Aldehyde and ketone

 Introduction, nomenclature and isomerism

 Preparation of aldehydes and ketones from:
 Dehydrogenation and oxidation of alcohol,
 Ozonolysis of alkenes,
 Catalytic hydration of alkynes
 Acid chloride,
 Gem dihaloalkane,
 Physical properties of aldehydes and ketones ;
 Chemical properties
 Structure and nature of carbonyl group ;
 Distinction between aldehyde and ketones by using 2,4- DNP
reagent, Tollen’s reagent, Fehling’s solution ;
 Addition reaction: addition of H2, HCN and NaHSO3
 Action of aldehyde and ketone with ammonia derivatives; NH2OH,
NH2-NH2, phenyl hydrazine, semicarbazide ;
 Aldol condensation ; Cannizzaro’s reaction ; Clemmensen’s
reduction, Wolf-Kishner reduction ; Action with PCl5 and action
with LiAlH4 ; Action of methanal with ammonia and phenol ;
Formalin and its uses

Aromatic aldehydes and Ketones :

 Preparation of benzaldehyde from toluene and acetophenone
from benzene ;
 Properties of benzaldehyde ; Perkin condensation ; Benzoin
condensation ; Cannizzaro’s reaction ; Electrophilic substitution
reaction .

Carbonyl compound
Aldehydes and ketones are the compounds containing carbonyl group,
so are collectively called carbonyl compounds.
Nomenclature
IUPAC: PREFIX+WORD ROOT +PRIMARY SUFFIX +SECONDARY SUFFIX
ALDEHYDE KETONE

Formaldehyde Acetone
Acetaldehyde methylethylketone
Popaionaldehyde
Butyraldehyde

Isomerism in aldehydes and ketones

1 . Chain Isomerism: Aldehydes having at least 4 carbon atoms and
ketones having at least 5 carbon atoms show chain isomerism.
2. Position isomerism: Ketones having at least 5 carbon atoms and
aromatic aldehydes show position isomerism.Eg.

Positional isomerism of ketones is also an example of metamerism due

to difference in alkyl group present on either side of carbonyl group.

3. Functional isomerism: Ketone and aldehyde having same molecular

formula are functional isomers of one another.

Q. Write down functional isomer of compound having molecular

formula C3H6O.
Methanal and ethanal do not have functional isomers.

Q) Write the possible isomeric aldehydes and ketones that can be

formed from C4H8O.
General methods of preparation of aldehydes and ketones
1. From alcohol:
(i) By oxidation of alcohols:

(ii) By dehydrogenation of alcohols:

Secondary alcohols are dehydrogenated to ketones. Eg.

2. By ozonolysis of alkene:
Alkene reacts with ozone to give ozonide. On warming ozonide with Zn
in water, it breaks down to give two molecules of carbonyl compounds
(aldehyde or ketone). This process of formation of ozonide and it’s
decomposition to give carbonyl compounds is called ozonolysis.
Q) How would you prepare acetone and acetaldehyde from ozonolysis
of 2-methylbut-2-ene?
Q) How would you prepare two molecules of acetone from ozonolysis of
2,3-dimethylbut-2-ene?
3. By catalytic hydration of alkynes :
Alkynes react with water in presence of mercuric sulphate and sulphuric
acid to give vinyl alcohol which rearranges to give aldehyde or ketone.

For example, ethyne gives ethanal (i.e. aldehyde).

Propyne gives propanone (i.e. ketone).

Among alkynes only ethyne gives aldehyde and all other alkynes give
ketones.
4. From acid chlorides:

(i) By Rosenmund reduction: Aldehydes can be prepared by reducing

acid chloride solution with hydrogen in the presence of Palladium(Pd)
catalyst deposited on barium sulphate and partially poisoned with
sulphur or quinoline. This reaction is called Rosenmund reduction.

(Acetyl chloride)

Q. How would you prepare propanal from propanoyl chloride ?

Q. Can you prepare the methanol from methanoyl chloride by rosemund
reduction ?

(ii) Ketones can be prepared by treating acid chloride with dialkyl

cadmium.

(Ethanoyl chloride) (Propan-2-one)

Acetyl chloride Dimethyl cadmium
acetone

5. From gem-dihalides:
The hydrolysis of gem dihalides with an alkaline solution gives diol as an
intermediate which is unstable and undergoes dehydration gives
carbonyl compound as final product
Aldehydes are formed when two halogen atoms are attached to
terminal carbon atom.

