GROUP A6:

TABLE OF CONTENTS
A) Aliphatic Aldehydes and Ketones

❖ Introduction, Nomenclature, and Isomerism

❖ Preparation of Aldehydes and Ketones
•Dehydrogenation and oxidation of alcohols
•Ozonolysis of alkenes
•Acid chlorides
•Gem dihaloalkanes
•Catalytic hydration of alkynes
❖ Physical Properties of Aldehydes and
Ketones
❖ Chemical Properties
❖ Structure and Nature of the Carbonyl Group
❖ Distinction Between Aldehydes and Ketones
•Using 2,4-DNP reagent
•Tollen's reagent
•Fehling's solution
❖ Addition Reactions
•Addition of H₂
•HCN
•NaHSO₃
❖ Reactions with Ammonia Derivatives
•NH₂OH (hydroxylamine)
•NH₂-NH₂ (hydrazine)
•Phenyl hydrazine
•Semi carbazide
❖ Aldol Condensation
❖ Cannizzaro's Reaction
❖ Clemmensen's Reduction
❖ Wolf-Kishner Reduction
❖ Reactions with PCl₅ and LiAlH₄
❖ Reactions with Methanal
▪ Ammonia
▪ Phenol
❖ Formalin and Its Uses
B) 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
A) Aliphatic Aldehydes and Ketones

Introduction
Aldehydes and ketones are the compounds containing carbonyl group, so are
collectively called carbonyl compounds. In aldehydes, the carbonyl group is linked
to an alkyl group and a hydrogen atom while in ketones, it is linked with two alkyl
groups.

The properties of aldehydes and ketones are due to the presence of the carbonyl
group as a functional group.
Nomenclature of aldehydes and ketones
Aldehydes are organic compounds containing a carbonyl group (C=O) at the terminal
carbon atom.

Common System
In the common system, aldehydes are named after the corresponding alkane with the
suffix "-aldehyde".

IUPAC System
In the IUPAC system, aldehydes are named as derivatives of alkanes with the suffix "-
al". The carbonyl carbon is always considered as carbon number 1.

Note: If the aldehyde group is attached to a ring, the ring name is used with the
suffix "-carbaldehyde". For example, an aldehyde attached to a benzene ring is called
benzaldehyde.
Ketones are organic compounds containing a carbonyl group (C=O) bonded to two
alkyl or aryl groups.

Common System
In the common system, ketones are often named using the common names of the
alkyl groups attached to the carbonyl group, followed by the word "ketone".

IUPAC System
In the IUPAC system, ketones are named as derivatives of the longest carbon chain
containing the carbonyl group, with the suffix "-one" indicating the presence of the
ketone functional group.

Note:
If the ketone group is attached to a ring, the ring name is used with the suffix "-
one". For example, a ketone attached to a benzene ring is called benzophenone.
When a molecule contains both an aldehyde and a ketone group, the
aldehyde takes priority in naming. This means that the molecule will be
named as an aldehyde, and the ketone group will be treated as a
substituent.

Additional notes:
•If there are multiple ketone groups present, they are
numbered individually and the prefix "oxo-" is used for each.
•If there are other functional groups present, they are named
according to their priority rules.
❖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. E.g.
2. Positional isomerism:

Ketones having at least 5 carbon atoms and aromatic aldehydes show

positional isomerism. E.g.
3. Functional isomerism:
Ketone and aldehyde having same molecular formula are functional
isomers of one another.

4. Metamerism:
Metamerism occurs when two compounds have the same molecular
formula but differ in the arrangement of their atoms around a central
atom. The isomers are called metamers. Ketones exhibit metamerism
due to difference in alkyl group present on either side of carbonyl
group.
No, metamerism does not occur in aldehydes because the functional group in an aldehyde only
has one alkyl group attached to it, making it impossible to have different alkyl groups on either
side of the functional group, which is a key requirement for metamerism; therefore, only
compounds like ethers and ketones can exhibit metamerism.
[Link]:
It occurs when two compounds can interconvert through a rapid,
reversible chemical reaction, typically involving the movement of a
proton (hydrogen ion). The two forms are called tautomers.
Preparation of Aldehydes and Ketones
1. From alcohol:

(i) By oxidation of alcohols:

•Alcohols on controlled
oxidation give aldehydes and
ketones.
•Acidified KMnO4 or K2Cr2O7 is
used as oxidizing agent.
•10 alcohol gives aldehyde
while 20 alcohol gives ketone.
Eg.

