MODULE - 7 Aldehydes, Ketones and Carboxylic Acids

Chemistry of Organic
Compounds

27
Notes
ALDEHYDES, KETONES AND
CARBOXYLIC ACIDS

In the last lesson, you studied about organic compounds containing functional
groups having carbon-oxygen single bond. There are other classes of organic
compounds in which the functional group contains the carbon- oxygen double
bond. The examples of these classes of compounds being carbonyl compounds
such as aldehydes and ketones as well as carboxylic acids and their derivatives.
These organic compounds are very important both in the industry and in the
synthesis of other organic compounds. Therefore, their study forms an important
part of the organic chemistry. Let us study the chemistry of these classes of
compounds in detail.

OBJECTIVES
After reading this lesson, you should be able to
z give IUPAC names of aldehydes and ketones;
z describe the general methods of preparation of aldehydes and ketones;
z discuss the trends in physical properties of the aldehydes and ketones in the
light of the polar nature of the carbonyl group;
z explain important reactions exhibited by aldehydes and ketones;
z distinguish between aldehydes and ketones on the basis of certain reactions
and tests based on them;
z give IUPAC names of carboxylic acids;
z explain general methods of preparation of carboxylic acids;
z discuss the physical properties and their trends for simple monocarboxylic
acids;
z describe important reactions exhibited by carboxylic acids;

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z explain the preparation and some interconversion reactions of carboxylic Compounds
acid derivatives, and
z highlight the importance of aldehydes, ketones and carboxylic acids.

27.1 ALDEHYDES AND KETONES

You have some familiarity with these classes of compounds from previous
Notes
lessons. These compounds are also referred to as carbonyl compounds and have
O
C functionality present in them. These compounds exist widely in nature
and are responsible for the flavour and aroma of many foods. They are also
important industrially both as reagents in synthesis and as solvents.
Aldehydes have at least one hydrogen atom bonded to the carbonyl group, the
other group may be either a hydrogen or an alkyl (or aryl) group. In ketones,
the carbonyl group is bonded to two alkyl or aryl groups. The two groups
bonded to a ketone may be similar or different resulting in a symmetrical or
an unsymmatrical ketone, respectively.

:O : :O : :O :

C C C
R H R R
Carbonyl group an aldehyde a ketone

You must be familiar with vanilin and camphor. Their structures are given below.
You can see that they contain an aldehyde and a keto functional group,
respectively.

O
C H CH3 CH3

HO
O
OCH3 CH3
Vanilin
(used for vanila flavour) Camphor

27.1.1 Nomenclature of Aldehydes and Ketones

In the IUPAC system of nomenclature, aliphatic aldehydes are named as
alkanals. The final -e in the name of the corresponding alkane is substituted
by -al.

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Compounds Some common examples of aldehydes and their names are given below :

O O O O

H C H CH3 C H CH3CH2 C H C H

Methanal Ethanal Propanal Benzenecarbaldehyde

(Formaldehyde) (Acetaldehyde) (Propionaldehyde) (Benzaldehyde)
Notes
Note that when the -CHO group is attached to a ring, then the compound is
called a carbaldehyde.
Remember that the carbonyl carbon of the aldehydes is present at the end of
the chain and is assigned 1 position. Therefore, it is not necessory to specify
its position in the name of the aldehyde. The examples given below illustrate
this point.

Br

CH3CHCHO ClCH2CH2CH2CHO
3 2 1 4 3 2 1

2-Bromopropanal 4-Chlorobutanal

Ketones are named as alkanones in the IUPAC namenclature. Their names are
obtained by replacing final -e in the name of alkane by -one. The carbon chain
is numbered in such a way that the carbonyl group gets the lowest number. Some
examples of ketones are mentioned below :
O
O O

CH3CCH3 CH3CH2CCH3
4 3 2 1
Propanone
(Acetone) Butan-2-one Cyclohexanone
(Ethyl methyl ketone)

O O

CH3CH2CCH2CH3 CH3CCH2CH CH2

5 4 3 2 1
Pent-4-en-2-one
Pentan-3-one
(Diethyl ketone)