Ketones are formed when two halogen atoms are attached to non-
terminal carbon atom.
Q. How would you prepare propanal from gem dichloride (1,1
dichloropropane)
Q. how would you prepare butan-2-ene from 2,2-dichlorobutane?

Physical Properties of aldehydes and ketone

1. State: Formaldehyde is gas, Acetaldehyde is a volatile liquid and
other aldehydes from C2 to C11 and ketones up to C11 are liquid at
room temperature, while higher aldehyde and ketone are solids.

2. Boiling point: Aldehydes and ketones have higher boiling point

than hydrocarbon of comparable molecular masses. This is because
aldehydes and ketones contain polar carbonyl group and therefore
there exists strong dipole-dipole interaction between the opposite
end of C=O dipoles.

However, aldehydes and ketones have lower boiling point than alcohols
and carboxylic acid of comparable molecular masses. This is because
dipole-dipole interaction is weaker than intermolecular H-bonding.

Ketones have higher boiling point than isomeric aldehyde due to the two
alkyl groups by which become more polar.

Alcohol > ketone >aldehyde > Hydrocarbon

Decreasing boiling points of compounds with comparable mol. Mass

 3. Solubility:
Lower aldehydes and ketones containing up to 4 carbon atoms are
soluble in water due to formation of hydrogen bond between the
polar carbonyl group and water molecule.
Higher members containing more than 5 carbon are insoluble in
water due to the increase in the rise of water insoluble part.

Chemical Properties
Structure and nature of the carbonyl group
In carbonyl group, there is carbon to oxygen double bond, which consist
of a sigma (σ) bond and a pi (π) bond

.
Both of the carbon and oxygen atoms are sp2 hybridized. One sp2 hybrid
orbital of carbon forms σ-bond with oxygen atom and remaining two
hybrid orbitals form σ-bond with hydrogen or carbon atom. π -bond is
formed by the overlap of unhybridized p- orbitals of carbon and oxygen
atom.
This carbonyl group is trigonal and planar with bond angle of 1200.
In carbonyl group, carbon atom is bonded with oxygen atom which is
more electronegative than carbon. Thus, the bonded pair of electrons
lie more closer to the oxygen atom than carbon atom which leads to the
polarization in carbon-oxygen bond. There is charge separation, oxygen
atom acquires slightly negative charge while the carbon atom acquires
slightly positive charge.

Factors affecting the reactivity of carbonyl compounds towards

nucleophiles
i) Inductive effect

ii) Crowding around a carbonyl carbon atom (steric effect)

The presence of bulkier alkyl or aryl groups on carbonyl carbon
increases the crowding i.e steric hindrance that decreases the
reactivity.

Thus, formaldehyde is more reactive than other aldehydes which in

turn are more reactive than ketones.
 Increasing reactivity order towards nucleophilic addition reaction

Distinction between aldehyde and ketones by using 2,4- DNP reagent,

Tollen’s reagent, Fehling’s solution
A) 2,4-DNP test
Aldehydes and ketones react with 2,4-dinitrophenyl hydrazine (2,4-DNP)
to form yellow, orange or red ppt. of 2,4-dinitrophenyl hydrazone. Eg.

Q) Write a chemical test to distinguish ethanal from ethanol?

Note : 2,4-DNP = Brady’s reagent.

 B)Oxidation reactions of aldehydes
Weak oxidizing agents like Br2 water, Ag+, Cu++, etc. So, aldehydes are
strong reducing agents.

i) Reaction with Tollen’s reagent: [Silver mirror test]

 Note: Tollen’s reagent is an ammonical solution of silver nitrate. It
is prepared by adding dilute solution of NH4OH to AgNO3 solution
till the precipitate of Ag2O once formed gets dissolved.

 It is a mild oxidizing agent. It oxidizes only aliphatic and aromatic

aldehyde but not ketones.
 Aldehydes on heating with Tollen’s reagent, it reduced into metallic
silver and the aldehyde is oxidized into carboxylic acid.

Eg.

Note: The silver deposits on the inner wall of test

tube forming a shining layer like mirror. Hence,
this test is known as silver mirror test.

Q) Write the functional isomer of C3H6O and give a chemical test to

distinguish them.
ii) Reaction with Fehling’s solution: [Fehling’s test]
Note: Fehling’s solution is prepared by adding alkaline solution of
Rochelle salt [Fehling solution B] to CuSO4 solution [Fehling solution A].
 It is an weak oxidizing agent. It oxidizes only aldehyde but not
ketones.
When an aliphatic aldehyde is heated with Fehling’s solution, a brick red
ppt. of cuprous oxide is formed. This reaction is known as Fehling’s test.