Primary alcohol is oxidized to aldehyde by using mild oxidizing agents like

pyridinium chlorochromate (PCC ),Coolin's reagent (dipyridinium chromium trioxide
complex), etc. to prevent further oxidation.
(ii) By dehydrogenation of alcohols:
When alcohol vapors are passed over heated copper at 3000C, different types of
alcohols give different products.
[Link] alcohols are dehydrogenated to aldehydes. E.g.

(Ethanol) (Ethanal)
2. Secondary alcohols are dehydrogenated to ketones. E.g.

(Propan-2 –ol) (Propanone)

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.
Ozonolysis of branched-chain alkene(olefins) like R2C=CR2 gives
ketone.
3. By catalytic hydration of alkynes :

Alkynes(acetylene) react with water in presence of mercuric sulphate

and sulphuric acid to give vinyl alcohol which rearranges to give
aldehyde or ketone at 60oC.

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

Note: Besides acetylene, all alkynes give ketones on hydration.

For example: Propyne gives propanone (i.e. ketone).

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.

Note:
Pd/BaS04 is poisoned by Sulphur or quinoline(a colorless, oily, aromatic liquid with a
strong odor) to prevent further reduction. Pd/BaS04 is called Rosenmund or Lindlar
(H2/Pd /CaCO3 )catalyst.
(ii) Ketones can be prepared by treating acid chloride with
dialkyl cadmium.

Acetyl chloride Diethyl cadmium Acetone

Note:
Methanal (formaldehyde) cannot be prepared by the
Rosenmund reduction.

The Rosenmund reduction is a chemical reaction used to

reduce acyl chlorides to aldehydes using hydrogen gas and a
palladium catalyst poisoned with barium sulfate or lead
acetate.
5. Hydrolysis of gem-dihalides:
The alkaline hydrolysis of gem-dihalide gives aldehyde and ketone.
• 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.
Physical Properties of Aldehydes and Ketones

1. 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.

2. Odour: Many aldehydes and ketones have distinct odors. Some aldehydes have
pleasant aromas, while others have pungent or unpleasant smells. Ketones often
have a sweet or fruity odor.
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.

4. Polarity: Both aldehydes and ketones are polar molecules due to the presence of
the polar C=O bond. This polarity allows them to form hydrogen bonds with water
molecules, making them soluble in water.

5. Reactivity: Both aldehydes and ketones are reactive compounds due to the
presence of the carbonyl group. They can undergo various reactions, such as
nucleophilic addition, oxidation, and reduction.

6. State and color: Formaldehyde is a gas having pungent odour whereas aldehydes
and ketones up to Cll are colorless volatile liquids having pleasant odour. Higher
members are colorless solid.
Chemical Properties
Carbonyl compounds commonly give nucleophilic addition reactions. Nucleophiles
attack the carbon atom of a carbon-oxygen double bond because carbon has a
partial positive charge. Aldehydes are more reactive than ketones towards the
nucleophilic addition reaction due to the following two factors:

❑ Inductive effect
Alkyl groups are electron releasing in nature having a +1 effect. Ketones contain
two alkyl groups whereas aldehydes contain one alkyl group. Hence, carbonyl
carbon becomes less electropositive in ketones and causes low reactivity than
aldehydes.

❑ Steric effect
Ketones contain two bulky alkyl groups attached with carbonyl carbon. More the
number of alkyl groups attached with carbonyl carbon more will be the steric
hindrance to nucleophilic attack and less would be the reactivity. Aldehydes give
reducing properties that are absent in ketones.
➢ 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
In the carbonyl group (>C=O), the carbon atom is sp2 hybridized. One of
the p-orbitals of the carbonyl carbon remains unhybridized. The three
sp2 hybrid orbitals of carbon lie in the trigonal plane with an angle of
about 1200 between them. These three sp2 hybrid orbitals form three a-
bonds; one with the half-filled p-orbital of oxygen and the other two
with the other atoms attached with this carbon. The unhybridized p-
orbital of the carbonyl carbon undergoes sidewise overlapping with the
remaining half-filled p-orbital of the oxygen atom to form a π -bond.
Since oxygen is more electronegative than carbon, partial positive charge is
developed in carbon atom whereas partial negative charge is developed in oxygen
atom, So, carbonyl compounds are highly polar compounds with dipole moments
ranging from 2.3-2.7 D.
➢ Distinction Between Aldehydes and Ketones:
•Using 2,4-DNP reagent
Formation of 2,4-dinitrophenyl hydrazone [2,4-DNP test]- Aldehydes and ketones react with 2,4-
dinitrophenyl hydrazine to form yellow , orange or red ppt. of 2,4-dinitrophenyl hydrazone. E.g.

