ ∥ conc.NaOH ∥
H-C –H + H-C –H CH3-OH
+ H-C –O-Na+
methanal methanal methanol Sodium
methanoate
 SOME SPECIAL REACTIONS OF
ALDEHYDES AND KETONES
O O O
∥ ∥ ∥
C-H C-H CH2-OH C-O-Na+
conc.NaOH
+ +

benzaldehyde benzaldehyde Benzyl alcohol Sodium

benzoate

The Cannizzaro reaction between different aldehyde molecules is called Cross-Cannizzaro

reaction.
O
∥ CH2-OH
C-H
O O
∥ conc.NaOH ∥
+ H-C –H + H-C –O-Na+

methanal Sodium
benzaldehyde Benzyl alcohol methanoate
 SOME SPECIAL REACTIONS OF
ALDEHYDES AND KETONES
3. Clemmensen’s reduction:
When aldehydes and ketones are treated with amalgamated zinc and conc. HCl, they are
reduced into corresponding alkanes. This is called Clemmensen’s reduction.
This reaction is used to convert aldehydes and ketones directly into alkanes.

C=O + 4[H] Zn-Hg -CH2- + H2 O

Conc.HCl
methylene
Carbonyl
compound
O
∥ Zn-Hg
CH3-C –H + 4[H] CH3-CH3 + H2 O
Conc.HCl
ethanal ethane

O
∥ Zn-Hg
CH3-C –CH3 + 4[H] CH3-CH2–CH3 + H2O
Conc.HCl
propanone propane
 SOME SPECIAL REACTIONS OF
ALDEHYDES AND KETONES
4. Wolff-Kishner reduction:
On heating aldehydes and ketones with hydrazine and strong alkali in presence of ethylene
glycol at 200℃, the carbonyl group is reduced into methylene group. This is called
Wolff-Kishner reduction.

NaOH/200℃
C=O + NH2-NH2 -CH2- + N2 + H2O
Ethylene glycol
methylene
Carbonyl
compound

O NaOH/200℃
∥
CH3-C –H + NH2-NH2 Ethylene glycol CH3–CH3 + N 2 + H 2O
ethanal ethane

O
∥ NaOH/200℃
+ NH2-NH2 CH3-CH2–CH3 + N 2 + H 2O
CH3-C –CH3 Ethylene glycol
propanone propane
 SOME SPECIAL REACTIONS OF
ALDEHYDES AND KETONES
5. Action with PCl5:
On reacting aldehydes and ketones with PCl5, two chlorine atoms are bonded to the carbonyl
carbon and gem-dichloroalkanes (two chlorine atoms are bonded to same carbon) are formed.

C=O + PCl5 CCl2 + POCl3

Gem-dichloride
Carbonyl
compound
O Cl
∥
CH3-C –H + PCl5 CH3-CH + POCl
3

ethanal
Cl
1,1-dichloroethane
O Cl
∥
CH3-C –CH3 + PCl5 CH3-C-CH3 + POCl3

propanone
Cl
2,2-dichloropropane
 SOME SPECIAL REACTIONS OF
ALDEHYDES AND KETONES
6. Action with LiAlH4:
Aldehydes and ketones are reduced into primary and secondary alcohols respectively when
heated with LiAlH4 .
LiAlH4
C=O + 2[H] CH-OH
△
Carbonyl compound alcohol
O
∥ LiAlH4
CH3-C –H + 2[H]
CH3-CH2-OH
△
ethanal
ethanol
O OH
∥ LiAlH4
CH3-C –CH3 + 2[H] CH3-CH-CH3
△
propanone Propan-2-ol
 SOME SPECIAL REACTIONS OF
METHANAL
1. Action with ammonia:
Methanal reacts with ammonia to for hexamethylene tetramine [(CH2)6N4], also commonly
called as urotropine, is formed.
Urotropine is used as an antiseptic for urinary disorder like rheumatism.
O
∥
H-C –H + 4NH3 (CH2)6N4 + 6H2O
ethanal urotropine

