ALDEHYDES

AND KETONES

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Aldehydes and Ketones

Carbonyl Group Ketone

In carbonyl group, carbon atom is bonded “The organic compounds in which

with oxygen. carbonyl carbon is attached with two
similar or dissimilar alkvl groups are called
O ketones. ” They have general formula
||
—C— O
||
This carbonyl group > C = O is present in R —C—R
aldehydes, ketones, carboxylic acid,
esters, anhydrides, acid halides and acid
amides. For Example

O
Aldehydes ||
CH₃ — C — CH₃
Propanone
The organic compounds in which
(Dimethyl Ketone)
carbonyl carbon is attached with at least
(Acetone)
one hydrogen atom, are called aldehydes.
The general formula of aldehydes s.

O
O
||
||
CH₃ — C — CH₂ — CH₃
R /H—C—H
2 - Butanone
(Ethyl Methyl Ketone)

For Example
The homologous series of both
O O aldehydes and ketones have general
|| || formula CnH₂ₙO
H —C—H CH₃—C—H
Formaldehyde Acetaldehyde

O
||
CH₃ — CH₂—C—H
Propionaldehyde

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Occurance of Aldehydes
and Ketones
Aldehydes and ketones are
present mm many naturally
occurring compounds. The
aldehyde group is present in most
sugars. They are the principal
constituents of a number of
essential oils used as fragrances
and flavours Ketonic group s
present in camphor and
menthone.

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Nomenclature of
Aldehydes
Common Names For Example

The common names of aldehydes

are obtained from the common CH₃ CH₃ O
names of carboxylic acids | | ||
containing the same number of CH₃ — CH — CH— C — H
carbon atoms. The ending —ic acid
in the common name of the acid is α-β-dimethyl butyraldehyde
replaced by the word aldehyde.

O IUPAC System
||
R /H—C—H Select longest continuous chain of
carbon atoms also containing carbonyl
carbon atom.
Numbering is always started from
O
O carbonyl carbon atom.
||
|| The suffix “—e” of alkane is s replaced
H—C—H
CH₃ — C — H “—al” in aldehydes.
The position and name of the branches
Formaldehyde Acetaldehyde
are written before the name of
aldehyde.
Since aldehyde group is always at one
O terminal of the chain, no prefix is
|| necessary to locate the position of the
CH₃ — CH₂— C — H aldehyde group.

Propionaldehyde
For Example

O O
The position of substituents on the chain || ||
are indicated by Greek letters (α, β, γ, δ). H—C—H CH₃ — C — H
Lettering on the carbon adjacent to the Methanal Ethanal
carbonyl group. O
||
CH₃ — CH₂ — C — H
O Propanal
δ γ β α ||
C— C — C — C — C — H O
||
CH₃ — CH₂ — CH —C —H
|
Cl
2 - Chlorobutanal

O
||
C₆H₅ — C —H
Benzaldehyde

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Formula IUPAC Name Common Name

H—CHO Methanal Formaldehyde

CH₃ —CHO Ethanal Acetaldehyde

CH₃ — CH₂ —CHO Propanal Propionaldehyde

CH₃ — CH₂ —CH₂ —CHO Butanal Butyraldehyde

CH₃ —(CH₂)₃ —CHO Pentanal Valeraldehyde

CH₃ —(CH₂)₃ —CHO Hexanal Caproaldehyde

α-methyl
CH₃
propionaldehyde or
| 2-Methyl propanal
iso-
CH₃ — CH — CHO
butylaldehyde

CH₃ CH₃
| |
CH₃ — CH — CH— CHO 2, 2, 3 trimethyl α, α, β trimethyl
| butanal butyraldelyde
CH₃

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Nomenclature of
Ketones
Common Names For Example

Common names of ketones are O

obtamed simply naming the two- ||
alkyl groups CH₃ — C — CH₃
attached to the carbonyl group Propanone
and adding the word ketones. (Dimethyl Ketone)
Prefix di is used for similar alkyl (Acetone)
groups.
The names of alkyl group are
written according to mass of O
group. Alkyl groups with less mass ||
is written first. CH₃ — C — CH₂ — CH₃
2 - Butanone
For Example (Ethyl Methyl Ketone)

O
|| O
CH₃ — C — CH₃ ||
Dimethyl Ketone C₆H₅ — C — CH₃
Acetophenone
O
||
CH₃ — C — CH₂ — CH₃
Ethyl Methyl Ketone
CH₃ O CH₃
| || |
CH₃ — CH — C — C — CH₃
IUPAC Names |
CH₃
Select longest continuous carbon
chain including carbonyl carbon 2, 2, 4-trimethyl-3-pentanone
atom.
From the name of an alkane having
corresponding number of carbon
atoms “—e” is replaced by “—one”.
Start numbering from that end which
is nearest to carbonyl carbon atom.
Mention the position of carbonyl
carbon before the stem name.
The position and name of branches
are written before the name of
ketone.

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Table — Some Common Names and IUPAC Names of Ketones

Formula IUPAC Common Name

O
Dimethyl ketone
|| 2-Propanone
(Acetone)
CH₃ — C — CH₃

O Ethyl methyl
2-Butanone
|| ketone
CH₃ — CH₂— C —CH
O
Methyl-n-propyl
|| 2-Pentanone
ketone
CH₃ —C —CH₂ —CH₂ —CH₃

If similarly alkyl group are present an

both side of carbonyl carbon, it is
called symmetrical ketone and if
dissimilar groups are present on both
side of carbonyl carbon, it is called
unsymmetrical ketone.