H+

H+

2,4-dinitrophenyl hydrazine is known as Brady's reagent. It is dissolved in ethanol containing a

small amount of H2SO4 or HCL. But ethanol does not give this test.
•Tollens' reagent
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.

Aldehydes on heating with Tollen’s reagent reduces the reagent to metallic silver.

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.
•Both aliphatic and aromatic aldehydes give this test but ketones do not give this
test (because they cannot be easily oxidized by the mild oxidizing agent in Tollen's reagent).
Reaction with Fehling’s solution: [Fehling’s test]
Fehling’s solution is an alkaline solution of CuSO4 containing some
Rochelle salt (i.e. sodium potassium tartarate in equal volume. It is
prepared by adding alkaline solution of Rochelle salt [Fehling solution
B] to CuSO4 solution [Fehling solution A]. 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.

Note: It is used to diagnose diabetes in human urine. It is only given by aliphatic aldehydes. It
is not given by aromatic aldehydes and ketones (because they lack a hydrogen atom directly
bonded to the carbonyl carbon, which is necessary for these tests to occur).
❖Addition Reactions
➢Addition of H₂
Aldehydes and ketones are easily reduced to primary and secondary
alcohols respectively by using reducing agents like H2/Ni or LiAlH4,
etc.
➢ Addition of HCN (Hydrocyanic acid)
NaCN (sodium cyanide) reacts with H2SO4 (sulfuric acid) to produce HCN (hydrogen cyanide)
and Na2SO4 (sodium sulfate).
2 NaCN + H2SO4 → 2 HCN + Na2SO4
Important Note: This reaction is highly dangerous and produces toxic hydrogen cyanide gas. It
should only be performed under controlled laboratory conditions by experienced chemists with
proper safety equipment.

Aldehydes and ketones are added with HCN to form cyanohydrin.

Note: Hydrogen cyanide or hydrocyanic acid (HCN) is a poisonous compound. It is
prepared in situ by the action of sodium cyanide with dilute mineral acid.
The hydrolysis of cyanohydrin either in acidic or basic medium gives a-hydroxy
carboxylic acid.
For example,
Addition of NaHSO₃
Aldehydes and ketones react with saturated solution of sodium bisulphite(NaHSO₃)to
form crystalline bisulphite addition products. E.g.

Bisulfite addition compounds are formed when aldehydes or ketones react with sodium or
potassium bisulfite. This reaction is reversible, and the original aldehyde or ketone can be
regenerated by treating the bisulfite addition compound with an acid or base.
Reactions with Ammonia Derivatives(H2N-G)
Aldehydes and ketones react with number of ammonia derivatives
such as hydroxylamine(NH2OH), hydrazine(NH2-NH2),
phenylhydrazine(C6H5NHNH2), etc. in weakly acidic medium to form
compounds containing C=N group.

1. Reaction with hydroxyl amine: Aldehydes and ketones react with

hydroxylamine to form oximes. E.g.
2. Reaction with hydrazine: Aldehydes and ketones react with hydrazine to form
hydrazone. E.g.

3. Reaction with phenyl hydrazine: Aldehydes and ketones react with phenyl
hydrazine to form phenylhydrazones. E.g.
4. 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. E.g.

5. Reaction with semi carbazide: Aldehydes and ketones react with semi carbazide
to give crystalline ppt. of semi carbazone. E.g.
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:

(ß-hydroxy ketone)

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.

Note: Methanal, benzaldehyde and benzophenone does not

undergo aldol condensation as they do not contain α -
hydrogen.
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.