Structure of
urotropine
• Nitration of urotropine under controlled conditions gives an explosive, RDX (research and
development explosive).
 SOME SPECIAL REACTIONS OF
METHANAL
2. Action with phenol:
Methanal condenses with phenol in presence of acid or base to give highly synthetic
polymer called bakelite. Bakelite is used to make electric switches, handle of pressure cooker, etc.
OH OH OH
O CH2-OH
∥ -
+ OH+
H-C –H
methanal
phenol o-hydroxy CH2-OH
benzyl alcohol p-hydroxy
benzyl alcohol
Formation of bakelite:

OH OH
CH2-OH
+ H2O

CH2-OH
 FORMALIN AND ITS USES
• Methanal is highly soluble in water.
• Since it is gaseous in normal condition, it is marketed as 40% aqueous solution under the
trade name of formalin.
• Composition of formalin: 40% HCHO + 8% CH3OH + 52% H2O

• The main use of formalin is as disinfectant for the preservation of biological specimen.
• Also used as preservative is some foods and some products like antiseptics, cosmetics, etc.
 AROMATIC ALDEHYDES AND KETONES
• Aromatic aldehydes are the organic compounds in which one aryl group is bonded to
carbonyl carbon.

CHO CHO
CHO OH

benzaldehyde naphthaldehyde salicyladehyde

• Aromatic ketones are those compounds where the carbonyl carbon is bonded to one or two
aryl groups.

O O
∥ ∥
-C –CH3 -C –

acetophenone benzophenone
 PREPARATION
1. Benzaldehyde from toluene:
When toluene is oxidised by CrO3 in presence of acetic anhydride followed by alkaline
hydrolysis, benzaldehyde is formed.
CH3 CH(OOCCH3)2 CHO
CrO3 H2O/OH- + 2CH3COOH
(CH3CO)2O

toluene benzaldehyde

Laboratory preparation of benzaldehyde:

In laboratory, benzaldehyde is prepared by oxidation of toluene with cerium oxide (CeO2) in
presence of conc. H2SO4 at 60℃.
CH3 CHO

+ [O] CeO2/60℃ + H2O

conc.H2SO4
toluene benzaldehyde
 PREPARATION
2. Acetophenone from benzene (Friedel-Craft’s acylation):
Acetophenone can be prepared by heating benzene with acetyl chloride in presence of
anhydrous AlCl3 as catalyst. O
∥
O C-CH3
∥
+ + anhy.AlCl3 + HCl
CH3-C –Cl
△

benzene acetyl chloride acetophenone

 PROPERTIES OF BENZALDEHYDE
• PHYSICAL PROPERTIES
• It is an oily, colourless liquid.
• It has bitter almond smell.
• It is insoluble in water but soluble in organic solvents like ether, alcohol, etc.
• It boils at 179℃.

• CHEMICAL PROPERTIES
1. Perkin condensation:
When aromatic aldehyde is heated with anhydride of aliphatic acid in presence of sodium
salt of same acid from which anhydride is derived, α,β-unsaturated acid is obtained.
On heating benzaldehyde with acetic anhydride in presence of sodium acetate, it produces
cinnamic acid.
CHO CH=CH-COOH
O
∥ CH3COONa
+ CH3-C O + CH3COOH
CH3-C 180℃
∥
benzaldehyde O Cinnamic acid
acetic anhydride
 PROPERTIES OF BENZALDEHYDE
2. Benzoin condensation:
Two molecules of benzaldehyde undergo condensation on heating with aqueous or
alcoholic solution of NaCN or KCN to give α-hydroxy ketone i.e. Benzoin.
This reaction is called Benzoin condensation.
CHO CHO
O OH
∥
+ KCN, reflux -C-CH –
C2H5OH, H2O