O O
CCH3 C

1-Phenylethanone (Benzophenone)
(Acetophenone)

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27.1.2 Preparation of Aldehydes and Ketones Compounds
You have already studied most of the methods used in the synthesis of aldehydes
and ketones in the previous lesson. Let us now refresh them.
1. Oxidation of Primary and Secondary Alcohols
From the last lesson, you know that primary alcohols can be oxidised to
aldehydes and secondary alcohols can be oxidised to ketones. Notes
2. Ozonolysis of Alkenes
This reaction has been discussed in lesson 26. The products obtained are
aldehydes or ketones depending upon the structure of the starting alkene.
3. Hydration of Alkynes
Hydration of alkynes can give an aldehyde or a ketone. Markovnikov’s hydration
yields ketones whereas anti-Markovnikov’s hydration gives aldehydes.
O
HO H
Hg2+, H+
RC CH C C RCCH3
H2O
Alkyne R H Ketone

( ) BH
2
R
C C
H
RC CH
Alkyne
H B ( )
2
–
H2O2, HO

R H
RCH2CH C C
H OH
O
Aldehyde

You can go through the details of these reactions as discussed in lesson 26.
4. Friedal-Crafts Acylation
Aromatic ketones can be prepared by Friedel-Crafts acylation (alkanoylation)
reaction. One example of this reaction is given below:

O
1. CH3COOCOCH3, AlCl3, CS2
CH3O 2. HCl, H2O
CH3O C

Similar acylation reaction using ethanoyl chloride was also discussed in lesson
26 under the electrophilic substitution reactions of aromatic hydrocarbons.

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Compounds 27.1.3 Structure and Physical Properties
In both aldehydes and ketones, the carbonyl carbon and oxygen atoms are sp2
hybridised. Therefore, the groups attached to the carbon atom and oxygen are
present in a plane. This is shown in Fig. 27.1.
pi bond formed by
p-orbitals
Notes

:
R
C O Lone pairs of electrons

:
R¢

Fig. 27.1 : The structure of the carbonyl functional group

You can see in the figure that a π-bond is formed by the overlap of p-orbitals
of carbon and oxygen atoms. The p-orbitals are present in a plane perpendicular
to the plane of the molecule. Note the presence of two lone pairs of electrons
on oxygen atom.
You also know that oxygen is more electronegative than carbon. Hence, it
attracts the electrons of the carbon-oxygen double bond ( C O bond)
resulting in its appriciable polarisation.
+ d+ d–
–
[ [ or
: :

: :

: :

C O C O C O

The oxygen atom, thus, acquires a partial negative charge (δ − ) whereas the
carbon atom gets a partial positive charge (δ + ) . This polar nature of the carbonyl
group makes the oxygen atom nucleophilic and basic while the carbon atom
becomes electrophilic. The physical properties and chemical reactions of
aldehydes and ketones are a direct consequence of this polarisation.
The dipole-dipole attraction between the molecules of aldehydes and ketones
results in their higher boiling points as compared to the hydrocarbons of similar
molecular weight. The physical properties of some aldehydes and ketones are
given in Table 27.1.
Table 27.1 Physical properties of some representative aldehydes and ketones

Compound m.p. b.p. Water Solubility

(K) (K) (%)

Methanal 181 252 55

Ethanal 150 294 ∞
Propanal 192 322 20

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Butanal 166 348 7.1 Compounds
Benzaldehyde 217 452 0.3
Propan-2-one 178 329 ∞
Butan-2-one 187 353 25.6
Pentan-2-one 195 375 5.5
Pentan-3-one 232 374 4.8
Notes
Acetophenone 294 475 15
Benzophenone 321 578 –

You can see from Table 27.1 that these compounds have appriciable water
solubility. This is because of the hydrogen bonding possible between the oxygen
atom of the aldehyde (or the ketone) with hydrogen atom of water molecule,
as shown in Fig 27.2.
d– d–
: :