O
||
CH₃ — CH₂ — C — CH₂ — CH₃
Symmetrical Ketone
Diethyl Ketone

O
||
CH₃ — C — CH₂ — CH₃
Unsymmetrical Ketone
(Methyl - n - Propyl Ketone)

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Preparation of
Aldehydes
Mostly aldehydes are prepared by the (ii) Industrial Method
oxidation of primary alcohol.
Formaldehyde is manufactured by
(a) Preparation of Formaldehyde or passing a mixture of methanol vapours
Methanal (Formalin) and air over tron oxide, moleybdenum
oxide or silver catalyst at 500°C.
(i) Laboratory Method
O
Formaldehyde is prepared in the Fe(Q, Mo₂O₄ ||
laboratory by passing a mixture of 2CH₃OOH + O₂ 2H—C —H + 2H₂O
500 °C
methyl alcohol vapours and air over
platinized asbestos or copper or silver
catalyst at 300°C.
(b) Preparation of Acetaldehyde
O
Pt-asbestos || (i) Laboratory Method
2CH₃OH + O₂ 2H—C —H + 2H₂O
300 °C Acetaldehyde is prepared in the
laboratory by the oxidation of ethyl
alcohol with acidified sodium
Set up the apparatus is shown in figure.
dichromate solution.
Air is drawn through methyl alcohol
with the help of a suction pump. Methyl
alcohol is oxidised to gaseous Na₂Cr₂O₇ + H₂SO₄
formaldehyde which is absorbed in CH₃CH₂OH + [O] CH₃CHO + H₂O
Δ
water. The resulting mixture is called
formalin. Formalin is a mixture of 40%
formaldehyde, 8% methyl alcohol and
A mixture of ethyl alcohol and sodium
52% water.
dichromate solution is run into boiling
dilute sulphuric acid. Immediately a
vigorous reaction takes place and the
acetaldehyde formed in liquid state is
immediately distilled off. This prevents
the oxidation of acetaldehyde to acetic
acid. Ethyl alcohol remains in solution
untill it is oxidized. Pure acetaldehyde
is obtained by re-distillation.

Preparation of Formaldehyde
(formalin)

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(c) Preparation of Acetone

Acetone is prepared by the dry
distillation of calcium acetate
Ca(CH₃COO)₂

O
||
CH₃ — C— O
Ca
CH₃ — C— O
||
O

Dry Distillation

(ii) Acetaldehyde can also be prepared by

the dry distillation of a mixture of
calcium salts of formic acid and acetic
acid. O
||
O O CH₃ — C— CH₃ + CaCO₃
|| ||
H—C—O H — C— O
Ca + Ca
H—C—O H — C— O
|| ||
O O

Heat

O
||
2CH₃ — C—H + 2CaCO₃

(ii) Industrial Method for Preparation of

Acetaldehyde

Acetaldehyde is prepared industrially by

air oxidation of ethylene using palladium
chloride catalyst with a cupric chloride
promoter.

O
PdCl₂ + CuCl₂ ||
2CH₂ = CH₂ + O₂ 2CH₃—C —H
H₂O

Ethylene Acetaldehyde

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Reactivity of
Carbonyl group
The carbonyl group > C = O, has double Nucleophilic Addition Reaction
bond between carbon and oxygen atom,
one is sigma and other is n-bond. Carbon Suppose H-Nu is a general
of carbonyl is sp² hybridized. nucleophile, Nu- attacks at the carbon
Most of the reactions of aldehyde and atom of the carbonyl group and
ketones are addition reactions.Due to donate a pair of electron to it. Double
greater electronegativity of oxygen, the bond between carbon and oxygen
carbonyl group is polar. &t electrons are > C = 0 changes to hydroxyl group.
attracted toward oxygen and it has
partial negative charge while carbon has
partial positive charge.

In nucleophilic addition reaction, the

product will be either acid catalysed
or base catalysed. A base catalyst
increases the nucleophilic characters
of the reagent. Acid catalyst, promotes
the nucleophilic attack by increasing
positive characters of carbonyl
carbon atom.

Due to unsymmetrical distribution of

electrons, carbon of the carbonyl
group behave as an electrophilic
center.
Both electrophile or nucleophile can
attack on carbonyl group depending
upon the reaction conditions and
nature of electrophile or nucleophile.
Whatever the case may be, the
addition product or adduct will be
same. In aldehydes and ketones,
however, nucleophilic addition is
more common.

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Reactions of Carbonyl
compounds
(a) Nucleophilic Addition Reactions

(i) Laboratory Method

The most important reactions which

takes place in aldehydes and ketones
are nucleophilic addition reactions.
Nucleophilie attacks at carbonyl
carbon atom which has partial
positive charge. A general reaction of
a nucleophile is given below.

H H
|
C=O + H - Nu Nu — C — OH
|
H H

δ+ δ−

Reagent

An acid or base is used as catalyst in

Substrate Addition
nucleophilic addition reactions. In
Product
both cases, addition product is same.
Mechanism of base catalyzed reaction
is discussed below.

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Base Catalysed
Nucleophilic Addition
Reaction
A base-catalysed nucleophilic addition
reaction will take place with a strong CH₃ NaCN/HCl OH
nucleophilic reagent. The base reacts |
with the reagent and generates the C = O + HCN H — C — CN
nucleophile. The addition is initiated |
by the attack of a nucleophile on the H CH₃
electrophilic carbon of the carbonyl Acetaldehyde
group. The general mechanism of the
reactions is as follows.