Eg;

Nucleophilic addition reactions:

A. Addition of H2

B. Addition of HCN: Aldehydes and ketones react with hydrogen

cyanide to form addition product called cyanohydrins. Eg.
Cyanohydrin on acidic hydrolysis gives α-hydroxy acids which on heating
loses a molecule of water to form α,β-unsaturated acid.

Q) Identify A, B , C and D.

Q) How would you obtain 2-hydroxy-2-methylpropanoic acid from

propanone?

C. Addition of sodium bisulphite: Aldehydes and ketones react with

saturated solution of sodium bisulphite to form crystalline
bisulphite addition products. Eg.
 D. Addition followed by elimination of water molecule [Addition of
ammonia derivatives]
Aldehydes and ketones react with number of ammonia derivatives such
as hydroxylamione(NH2OH),hydrazine(NH2-NH2),
phenylhydrazine(C6H5NHNH2), etc. in weakly acidic medium to form
compounds containing C=N group.
1. Reaction with hydroxylamine: Aldehydes and ketones react with
hydroxylamine to form oximes. Eg.

2. Reaction with hydrazine: Aldehydes and ketones react with

hydrazine to form hydrazone. Eg.
3. Reaction with phenyl hydrazine: Aldehydes and ketones react with
phenyl hydrazine to form phenylhydrazones. Eg.

Reaction with 2,4-dinitrophenyl hydrazine : Aldehydes and ketones

react with 2,4-dinitrophenyl hydrazine (2,4-DNP) to form yellow, orange
or red ppt. of 2,4-dinitrophenyl hydrazone. Eg.

5. Reaction with semicarbazide: Aldehydes and ketones react with

semicarbazide to form semicarbazone. Eg.
 E. Aldol condensation reaction
Condensation between two molecules of aldehydes or ketones having
at least one α – hydrogen atom in presence of dilute alkali to form β-
hydroxy aldehyde or β-hydroxy ketone is known as aldol condensation
reaction. Examples:

Aldehydes and ketones which do not contain any α – hydrogen atom

such as HCHO, (CH3)3CCHO, C6H5CHO, etc. do not undergo aldol
condensation reaction.
Note : Dehydration of aldol product gives α, β-unsaturated aldehyde or
ketone.

F. Cannizzaro’s reaction
Aldehydes which do not contain α-hydrogen like HCHO, C6H5CHO,etc.
undergo self oxidation and reduction on treatment with conc. alkali. In
this reaction one molecule is oxidized to carboxylic acid and other
molecule is reduced to alcohol. Thus, a mixture of an alcohol and a salt
of carboxylic acid is formed by Cannizzaro’s reaction
G Reduction reaction
1. Reduction to alcohols: Aldehydes and ketones are reduced to primary
and secondary alcohols respectively using H2 in presence of Ni, Pt, Pd or
LiAlH4. Eg.

2 . Clemmensen’s reduction: The reduction of aldehydes and ketones to

alkane using zinc amalgam and conc. HCl is Clemmensen’s reduction. In
this reaction, carbonyl group (-CO-) is reduced to methylene group (-
CH2). Eg.
3 . Wolff-Kishner reduction : In this method aldehyde and ketone is
treated with hydrazine to form hydrazone which is then heated with
KOH in presence of glycol to give alkane. Eg.

4 . Reduction with HI in presence of red P : Aldehydes and ketones can

be reduced into corresponding hydrocarbon when heated with HI in
presence of red phosphorus at 1500C.

5. Action with PCl5:

Aldehydes and ketones react with PCl5 to give gem-dichloroalkane (gem-
dihalide).
[F] Special reactions of methanal (formaldehyde)
1. Reaction with ammonia: Formaldehyde reacts with ammonia to form
hexamethylene tetramine which is commonly known as ‘urotropine’. It
is used as medicine to treat urinary infections.

2. Reaction with phenol:

Phenol condenses with formaldehyde in the presence of an acid or basic
catalyst to form a polymer called Bakelite.
Formation of linear polymer:

Formation of cross-linked polymers

Formalin and its Uses

A 37-40% solution of formaldehyde in water is called formalin. Its
molecular formula is HCHO (i.e. formaldehyde).
Uses of Formalin:
1. It is used in preservation of biological specimens.
2. It is used as an antiseptic and disinfectant.
3. It is used to manufacture urinary antiseptic i.e. Urotropin.
4. It is used to manufacture polymers like Bakelite, resins, etc.
5. It is used in the manufacture of dyes like indigo, pararosaniline, etc.