:O: O
d+ d+
C H H
d+
R R¢ Hydrogen bonding

Fig. 27.2 : Hydrogen bonding between carbonyl compound and water molecule

27.1.4 Reactions of Aldehydes and Ketones

If you examine the structure of a molecule of the carbonyl compound, you will
find that there are three centres of reactivity in it as shown below :

d–
Prone to attack by
O electrophiles

a–Carbon C C+
d
H R
Susceptible to attack
Acidic hydrogen by nucleophiles
Since the oxygen atom is nucleophilic in nature, it is attacked by the
electrophiles, whereas the carbonyl carbon is electrophilic in nature and hence
is attacked by nucleophiles. The third site of reactivity is hydrogen atom present
at the α - carbon atom. It is acidic in nature and gives typical reactions which
you will study in this section.
It is also important to know here that aldehydes are more reactive than ketones.
This is because of the following two reasons :
(i) Aldehydes have only one alkyl group whereas ketones have two. Since the
alkyl groups are electron donating in nature, the carbonyl carbon in ketones
which is bonded to two alkyl groups, is less positive (electrophilic) as
compared to the aldehydic carbonyl carbon. Hence, it is less susceptible to
attack by nucleophiles.

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Compounds (ii) The two alkyl groups in ketones also make the carbonyl carbon more
crowded as compared to carbonyl carbon in aldehydes. This factor also
makes the aldehydic carbonyl carbon more accessible for attack by the
nucleophiles as compared to carbonyl carbon of the ketone.
With this background in mind, let us now study the reactions of aldehydes and
ketones.
Notes
A. Nucleophilic Addition Reactions
The general reaction of addition of nucleophiles on the carbonyl group can be
represented as follows :
Nu
R d+ d– d+ d–
C O+H Nu R C OH
H
H

Mechanism of Nucleophilic Addition

Under basic conditions, the nucleophile attacks at the carbonyl group yields a
tetrahedral intermediate. Subsequent to this, the protonation from a solvent
(H2O or alcohol) takes place. This is shown below:

d+ d. – –
: :

– HOH

: :
: :
: :

C O. : C O: C OH + : OH
–H2O
Nu Nu
– Tetra hedral Tetra hedral
Nu:
intermediate product

However, in acidic additions, in the first step the protonation of the carbonyl
oxygen takes place.
:

:
: :

C :O– + H A C OH C OH
d+ d +

The nucleophile then attacks in the second step to carbonyl carbon and the
addition process is completed.
+ Nu H
:NuH –
+ :A
:

C OH C OH
:

oxonium Nu
cetron
:

C O. H + HA
+

Some specific reactions of this category are discussed below :

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1. Formation of Cyanohydrins Compounds

Carbonyl compounds react with hydrogen cyanide to yield cyanohydrins.

O CN

H3C C CH3 + H CN CH3 C OH

Propanone CH3 Notes
Cyanohydrin

Note that one more carbon atom is present in the cyanohydrin as compared to
the starting carbonyl compound.
Cyanohydrins are useful in the synthesis of carboxylic acids about you will study
in the next section.
2. Formation of Hemiacetals
Aldehydes and ketones react with alcohols to give hemiacetals. Hemi in Greek
means half. Hemiacetals have an –OH and an –OR group attached to the same
carbon atom in their molecules.
When an excess of the alcohol is used, a second molecule of the alcohol reacts
to give an acetal.

O OH OCH3
HCl (g) CH3OH
CH3CH + CH3OH CH3CH CH3 C OH
Ethanal Methanol
OCH3 OCH3
a Hemiacetal an Acetal

O OH OCH3
HCl (g) CH3OH
CH3CH + CH3OH CH3CH CH3 CH3 C OH
Propanone Methanol
OCH3 OCH3
a Hemiacetal an Acetal

Note that an acetal has two —OR groups attached to the same carbon atom.
Acetals are stable in basic solutions and are ‘therefore’ used as protecting groups
for aldehydes and ketones. Acetals can be converted back to the carbonyl
compounds by treating them with dilute acids because of the reversible nature
of the above reaction.