-
OH +
δ+
H — Nu
δ−
⇌ Nu- + HOH CH₃ NaCN/HCl OH
|
C = O + HCN H — C — CN
H |
| CH₃ CH₃
Nu + C=O
δ+ δ−
⇌ Nu — C — O
-
Acetone
|
H
The cyano group — C =N is hydrolysed
by an aqueous acid into a carboxylic
| acid through an acid amide.
⇌ Nu — C — OH + OH-
δ+ δ−
-
Nu — C — O + H-OH
| OH
|
CH₃ —CH —CN + 2H₂O + H₂SO₄
Some base catalysed nucleophilic
Acetaldehyde Cyanohydrin
addition reactions of aldehydes and
ketones are given below

OH
|
(1) Addition of Hydrogen Cyanide CH₃ —CH —COOH + NH₄HSO₄
2-hydroxypropanoic acid
Hydrogen cyanide adds to aldehydes (Lactic Acid)
or ketones to form cyanohydrins. The
reaction is carried out by adding
The reaction is used for the synthesis of α-
slowly a mineral acid to an aqueous
hydroxy acids that contain one carbon atom
solution of sodium cyanide. The acid
more than the number of carbon atoms in
generates HCN from sodium cyanide
the starting aldehydes or ketones.
in situ.

NaCN + HCl ⇌ NaCl + HCN

H OH
NaCN/HCl |
C = O + HCN H — C — CN
|
H H
Formaldehyde
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Mechanism (2) Addition of Grignard’s Reagent

The reaction is base-catalysed Aldehydes reacts with Grignard’s

because HCN has no lone pair of Reagent to form secondary alcohol.
electrons on its carbon. the base (OH-) However, formaldehyde form primary
generates cyanide ions which act as alcohol.
nucleophiles. The mechanism
of the reaction is as follows.
H H
δ+ δ− δ− δ+
| - +
C = O + R-MgX R — C — OMgX
|
H H
dilHCl
- + + HOH
R-CH₂-OMgX R — CH — OH + Mg(OH)X

R’ R
|
δ+ δ− - +
C = O + R-MgX R’ — C — OMgX
The hydroxide ion liberated in the |
formation of cyanohydrin reacts with H H
undissociated hydrogen cyanide and
produces more cyanide ions, which in
turn react with more carbonyl R R
compound. | dilHCl |
- +
R’ — C — OMgX + HOH R’— C — OH + Mg(OH)X
| |
OH H H
|
CH₃ — CH — CN + 2H₂O + H₂SO₄
Acetaldehyde
cyanohydrin

OH
|
CH₃ — CH — COOH + NH₄H
2-Hydroxypropanoic
Acid
(Lactic Acid)

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(3) Addition of Sodium Bisulphite Mechanism

Sodium sulphite ionises to form
Aldehydes and small ketones react
hydrogen sulphite ion and sodium
with a saturated aqueous solution of
ion.
sodium bisulphite to form a crystalline
white precipitate of sodium bisulphite
adduct.

Hydrogen sulphite ion act as

nucleophile.

Ketones in which both alkyl groups

are larger in size do not react with
sodium bisulphite NaHSO₃.
Bisulphite on heating with a dilute
mineral acid (HCI or H₂SO₄),
(4) Condensation Reactions
regenerates the parent aldehyde or
ketone.
“The reactions in which two molecules
of same or different compounds
combine to form new compound is
called condensation reaction.”

The reaction is used for the separation (a) Aldol Condensation

and purification of carbonyl
compounds from non-carbonyl
“Aldehydes and ketones possessing a-
compounds such as alcohols.
hydrogen atoms react with a cold
dilute solution of an alkali to form
addition products known as Aldol.”

The name “aldol’ is given to the

product because it contains both
aldehyde and alcohol functional
groups. Note that the name aldol
condensation is reserved for the
reaction that starts with two identical
carbonyl compounds.

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(i) Two Similar Aldehydes

Mechanism of Aldol Condensation

(Between Similar Aldehydes)
The hydroxide ion acts as a base. It
(i) Two Dissimilar Aldehydes removes a proton from w-carbon of
one molecule of the carbonyl
compound to form a carbanian.

The carbanion acts as a nucleophile. It

attacks the electrophilic carbonyl carbon
atom of the unchanged second
molecule of ethenal to form an alkoxide
ion.

(iii) Two Similar Ketones

The alkoxide removes a proton from

water to form aldol.

The aldol compound readily losses

water on heating in the presence of
dilute acid to form an unsaturated
carbonyl compound. A carbon-carbon
The basic catalyst hydroxide ion is
double bond is formed between the a-
regenerated.
and B-carbon atoms.
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(b) Cannizzaro's Reaction Mechanism

The aldehydes having no a-hydrogen (1) The reaction of methanal with base
at a-carbon atom do not undergo gives alcohol and salt of carboxylic
aldol condensation in the presence of acid. The hydroxide ion acts as a
base. nucleophile. It attacks on the
electrophilic carbonyl carbon to form
“The aldehydes having no a-hydrogen a complex anion.
at a-carbon atom in the presence of
base are converted to corresponding
alcohol and carboxylic acid salt is
called Cannizzaro reaction.

Cannizzaro reaction is a self oxidation- (ii) The anion transfers a hydride ion to
reduction reaction. In this reaction second molecule of formaldehyde.
one molecule of aldehyde is oxidised The presence of the negative charge
to carboxylic acid while the other on oxygen of the anion helps in the
molecule is reduced to corresponding loss of hydride ion.
alcohol. This reaction is also called
disproportionation reaction. For
example, methanal or benzaldehyde
have no a-hydrogen at a-carbon atom
and undergo Cannizzaro reactions.

(iii) The methoxide ion acts as a base

and attracts a proton from formic acid
to form methanol and formate ion. The
formate ion in the presence of alkali
gives a salt of the acid.