Note: Cannizzaro reaction is an example of auto-redox or disproportional reaction in

which an aldehyde is oxidized to its corresponding salt of carboxylic acid and the
other is reduced to a corresponding primary alcohol.
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-). E.g.
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. E.g.
Action with PCl5:

Aldehydes and ketones react with PCl5 to give gem-

dichloroalkane (gem-dihalide).

Acetaldehyde

Acetone
Reduction to alcohols:
Aldehydes and ketones are reduced to primary and secondary alcohols
respectively using H2 in presence of Ni, Pt, Pd or LiAlH4. E.g.
Extra: 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.
Special reactions of methanal :
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 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:

[Link] is used in preservation of biological specimens.

[Link] is used as an antiseptic and disinfectant.
[Link] is used to manufacture urinary antiseptic i.e. Urotropin.
[Link] is used to manufacture polymers like Bakelite, resins, etc.
[Link] is used in the manufacture of dyes like indigo, pararosaniline, etc.
B) Aromatic aldehydes and Ketones
Aromatic aldehydes are the compounds in which –CHO group is bonded directly to an
aromatic ring. E.g.

Aromatic ketones are the compounds in which carbonyl group is bonded with either
both aryl group or aryl and alkyl group. E.g.
Preparation of benzaldehyde from toluene and
acetophenone from benzene:

Preparation of benzaldehyde:
1. From toluene:
Benzaldehyde is prepared by oxidation of toluene with cerium oxide
(CeO2) in the presence of conc. H2SO4.
2. From Rosenmund’s reduction :
Benzaldehyde is obtained by reducing benzoyl chloride with hydrogen
in the presence of Pd catalyst deposited in BaSO4.
❖ Preparation of acetophenone from benzene:
Acetophenone(Methyl phenyl ketone) is prepared by the
treatment of benzene with acetyl chloride in the presence
of anhydrous AlCl3.
For Conversion
Properties of benzaldehyde

Physical properties of benzaldehyde:

1. It is colorless liquid with bitter almond odour.

2. It is insoluble in water.
3. Its boiling point is 1790C.
Chemical Properties
1. 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.
2. Perkin’s (condensation) reaction:

The condensation of an aromatic aldehyde with an acid

anhydride in the presence of sodium or potassium salt of the
same acid to produce α,β-unsaturated acid is known as the
Perkin’s condensation.
3. Benzoin condensation reaction:

Benzaldehyde when heated with alcoholic solution of

potassium cyanide, undergoes self condensation between
two molecules to form an α-hydroxy ketone known as
benzoin. This reaction is called benzoin condensation
reaction. E.g.

(α-hydroxy benzene)
4. Electrophilic substitution reaction:

-CHO group is electron withdrawing group. It withdraws π- electrons

from benzene ring, decreasing electron density of aromatic ring.
Benzaldehyde is resonance hybrid of following resonance structures:

From the above resonating structures, it is clear that electron density

is comparatively high at meta position. Thus, incoming electrophile
attacks at meta position to give meta substituted product. Thus –CHO
is a meta directing group.
Some Important Questions
1. Write any three methods of preparation of
i. Acetaldehyde ii. Propionaldehyde iii. Iso butyraldehyde iv. Acetone
v. Ethyl methyl ketone
2. How can you distinguish:
i. Methanal and Ethanal ii. Ethanal and Benzaldehyde
iii. Propanal and propanone iv. Benzaldehyde and acetophenone
3. How can you convert
i. Methanal to ethanal ii. Ethanal to methanal
iii. Ethanal to propanone iv. Ethanal to propanal
v. Propane to 2-hydroxy 2-methyl propanoic acid
4. Give the example each of
i. Rosenmund reduction ii. Ozonolysis
iii. Clemmenson reduction iv. Wolff-Kishner reduction
v. Aldol reaction vi. Cannizaro reaction
vii. Tollen's test viii. Fehling's test
5. An organic compound C2H40 gives a red precipitate with Fehling's solution. It also
undergoes aldol reaction. Write the IUPAC name of the compound.
6. An organic compound A(C4H80) forms phenyl hydrazone with phenyl hydrazine and
reduce Fehling’s solution. It has negative iodoform test. Identify the compound.
7. Write the structure and one use of the main product obtained by the reaction of
formaldehyde with ammonia.