3. Formation of Alcohols
Grignard reagents (RMgX) react with aldehydes and ketones to give alcohols
as shown below :

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Chemistry of Organic
Compounds O H

CH3CH2MgBr + H C H H C OH
Ethyl Methanal
magnesium bromide CH2CH3
a Primary alcohol

O H
Notes CH3CH2MgBr + CH3 C H CH3 C OH
Ethyl magnesium Ethanal
bromide CH2CH3
a Secondary alcohol

O CH3

CH3CH2MgBr + CH3 C CH3 CH3 C OH

Ethyl magnesium Propanone
bromide CH2CH3
a Tertiary alcohol

You have already studied these reactions under the preparation of alcohols in
lesson 28.
B. Addition-Elimination or Condensation Reactions
1. Reaction with Ammonia and its Derivatives
Aldehydes and ketones react with ammonia and primary amines to give imines
which are compounds having carbon-nitrogen double bond.
O NH
H+
+ NH3
Ammonia
Imine
H3O+
: :

R NH2 + O C R N C or C N R
:

Primary Imine
amine (a Schiff base)
It appears that during the above reaction a molecule of water is lost from the
primary amine and the carbonyl compound. The reactions with other derivatives
of ammonia are given below:

CH H2NOH CH N OH + H2O
Hydroxylamine
an Oxime
CH3 CH3

C O + H2NNH2 C NNH2
Hydrazine
a Hydrazone

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Compounds
O + H2NNH NNH

Phenylhydrazine a Phenylhydrazone

NO2 NO2

CH3CH2CHO + N2NNH NO2 CH3CH2CH NNH NO2

Notes
2, 4-Dinitrophenzylhydrazine 2, 4-Dinitrophenzylhydrazone

The compounds formed above are relatively insoluble solids and have characteristic
melting points. These compounds can be prepared for the unknown aldehyde
or ketone and their melting points can be determined. These melting points are
matched with the derivatives of already known aldehydes and ketones listed in
standard tables and the carbonyl compound is thus identified.
C. De-oxygenation Reactions
De-oxygenation reactions are reactions involving removal of oxygen. Aldehydes
and ketones can be reduced to the corresponding alkanes by the following two
reactions:
1. Wolff-Kishner Reduction
When an aldehyde or a ketone is heated in a basic solution of hydrazine in a
high-boiling alcohol, then the carbonyl group gets converted to a methylene
( CH2) group.
O
1. NH2NH2– , OH/D
CCH3 2. H2O
CH2CH3

Ethylbenzene

2. Clemmensen Reduction
It is carried out in acidic medium using amalgamated zinc and hydrochloric acid.
Zn(Hg)
CH3(CH2)5CHO HCl, H2O
CH3(CH2)5 CH3
Heptanal Heptane

D. Oxidation of Aldehydes
Unlike ketones, aldehydes can be easily oxidised to carboxylic acids using a
variety of oxidising agents. These reagents can be chromic acid, chromium
trioxide, permanaganate or silver oxide. You have already read about oxidation
with some of these reagents. Silver ions selectively oxidise —CHO group. This
forms the basis of Tollen’s test. It involves the addition of a mixture of aqueous
silver nitrate and aqueous ammonia which is known as Tollen’s reagent to the

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Compounds carbonyl compound. Tollen’s reagent contains [Ag(NH3)2]+ complex ion. If an
aldehyde is present, it gets oxidised to the carboxylic acid whereas the Ag + ions
are reduced to form silver metal which gets deposited on the walls of the test
tube and this gives a mirror like shining appearance.

O O
[Ag(NH3)2]+
Notes R C H H2O
R C O– + Ag ¯
Aldehyde mirror

Aldehydes are also oxidised by Fehling solution, which contain Cu 2+ (cupric)

ions complexed with tartarate ions as the oxidant. These Cu 2 + ions are reduced
by the aldehydes in alkaline medium to give a brick red precipitate of cuprous
oxide.