(5) Haloform Reaction

The compounds which have methyl

O
||
ketone CH₃ — C — group in them
undergo haloform reactions. Only
acetaldehyde CH₃ — CHO and methyl
O
||
ketones CH₃—C —R reacts with
halogens in the presence of base NaOH.
The term haloform is derived from
halogen. The products of the reactions
are chloroform, bromoform or iodoform
e.g

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O
||
(1) Methyl ketones CH₃ — C — R and
other higher ketones. (R may be ethyl
or higher alkyl group).
(2) Methanol and Ethanol. Ethanol
forms CHI₃ while methanol does not
do so. Primary alcohols do not
perform iodoform test except ethanol.

Secondary alcohols containing the hydroxyl

group on the second carbon atom

Form a synthetic point of view the

halofrom reaction, affords a convenient
method for converting a methyl ketone
to a carboxylic acid containing one
carbon atom less than parent
compound.

lodoform Test

“The halogen reaction using iodine

and aqueous sodium hydroxide is
called iodoform test”.

In this test water insoluble, yellow

crystalline iodoform CHI³ is formed.
This iodoform can be used to
distinguish.

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Acid Catalyzed
Nucleophilic Reaction
The acid catalysed nucleophilic (1) Polymerization
addition reaction will take place with a
weak nucleophilic reagent. The Both formaldehyde and acetaldehyde
addition is intiated by the proton (H+) polymerize in the presence of dil.
liberated by the acid. The proton H₂S04 to give metaformaldehyde and
combines with the carbonyl oxygen paraldehyde respectively.
atom and increases the electrophilic
character on the carbonyl carbon. As a
result, the attack of the weaker
nucleophile on the electrophilic
carbon becomes easier.

Mechanism

Cᵟ⁺ =Oᵟ⁻ + H⁺ ⇌ C = O⁺ — H

|
Nu⁻ + C =O ⁺— H ⇌ Nu — C — OH
|

The acid-catalysed nucleophilic

addition reactions of aldehydes and (2) Addition of Ammonia Derivatives
ketones are the following.
Aldehydes and ketones react with
ammonia derivatives, G — NH₂ to form
compounds containing the group
> C = N — G and water. The reaction is
known as condensation reaction or
addition-elimination reaction because
water is lost during addition. The
reactions are acid catalysed.
The general reaction is

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Some commonly used ammonia (iii) Reaction with Hydrazine (NH₂ —

derivative are hydroxylamine, NH₂OH, NH₃)
hydrazine, NH₂NH₂, phenyldydrazine,
Aldehydes and ketones react with
C₆H₅NHNH₂, semicarbazide
hydrazine to form hydrazones in the
NH₂NHCONH₂ and 2, 4 dinitro-phenyl-
presence of an acid.
hydrazine.

The reaction of the above stated

ammonia derivatives with aldehydes
and ketones are as follow

(i) Reaction with Hydroxylamine

Aldehydes and ketones react with

hydroxylamine to form oximes in the (iv) Reaction with 2, 4
presence of an acid. Dinitrophenylhydrazine (2, 4, DNPH)

Aldehydes and ketones react with 2, 4-

dinitrophenylhydrazine to form 2, 4-
dinitrophyenylhydrazones in the presence of
acid.

(ii) Reaction with Phenyl Hydrazine

(NH₂ – NHC₆H₅)

Aldehydes and ketones react with

phenyldydrazine to form phenyl
hydrazones in the presence of an acid.

The reaction can be used for the

identification of aldehydes and ketones
because
2, 4-dinitropenylhydrazones are usually
yellow or orange crystalline solids.

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Mechanism of the Reaction of

Amonia Derivatives

A base-catalysed nucleophilic addition

reaction will take place with a strong
nucleophilic reagent. The base reacts
with the reagent and generates the
nucleophile. The addition is initiated
by the attack of a nucleophile on the
electrophilic carbon of the carbonyl
group. The general mechanism of the
reactions is as follows.

Step-I Protonation of the carbonyl group.

Addition of Alcohols

Cᵟ⁺= Oᵟ⁻ ⇌ C⁺ — O⁻ Aldehydes combine with alcohols in the

presence of hydrogen chloride gas to form
acetals. The hydrogen chloride acts as a
catalyst. Both the alcohol and the hydrogen
Step-II Nucleophilic attack on
must be dry.
nitrogen of ammonia derivative on
the electrophilic positively charged
carbon and deprotonation of the
adduct.

The reaction may be used to protect the

aldehyde group against alkaline
oxidizing agents. To regenerate
aldehyde, the acetal is hydrolysed in the
presence of an acid.
Step-III Protonation of oxygen of
hydroxyl group followed by the
removal of water.

Ketones do not react under these

conditions.

Step-IV Formaldehyde reacts with

NH₃ to form hexamethylene tetra-
amine (urotropine).

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The alkoxide ion is protonated with water

(3) Reduction of Carbonyl
to give an alcohol
Compounds

Aldehydes and ketones can both be

reduced. Aldehydes are reduced to
primary alcohols whereas ketones to
secondary alcohols. The carbonyl
group is converted into an alcohol.
(ii) Catalytic Reduction
(i)Reduction with Sodium Aldehydes and ketones on reduction
Borohydride with hydrogen in the presence of a
metal catalyst like Pd, Pt or Ni form
Aldehydes and ketones are reduced primary alcohols and secondary
to alcohols with sodium borohydride, alcohols respectively. Hydrogen is
NaBH₄. added across the carbonyl group.
The reaction is carried out by adding
sodium borohydride to an aqueous or
alcoholic solution of an aldehyde or
ketone.