Two molecules of benzaldehyde benzoin

3. Cannizzaro reaction:
Aldehydes that do not contain any α-hydrogen atom when treated with conc. alkali (aq. or
alc.), undergo self oxidation-reduction to give a mixture of alcohol and salt of carboxylic acid. This
is called Cannizzaro reaction.
This reaction is also called disproportionation reaction. One aldehyde molecule is oxidized into
salt of salt of carboxylic acid where another molecule is reduced into corresponding primary
alcohol.
 PROPERTIES OF BENZALDEHYDE
O O O
∥ ∥ ∥
C-H C-H CH2-OH C-O-Na+
+ + conc.NaOH +

benzaldehyde benzaldehyde Benzyl Sodium

alcohol benzoate
The Cannizzaro reaction between different aldehyde molecules is called Cross-Cannizzaro reaction.

O
∥ CH2-OH
C-H
O O
+ ∥ + ∥
conc.NaOH
H-C –H H-C –O-Na+

Benzyl Sodium
benzaldehyde methanal
alcohol methanoate
 ELECTROPHILIC SUBSTITUTION
REACTION
• Aromatic aldehydes and ketones give meta substituted products on electrophilic substitution
reaction.

Fig. :Resonating structures of benzaldehyde

• The carbonyl group deactivates the benzene ring and creates partial positive charge at ortho
and para position.
• This renders ortho and para position less reactive towards the incoming electrophile.
• Hence, electrophilic substitution reaction occurs in aromatic aldehydes and ketones less
readily and at meta position.
 ELECTROPHILIC SUBSTITUTION
REACTION
CHO
Cl2/FeCl3
+ HCl (Halogenation)
Cl
m-chlorobenzaldehyde

CHO CHO

SO3/△
+ H2O (Sulphonation)
fuming H2SO4
SO3H
benzaldehyde m-formyl benzene
sulphonic acid
CHO

Conc.HNO3/△
+ H2 O
Conc. H2SO4 (Nitration)
NO2
m-nitrobenzaldehyde
 ELECTROPHILIC SUBSTITUTION
REACTION
COCH3
Cl2/FeCl3
+ HCl (Halogenation)
Cl
m-chloroacetophenone

COCH3 COCH3

SO3/△ + H2O
(Sulphonation)
fuming H2SO4
SO3H
acetophenone m-acetophenone
sulphonic acid
COCH3

Conc.HNO3/△ + H2O (Nitration)