O
NaOH
R C H + Cu2+ H2O
Cu2O¯ + RCOOH
Aldehyde blue brick red ppt.

E. Reactions at α-carbon
The α − hydrogen in aldehydes and ketones is quite acidic and can be easily
abstrated by a strong base.

O O–
HO
C :C– C C
C C H + HO–
R enolate ion
keto form a-Hydrogen

The resulting anion can stabilise by resonance as shown above. It is called an

enolate ion. On protonation, it gives an enol.

–
O HO
C C + H2O C C + –OH
enolate enol

Thus, keto form and enol form are in equilibrium. This is also known as keto-
enol tautomerism.
Other reactions feasible due to the presence of α- hydrogen are as follows:
1. Halogenation
Ketones having an α- hydrogen atom react readily with halogens and
α- haloketones are obtained as the product. The reaction is promoted both by
acids and bases.

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H O X O Compounds
H+
C C + X2 or –OH
C C

a-halo product
(X 2 = Cl2 , Br2 or I 2 )
O O
Br2, CH3COOH
H CH2CCH3 H2O, 343 K
BrCH2CCH3 + HBr
Notes
Propanone Bromopropanone

In presence of the base, multiple halogenation occurs to give the trihalo product.
O H O X
3X2 + NaOH
C C H + C C X + 3NaX + 3H2O
H X
trihaloketone

The trihalo group is a good leaving group and the trihalo ketone reacts with
OH– which finally gives a carboxylate ion and a haloform.
– X
O X O
–
C C X + HO – C O + H C X

X X X
trihaloketone Carboxylate ion Haloform
This reaction is called the haloform reaction after the name of the product.
If iodine is used as the halogen, then we get iodoform (CHI3) as the product.
The iodoform is a bright yellow solid having a characterstic melting point. This
reaction, thus, forms the basis of the iodoform test. Thus, methyl ketones give
a positive iodoform test. You had studied the iodoform formation in lesson 27
also.
2. Aldol Condensation
Aldehydes having α − hydrogen atom on reaction with dil. NaOH give aldols.
The reaction is illustrated below by using ethanal as the example.
O OH
NaOH
CH3 C + H3CCHO H2O, 278 K
CH3 C CH2CHO

H H
Ethanal Ethanal 3-Hydroxybutanal
(an Aldol)
Note that the product contains both the aldehyde and the alcohol functional
groups and therefore, it is called an aldol. The aldol addition product on heating
undergoes dehydration to give an α, β– unsaturated aldehyde which is a
condensation product.

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Chemistry of Organic
Compounds OH
H CHO
D
R C CH2CHO C C + H2O
H3C H
H
Aldol trans-But-2-enal

This complete sequence of reactions is called aldol condensation.

Notes Aldol condensation is also possible with ketones. Can you now think of a little
more complex situation? What will be the products of aldol condensation when
two diffrent aldehydes having α − hydrogen atoms are used as reactants. In this
case, the reaction is called a crossed-aldol condensation. This is left as an
exercise for you. There is a hint of course. Suppose, the two aldehyde molecules
are represented by A and B; then condensation can occur between two molecules
of the same aldehyde or diffrent aldehydes. Thus, the products obtained would
be the following types:
A-A, B-B, A-B and B-A.
With this background in mind, you can now proceed to write the aldol addition
products of ethanal and propanal.

3. Cannizzaro Reaction
Aromatic or aliphatic aldehydes which do not have α-hydrogen, an reaction with
conc. KOH/NaOH give one molecule of and alcohol and sodium salt of the
carboxylic acids. This reaction is known as Carnizzaro reaction.
In this reaction, one molecule of the aldehyde is oxidised to carboxylic acid salt
(sod. or pot. salt) and another molecule of the aldehyde is reduced to alcohol
molecule. For example,
H
Conc. KoH
2 C O D
CH3 OH + H COOK
H Methanol Potassium torwate.
Methanol
H H
O
Conc. NaOH – +
C D
C OH + C O Na
H
H
Benzaldehyde
Benzyl alcohol Sodium benzoate