Sodium borohydride reduces the

carbon-oxygen double bond but not
the carbon-carbon multiple bond.

Mechanism
The tetrahydriborate (III) ion, BH is source
of hydride ion, H. The hydride ion acts as a
nulceophile. It attacks on the electrophilic
carbon of the carbonyl group to give an
alkoxide ion.

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Clemmenson's Reduction Oxidation state of silver in AgNO₃ is +1

which changes to Ag⁰. This test is not
Ketones react with zinc amalgam
performed by ketones.
and HCI ketones react with zinc
amalgam and
form alkanes. Fehling Solution
Fehling solution is a solution of copper
(II) sulphate CuSO₄, sodium hydroxide
and tartaric acid. Fehling solution
oxidizes aldehydes to carboxylic acids
and cupric Cu++ ions are reduced to
cuprous ion Cu+. When Fehling
(4) Oxidation of Carbonyl solution reacts with aldehydes, brick
Compounds red precipitate of cuprous oxide Cu₂O,
is formed.
(a) Oxidation of Aldehydes

(i) Strong oxidizing agents like K₂Cr₂O₇

or KMnO₄/H₂SO₄, or dilute HNO₃ can Benedict Solution
oxidize aldehydes as well as ketones.
It is a mixture of NaOH, CuSO₄ and
In aldehydes, hydrogen atom of
citric acid. Aliphatic aldehydes react
aldehyde changes to —OH and
with benedict solution and brick red
carboxylic acid is formed. Carboxylic
precipitate of Cu₂O is formed. In this
acid has some carbon atoms in
reaction, Cu²⁺ ions are reduced to Cu¹⁺
aldehydes.
ions.

Aromatic aldehydes and ketones do

not perform this test.

Oxidation of Ketones
Ketones are not oxidized by mild
oxidizing agents like Fehling solution,
Mild oxidizing agents like Benedict
Benedict solution or Tollen reagent.
solution Fehling solution or Tollen
Ketones are oxidizes by strong
reagent (ammonical silver nitrate) can
oxidizing agents like KMnO₄/H₂SO₄,
only oxidizes to aldehydes and not to
K₂Cr₂O₇/H₂SO₄, etc.
ketones, e.g;
In oxidation of ketones, only the carbon
Aldehydes reacts with ammonical silver
atoms adjacent to the carbonyl group
nitrate (Tollen's reagent) to form metallic
are attacked. The carbon atom joined to
silver. Silver deposit inside the test tube and
smaller number of hydrogen atoms is
seems like mirror so 1t also called silver mirror
preferentially oxidized. In case of
test.
symmetrical ketones only one carbon
atom adjacent to the carbonyl group is
oxidized and a mixture of two carboxylic
acids is always obtained

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However, in case of unsymmetrical ketones, the carbon

atom joined to the smaller number of hydrogen atoms
is preferentially oxdized and the carbonyl group
remains with
the smaller alkyl group.

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Identification tests for

Carbonyl compounds
Test Aldehyde Ketone

Aldehydes give this Ketones also give this

test and yellow test and yellow
2,4-DNPH test
crystalline ppt is crystalline ppt is
formed. formed.

Aldehydes give this Small ketones only

test and white give this and white
NaHSO₃ test
crystalline ppt is crystalline ppt. is
formed. formed.

Aliphatic aldehydes
Aromatic aldehyde
give this test and
Tollen’s test and ketones do not
silver mirror is
perform this test.
formed.

Aliphatic aldehydes Ketones do not

Benedict’s solution
give and brick red ppt perform this
test
of Cuz0 is formed. test.

Aliphatic aldehydes
Ketones do not
Fehling’s solution give and brick red ppt
perform this
test of Cu²O is formed.
test.

Ketones react with

sodium nitroprusside
Sodium Aldehydes do not and wine red or
nitroprusside test perform this test. orange red colour is
formed.

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Uses of Aldehydes
Uses of Formaldehyde

It is used in the manufacture of

resins like urea-formaldehyde and
plastics such as bakelite.
It is used in the manufacture of
dyes such as indigo, para-
rosaniline, etc.
Its 40% aqueous solution called
formalin is used as an antiseptic,
disinfectant, a germicide, a
fungicide and for preserving
animal specimens and sterilizing
surgical instruments.
It is used as a decolourising agent
in vat dyeing.
It is used n the silvering of mirrors.

Uses of Acetaldehyde

It is used in the production of

acetic acid, acetic anhydride, n-
butanol, ethanol, 2-ethy-1-hexanol,
vinyl acetate, paraldehyde,
ethylacetate, etc.
It is used to make acetaldehyde
ammonia used as a rubber-
accelerator.
It is used to make chloral hydrate,
ethanal trimer and tetramer.
Chloral hydrate and ethanal trimer
are both used as hypnotic drugs
(medicine having power to induce
sleep) whereas ethanal tetramer is
used as a slug poison.
It is used as an antiseptic inhalent
in nasal infections.
It is used in silvering of mirrors.
It is used to make phenolic resins
and synthetic drugs.