Conc. H2SO4
NO2
m-nitroacetophenone
 MCQs
1. 1. The molecular formula C3H6O represents which of the following compounds?
a. Propanol b. Propanoic acid c. Methoxy ethane d. Propanal
2. Distillation of calcium acetate gives,
a. Ethanal b. Propanone c. Methanal d. Butanone
3. When ethene is subjected to ozonolysis, it gives,
a. Methanal b. Ethanal c. Methanoic acid d. Methanol
4. A compound produced red precipitate with Fehling solution. It is probably,
a. Acetone b. Acetic acid c. Acetaldehyde d. Ethane
5. Which of the following compound produces ethanal on ozonolysis?
a. Ethene b. But-1-ene c. But-2-ene d. 2-methylpropene
6. An example of mixed or unsymmetrical ketone is,
a. Propanone b. Pentan-3-one c. Acetophenone d. Benzophenone
7. When ethyne gas is passed through dil. H2SO4 in presence of HgSO4, it gives,
a. Propanone b. Ethanal c. Butanone d. Methanal
8. Oxidation of isopropyl alcohol produces,
a. Propanone b. Propanal c. Ethanal d. Butanone
9. Ethanoyl chloride produces ethanal when reduced with H2 /Pd-BaSO4. The reaction is
called………….reduction.,
a. Clemmensen b. Mendius c. Rosenmund d. Wolf-Kishner
 MCQs
1. 1. Acetone can be prepared from ethanoyl chloride by reacting it with,
a. Chloromethane b. H2/Ni c. CH3-NH2 d. (CH3)2Cd
2. When 1,1-dichloroethane is boiled with aqueous KOH, it produces,
a. Ethanol b. Ethanal c. Methanal d. Butanone
3. The most suitable reagent used to distinguish ethanal from ethanol is,
a. 2,4-DNP b. NaOH/I2 c. Aq. KOH d. Conc. H2SO4
4. Which of the following pair of compounds can be distinguished by Tollen’s test?
a. Acetone and butanone b. Methanal and ethanal c. Propanal and propanone
d. Ethanal and propanal
5. Aldehyde can be distinguished from ketone by the use of which reagent?
a. Fehling Solution b. Tollen’s reagent c. Benedict’s solution d. All
6. Which of the following reagent is used in test of diabetes from urine?
a. NaOH/I2 b. H2/Pd-BaSO4 c. Fehling solution d. Zn-Hg/HCl
7. Addition of HCN on ethanal followed by hydrolysis of product gives,
a. Mandelic acid b. Lactic acid c. ethyl acetate d. Cinnamic acid
8. Biodegradable plastic like PLA are obtained by polymerisation of,
a. Lactic acid b. Acetone cyanohydrin c. Ethanoic acid d. 1,2-dichloroethene
9. Aldehyde and ketones are purified by the use of,
a. HCN b. NaOH c. NaHSO3 d.Na2SO4
 MCQs
1. 1. Ethanal is warmed with dilute NaOH. The product is,
a. Ethanoic acid b. 2-hydroxypropanoic acid c. But-2-enal d. 3-hydroxybutanal
2. Which of the following is an aldol?
a. 𝝰-hydroxy ketones b. 𝛃-hydroxy aldehyde c. 𝝰-hydroxy aldehydes d. poly aldehydes
3. Which of the following compound does not undergo aldol condensation?
a. 2,2-dimethylpropanal b. Ethanal c. Propanone d. 2-methylbutanal
4. Methanal condenses with conc. NaOH & give CH3OH and HCOONa. The reaction is called,
a. Aldol condensation b. Perkin’s reaction c. Cannizaro’s reaction d. Wittig reaction
5. A compound on clemenson's reduction produces propane. The compound is,
a. Ethanal b. Propanoic acid c. Propanol d. Propanone
6. Methanal and ethanal can be distinguished by,
a. Iodoform test b. Tollen’s test c. Fehling test d. 2,4-DNP test
7. Butan-2-ol and butanone can be separated by the use of which reagent?
a. Na2SO3 b. NaHSO3 c. NaOH d. KClO3
8. Iodoform test is given by,
a. Ethanal b. Ethanoic acid c. Propanal d. Methanal
9. Cannizaro’s reaction is possible in,
a. Acetaldehyde b. Acetone c. Benzaldehyde d.Acetophenone
 MCQs
1. 1. Ethanal produced ethane in a reaction. The reagent used is probably ,
a. NaOH/I2 b. NH2-NH2/KOH in glycol c. H2/Pd-BaSO4 d. LiAlH4
2. Condensation of formaldehyde with ammonia produces,
a. Methanamine b. Urotropine c. Hydrazone d. Bakelite
3. Catalytic dehydrogenation of primary alcohol produces,
a. Aldehydes b. Ketones c. Carboxylic acid d. Alkenes
4. Benzaldehyde can be converted to cinnamic acid via,
a. Aldol condensation b. Benzoin condensationc. Perkin’s reaction d. Wittig reaction
5. The Chlorination of benzaldehyde produces ………… as major product.
a. o-chlorobenzaldehyde b. benzoyl chloride c. Chlorobenzene d. m-chlorobenzaldehyde
6. Which of the following compound produces benzaldehyde when treated with CeO2/H+ ?
a. Toluene b. Benzyl alcohol c. Phenol d. Benzene
7. Methanal is condensed with ‘A’ to produce bakelite after polymerisation. ‘A’ is,
a. Benzaldehyde b. Phenol c. Benzene d. Aniline