CH3 CH3 CH3

Conc. NaOH – +
2 CH3 C CHO CH3 C CH2 OH + CH3 C COO Na
D

CH3 CH3 CH3

2,2 -dimethyl 2,2 -dimethyl
propanal propan-1-01

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This reaction takes place by nucleophilic addition of —OH to an aldehyde to Compounds
give tetrahedral intermediate. This intermediate expels a hydride ion as the
leaving group.
O
O –

: :
:O : C
H H O
C – C
: :

H : OH
:
OH C Notes
–H –
HO
+
tetra hedral
N
intermediate
–
O C

H
This hydride ion is accepted by second molecule of aldehyde

O H C H
C
OH +

H+

COOH CH2OH

Carboxylic
acid
alcohol

Thus, we can say, that disproportonation has occurred and simultaneous

oxidation and reduction has taken place to give one molecule of a carboxylic
acid and are molecule of an alcohol from the two molecules of the starting
aldehyde. This reaction is limited to those aldehydes only which have no
hydrogen on carbon next to the CHO group.

INTEXT QUESTIONS 27.1

1. Classify the following as aldehydes or ketones and give their IUPAC names:
(i) CH3CHO (ii) CH3COCH 2 CH3
COOH3

(iii) (iv) OHCCH 2 CH3

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Compounds 2. How will you prepare propanone from propyne ?
3. Why are aldehydes more reactive than ketones towards nucleophilic addition
reactions?
4. Write the general structure for the following :
(i) a cyanohydrin (ii) an acetal (iii) a hemiacetal

5. How can you convert the carbonyl C O group to CH2 group ?

Notes
6. What is an aldol?
7. Write the equation for cannizzaro reaction using a suitable example.

27.2 CARBOXYLIC ACIDS

You already know that carboxylic acids contain a carboxyl ( ⎯ COOH) funtional
group. They are most widely distributed in nature and are also industrially
important chemicals. Acetic acid in the form of vinegar is produced in large
quantities. It is also a very important building block in complex biological
molecules. You must have also heard about fatty acids which are long chain
aliphatic acids derived from the hydrolysis of fats and oils. Stearic acid is a fatty
acid containing a long chain of eighteen carbon atoms.

27.2.1 Nomenclature
Several carboxylic acids have been known since long and their common names
are based on their sources. However, in the IUPAC nomenclature, carboxylic
acids are named by choosing the longest carbon chain containing the −COOH
group. The final -e in the name of the alkane is replaced by -oic acid. While
numbering the carbon chain, the −COOH carbon is always given number 1 as
shown below :
O
C C C C C OH
5 4 3 2 1

The other groups and substituents are numbered and named according to the
usual rules of nomenclature which you have already studied.
Some common carboxylic acids and their names are given below :

O
O O
|| || C OH
H C OH CH 3 C OH
Methanoic acid Ethanoic acid Phenylmethanoic acid
(Formic acid) (Acetic acid) (Benzoic acid)

Carboxylic acids containing two carboxyl groups are called dicarboxylic acids.

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They are named by adding dioic acid as a suffix to the name of the corresponding Compounds
hydrocarbon. Both the carboxyl carbon atoms are numbered as a part of the
main chain. Note that in this case, final- e of the alkane is not dropped.

OO O O
|| || || || 43 2 1
HO C C OH HOC CH 2 COH HOO CC H 2C H 2C OOH
1 2 Propanedioic acid Butane-1,4-dioic acid
Ethanedioic acid (Malonic acid) (Succinic acid) Notes
(Oxalic acid)

COOH COOH COOH

COOH

COOH
o-Phthalic acid m-Phthalic acid
(Phthalic acid) COOH
(Isophthalic acid) o-Phthalic acid
(Terephtyhalic acid)

27.2.2 Preparation of Carboxylic Acids

The following methods are generally used for the synthesis of carboxylic acids.
You have already studied some of these methods in the earlier lessons.
1. Oxidation of Alkenes
Alkenes on oxidation with hot alkaline KMnO4 yield carboxylic acids.