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 NOTES

Exercise
Fill in the blanks True or False

(i) Aldehydes are the first oxidation (i) Formaldehyde is used in the silvering of
product of primary alcohol. mirrors.
True
(ii) Ketones are the first oxidation
product of secondary alcohol. (ii) Ketones combine with alcohols in the
presence of HCI gas to form acetals,
(iii) Aldehydes and ketones undergo False
nucleophilic addition reactions.
(iii) Acetaldehyde undergoes Cannizzaro’s
(iv) Formaldehyde reacts with reaction.
Grignard reagent to give primary False
alcohol.
(iv) Formaldehyde is used for silvering of
(v) Acetaldehyde reacts with mirrors.
C₂H₅MgBr to give 2-butanol. True

(vi) Aldehydes are strong reducing (v) Aldol condensation reaction is given by
agents. only those aldehydes and ketones which
contain an a-hydrogen atom.
(vii) The oxidation of an aldehyde True
always gives a carboxylic acid.
(vi) Cannizzaro’s reaction is given by only
(viii) The reduction of a ketone always those aldehydes containing no a-hydrogen
gives a secondary alcohol. atom.
True
(ix) Formaldehyde gives silver mirror
test with Tollen’s reagent. (vii) Propanol and propanone behave
differently with Tollen’s reagent.
(x) Acetaldehyde gives a brick red True
precipitate with Fehling’s solution.
(viii) Acetone reacts with sodium bisulphite to
give a yellow crystalline product.
False

(ix) Acetone on reduction gives a primary

alcohol.
False

(x) 40% aqueous solution of formaldehyde is

called formalin.
True

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 NOTES

Multiple Choice Questions

(i) The carbon atom of a carbonyl group (vii) Which of the following compounds
is will react with Tollen’s reagent
(a) sp hybridized
(b) sp² hybridized
(c) sp³ hybridized O
(d) None of these (a) ||
CH₃ — C — H
(ii) Formalin is
(a) 10% solution of formaldehyde in water + O
8% methyl alcohol (b) ||
(b) 20% solution of formaldehyde in water + CH₃ — C — CH₃
8% methyl alcohol
(c) 40% solution of formaldehyde in O
water + 8% methyl alcohol (c) ||
(d) 60% solution of formaldehyde n water + CH₃ — C — OH
8% methyl alcohol

(iii) Which of the following will have the O

highest boiling point (d) ||
(a) Mathanal CH₃ — C — CH₂ — CH₃
(b) Ethanal
(c) Propanal (viii) Cannizzaro’s reaction is not given by
(d) 2-Hexanone (a) Formaldehyde
(b) Acetaldehyde
(iv) Ketones are prepared by the (c) Benzaldehyde
oxidation of (d) Trimethylacetaldehyde
(a) Primary alcohol
(b) Secondary alcohol (ix) Which of the following reagents will
(c) Tertiary alcohol react with both aldehydes and ketones
(d) None of these (a) Grignard reagent
(b) Tollen’s reagent
(v) Acetone reacts with HCN to form a (¢) Fehling’s reagent
cyanohydrin. It is an example of (d) Benedict’s reagent
(a) Electrophilic addition
(b) Electrophilic substitution
(c) Nucleophilic addition
(d) Nucleophilic substitution

(vi) Which of the following compounds

will not give iodoform test on treatment
with I₂/NaOH
(a) Acetaldehyde
(b) Acetone
(c) Butanone
(d) 3-pentanone

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 NOTES

Short Questions
Question01

Q.5 How does formaldehyde react with

(v) Hydrogen
the following reagents?

(i) CH₃Mgl (ii) HCN

O
(iii) NaHSO₃ (iv) NaOH ||
NaBH₄
H — C — H + 2[H] CH₃ — OH
(v) Hydrogen (vi) Tollen’s Reagent
(vii) Fehling’s Reagent
(vi) Tollen’s Reagent
Answer
O
(i) CH₃Mgl ||
H — C — H + 2Ag(NH₃)₂ + 2OH

HCHO + CH₃MgI CH₃ — CH₂ — OMgI

aq KCl
CH₃ — CH₂ — OMgI + H₃O CH₃ — CH₂ — OH
O
|| ⁻ ⁺
+ Mg H — C — ONH₄ + 2Ag + 2NH₃ + H₂O

(vii) Fehling’s Reagent

(ii) HCN

O
O OH ||
|| | H — C — H + 2Cu(OH)₂ + 2NaOH
H — C — H + HCN H — C — CN
|
H

(iii) NaHSO₃
O OH HCOONa + Cu₂O + 3H₂O
|| |
H — C — H + NaHSO₃ H — C — SO₃Na
|
H

(iv) NaOH

O
||
2 H — C — H + NaOH CH₃OH + HCOONa

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29
 NOTES

Question02 (v) I₂/NaOH

How does acetaldehyde reacts with O

following? ||
CH₃ — C — H + 3I₂ + 4NaOH
(i) HCN (ii) C₂H₅Mgl
(iii) NaHSO₃ (iv) dil. NaOH
(v) I₂/NaOH (vi) NaBH₄/H₂O
HCOONa + CHI₃ + 3H₂ + 3NaIO
(vii) NH₂OH (viii) K₂Cr₂O₇/ H₂SO₄

Answer
(vi) NaBH₄/H₂O

(i) HCN

O OH O
|| | ||
CH₃ — C — H + HCN CH₃ — C — H CH₃ — C — H + 2[H] NaBH₄ CH₃ —CH₂ —OH
H₂O
|
CN
(vii) NH₂OH
(ii) C₂H₅Mgl
O
O OH ||
|| | CH₃ — C — H + NH₂OH
⁻ ⁺
CH₃ — C — H + C₂H₅MgI CH₃ — C — OMgI
|
CN
O
OH ||
H CH₃ — C — N — OH + H₂O
|
⁻ ⁺ H₂O Oxime
CH₃ — C — OMgI CH₃ — CH — OH + Mg
HCl
| |
C₂H₅ C₂H₅ (viii) K₂Cr₂O₇/ H₂SO₄
I

O O
(iii) NaHSO₃ || ||
K₂Cr₂O₇
CH₃ — C — H + [O] CH₃ —C —OH
H₂SO₄
O OH
|| |
CH₃ — C — H + NaHSO₃ CH₃ — C — H
|
⁻ ⁺
SO₃Na

(iv) dil. NaOH

O OH O
|| ⁻ | ||
OH
2 CH₃ — C — H CH₃ — CH — CH₂ — C — H

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30
 NOTES

Question04 Question05

Q.7 How does acetaldehyde reacts Q.16 How would you bring about the
with following? following conversions?
Answer (i) Acetone into t-Butyl alcohol
(i) Acetaldehyde ii) Propanal into 1-propanol
HgSO₄ (iii) Propanone into 2-propanol
CH = CH + H₂O CH₂ — CH — OH iv) Methanal into Ethanal
10% H₂SO₄
(v) Ethanal into propanone
O
|| (vi) Ethanal into 2-propanol
CH₂ — CH — OH CH₃ — C — H (vii) Ethene into Ethanal
(viii) Ethanal into Ethanol
(ii) Acetone (ix) Ethanol into 2-butanone

CH ≡ CH + NaNH₂ CH ≡ CNa
⁻ ⁺
+ NH₃
(x) Methanol into Ethanal
(xi) Ethanal into Ethanoic acid

Answer
CH ≡ ⁻ ⁺
CNa + NH₃ CH ≡ C — CH₂ + NaI (i) Acetone ——— Tert-butyl alcohol

OH OH CH₃
| | |
CH ≡ C — CH₂ + H₂O CH₃ — C — CH₃ CH₃ — C — CH₃ + CH₃MgBr
⁻ ⁺
CH₃ — C — OMgBr
|
CH₃
OH O
| ||
CH₃ — C — CH₃ CH₃ CH₃ Br
CH₃ — C — CH₃ | H₃O⁺ | |
⁻ ⁺
CH₃ — C — OMgBr CH₃ — C — OH + Mg
| | |
(iii) Ethyl Alcohol CH₃ CH₃ OH

CH ≡ CH + H₂O CH₂ — CH — OH
(ii) Propanal —— 1-propanol

O O
|| ||
CH₂ — CH — OH CH₃ — C — H CH₃ — CH₂— C — H + H₂
Pd

O
|| Pd CH₃ — CH₂ — CH₂ — OH
CH₃ — C — H + H₂ CH₃ — CH₂ — OH
(iii) Propanone ——— 2-propanol

O
||
CH₃ — C — H + H₂ Pd CH₃ — CH — CH₂
|
OH

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31
 NOTES

(iv) Methanal —— Ethanal (viii) Ethanal ——— Ethanol

O OMgBr O
|| | || K₂Cr₂O₇
H — C — H + CH₃MgBr H—C—H CH₃ — C — H + H₂O CH₃ — CH₂ — OH
H₂SO₄
|
H
H Br (ix) Ethanol —— 2-butanone
| ⁺ |
H₃O
H — C — OMgBr CH₃CH₂OH + Mg
| | CH₃ — CH₂OH + HBr CH₃ — CH₂Br + H₂O
CH₃ OH

O
CH₃ — CH₂Br + Mg CH₃ — CH₂MgBr
K₂Cr₂O₇ ||
CH₃ — CH₂ — OH + [O] H — C — H + H₂O O
H₂SO₄
||
CH₃ — CH₂MgBr + CH₃ — C — H
(V) Ethanal —— propanone
O H OMgBr
|| | |
CH₃ — C — H + CH₃MgBr CH₃ — C — OMgBr CH₃ — C — CH₂ — CH₃
| |
CH₃ OMgBr H
|
H — C — CH₂ — CH₃ + H₂O
H Br |
| ⁺ |
H₃O H
CH₃ — C — OMgBr CH₃ — CH — OH + Mg OH Br
| | |
| |
CH₃ CH₃ — CH — OH + Mg
CH₃ OH
| |
H OH
OH O OH
| || | K₂Cr₂O₇
K₂Cr₂O₇
CH₃ — CH — CH₃ + [O] CH₃ — C — CH₃ H — C — CH₂ — CH₃ + [O]
H₂SO₄ | H₂SO₄
H OH
(vi) Ethanal —— 2-propanol |
CH₃ — CH — CH₃ + H₂O
O H
|| | (x) Methanol —— Ethanal
CH₃ — C — H + CH₃MgBr CH₃ — C — OMgBr O
| ||
CH₃ CH₂ — OH + [O] H — C — H + H₂O

H O
Br
| ||
|
CH₃ — C — OMgBr H — C — H + CH₃MgBr CH₃ — CH₂OMgBr
CH₃ — CH — OH + Mg
| | | Br
CH₃ CH₃ OH H₃O
⁺ |
CH₃ — CH₂OMgBr + H₂O CH₃ — CH₂OH + Mg
|
(vii) Ethene ——— Ethanal OH
O
K₂Cr₂O₇ ||
CH₂=CH₂ + H₂O CH₃ — CH₂ — OH CH₃ — CH₂aOH + [O] CH₃ — C — H + H₂O
H₂SO₄

O (xi) Ethanal ——— Ethanoic Acid

H₃O
⁺ ||
CH₃ — CH₂ — OH + [O] O O
H — C — H + H₂O
|| ||
K₂Cr₂O₇
CH₃ — C — H + [O] CH₃ — C — OH
H₂SO₄

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 NOTES

Question 06 (iv) Acetone and ethyl alcohol

Both can be distinguished by
How will you distinguish between
reacting with phenylhydrazine.
i) Methanal and ethanal O
||
(ii) Ethanal and propanone
CH₃ — C — CH₃ + NH₂ — NHC₆H₅
(iii) Ethanal and propanal
(iv) Acetone and ethyl alcohol N — NH — C₆H₅
|
(v) Butanone and 3-pentanone CH₃ — C
| — CH₃ + H₂O
(vi) Acetaldehyde and benzaldehyde Acetolphenol
(vii) 2-pentanone and 3-pentanone hydrazine
CH₃ — CH₂ — OH + NH₂ — NHC₆H₅
Answer
No reaction
i) Methanal and ethanal
Both can be distinguish by (v) Butanone and 3-pentanone
iodoform test.
O Both can be distinguished by
|| iodoform test.
CH₃ — C — H + 4NaOH + 3I₂ O
|
CH₃ — CH₂ — C — H + 4NaOH + 3I₂
CHI₃ + 3NaI + 3H₂O + HCOONa |

O CHI₃ + CH₃COONa + 3NaI + 3CHI₃ + 3H₂O

|
CH₃ — C
| — H + 4NaOH + 3I₂ O
|
CH₃ — CH₂ — C — CH₂ — CH₃ + NaOH + I₂
No iodoform test |
(ii) Ethanal and propanal
No reaction
Both can be distinguished by
iodoform test. (vi) Acetaldehyde and benzaldehyde
O 1. Acetaldehyde give iodoform test
||
CH₃ — C — H + 4NaOH + 3I₂ while benzaldehyde give no
iodoform test.

CHI₃ + 3NaI + 3H₂O + HCOONa 2. Benzaldehyde give cannizzaro

O reaction while acetaldehyde gives
|| aldo product.
CH₃ — CH₂ — C — H + NaOH + I₂

(vii) 2-pentanone and 3-pentanone

No reaction O
(iii) Ethanal and propanone |
CH₃ — CH₂ — CH₂— C — H + 4NaOH + 3I₂
Both can be distinguish by mild
|
oxidizing agent. e.g., Benedict’s,
Fehling’s. CHI₃ + CH₃ — CHCOONa + 3NaI + 3CHI₃ +
O 3H₂O
|| O
CH₃ — C — H + 2Cu(OH)₂ + 2NaOH
|
CH₃ — CH₂ — C — CH₂ — CH₃ + NaOH + I₂
CH₃OONa + Cu₂O + 3H₂O |
Red ppt
O No reaction
|
CH₃ — C| — H + Bendict's
solution

PUNJAB BOARD No reaction

 NOTES

Question 07 (b) Oxidation of Ketones

Discuss oxidation of (a) aldehydes (b) O

ketones with ||
CH — C — CH₃ + 3[O]
(i) K₂Cr₂O₇

Conc. H₂SO₄
K₂Cr₂O₇
(ii) Tollen’s reagent
(iii) Fehling’s solution

(a)Oxidation of Aldehydes CH₃COOH + HCOOH

(i) Ketones are note oxidized by

Aldehydes are oxidized by strong tollen’s reagent.
as well as weak oxidising agents.
Mixture of conc. H₂SO₄ and (ii) Ketones are note oxidized by
K₂Cr₂O₇ is strong oxidizing Fehling’s solution or Banldict’s
agent. Fehling solution, solution.
Benedict’s solution and
ammonical silver nitrate are Question 08
weak oxidizing agent.
Discuss reduction of
O (a) aldehydes (b) ketones with
||
(i) R — C — H + [O] (i) NaBH₄/H₂O (ii) H₂/Pd
Conc. H₂SO₄

K₂Cr₂O₇

(a) Reduction of Aldehydes

Aldehyde after reduction

O
changes to primary alcohol.
||
R — C — OH
O
||
NaBH₄
CH — C — H + 2[H] CH₃ — CH₂ —OH
H₂O
O
|| O
(ii) R — C — H + [Ag(NH₃)₂⁺] + 2OH⁻ ||
Pd/Pt
CH — C — H + H₂ CH₃ — CH₂ —OH

(b) Reduction of Ketones

O
|| Ketones on reduction form
R — C — O⁻N⁺H₄ + Ag + H₂O + NH₃ secondary alcohols.

O
O ||
NaBH₄
|| CH — C — CH₃ + 2[H] CH₃ — CH —CH₃
H₂O
(iii) R — C — H + 2 Cu (OH) + 2NaOH |
OH
O
||
Pd/Pt
CH — C — CH₃ + H₂ CH₃ — CH —CH₃
|
RCOONa + Cu₂0 + 3H₂O
OH

PUNJAB BOARD
 NOTES

Do You Know
(1) Aldehydes and ketones are called (11) Aldehydes are strong reducing
carbonyl compounds. agents.

(2) Formaline contains 40% (12)Acetaldehvyde is used for silvering

formaldehyde 8% methyl alcohol and of mirrors.
52% water.
(13) Formaldehyde + Lactose
(3) Formaline is used as preservative (Formamint) is used as throat
for biological specimens. lozenges.

(4) Calcium acetate on heating forms (14) Formaldehyde is used in the

acetone. preparation of Bakelite (plastic).

(5) Acetone is used as nail polish (15) Ethyne on hydration with 10%
remover. H₂SO₄ and HgSO₄ forms acetaldehyde
while
(6) Aldehydes and Ketones having no propyne on hydration forms acetone.
α-hydrogen atom do not undergo
aldol condensation.

(7) Formaldehyde reacts with NH₃ to

form hexa methylene tetramine which
is used as
urinary antiseptic. Its trade name is
urotropine.

(8) Formaldehyde is also used to

prepare antipolio vaccine.

(9) (AgNO; + NH4OH) s called Tollen’s

reagent.

(10) Ketones produce orange red

colour with sodium nitro prusside afier
addition of
NaOH.

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