1⋅KMnO , −OH
RCH=CHR ′ ⎯⎯⎯⎯⎯⎯→
4
+ RCOOH + R ′COOH
2⋅ H3O

2. Oxidation of Alcohols and Aldehydes

You have read in the last lesson and the previous section of this lesson that
alcohols and aldehydes can be oxidized to carboxylic acids using a variety of
oxidising agent. You can refer back to the details of these reactions.
3. Oxidation of Alkylbenzenes
Primary and secondary alkyl groups attached to the benzene ring can be oxidised,
using alkaline KMnO4 , to the carboxyl group.

CH3 COOH

1. KMnO4, –OH, D
2. H3O+

Methylbenzene Benzoic acid

Acidified sodium dichromate can also be used for this oxidation.

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Compounds CH3
CH3 CH COOH

Cl Cl
Notes p-Chlorobenzoic acid

4. Carbonation of Grignard Reagents

Grignard reagents (RMgX) react with carbon dioxide to give magnesium
carboxylates which on acidification yield carboxylic acids.

O
+
R CO - Mg+ X
H
RMgX + CO 2 RCOOH

Mg
CH3 CH 2 Cl ⎯⎯⎯→ CH3 CH 2 MgCl 1⋅CO2
Et 2O ⎯⎯⎯⎯ → CH3 CH 2 COOH
Chloroethane Grignard reagent 2⋅H3O+
(an alkyl halide) Propanoic acid

MgBr COOH

1. CO2
2. H2O+

Phenyl magnesium bromide Benzoic acid

Note that there is an increase of one carbon atom in the carboxylic acid as
compared to the starting alkyl halide.

5. Hydrolysis of Nitriles and Cyanohydrins

Alkyl halides can be converted to nitriles which on hydrolysis yield carboxylic
acids having one more carbon atom than the starting alkyl halide.

– +
,D CH2 CH2
H3O
Ethene
–
R CH2X + CN RCH2CN –
OH, D (Alkene)
Alkyl halide Nitrile – H3O
+

+ RCH2COO RH2COOH
– + NH3
X

+
NaCN H3O
Br CH 2 CH 2 Br ⎯⎯⎯⎯
→ NC CH 2 CH 2 CN ⎯⎯⎯→ HOOCCH 2 CH 2 COOH
1, 2-Dibromoethane Butane dinitrile Butanedioic acid

322 CHEMISTRY
Aldehydes, Ketones and Carboxylic Acids MODULE - 7
Chemistry of Organic
Cyanohydrins obtained from aldehydes also yield 2-hydroxycarboxylic acids on Compounds
hydrolysis.
OH OH
+
H3 O
CH3CH2 C CN CH3CH2 C COOH

H H
2-Hydroxybutanenitrile 2-Hydroxybutanoic acid
Notes

27.2.3 Structure and Physical Properties

Similar to the aldehydes and ketones, the carboxyl carbon atom is sp 2

hybridised. Thus, the three atoms attached to this carbon which lie in the same
plane with an approximate bond angle of 120º between them, see Fig. 27.3.

O
120º 120º
C
C OH
120º

Fig. 27.3 : Structure of the carboxyl group

Carboxylic acids form hydrogen bonds because of the presence of polar carbonyl
and hydroxyl groups. Most carboxylic acids exist in dimeric form in which two
carboxylic acid molecules are held together by two hydrogen bonds. This is
shown below :

O H O
Hydrogen bond
R C C R
O H O

Dimer of a carboxylic acid

Intermolecular hydrogen bonding is in fact responsible for high melting and

boiling points of carboxylic acids. The melting and boiling points of some
carboxylic acids are listed in Table 27.2. You can also see in the table that the
lower members have appreciable solubility in water. This is also due to the
presence of hydrogen bonding between the carboxylic acid molecule and solvent
water molecules.
Table 27.2 : Some Physical Properties of Carboxylic Acids

Carboxylic Acid m. p. b. p. Water solubility

pKa
(K) (K) gmL–1 of H2O at 298K
HCOOH 281 373·5 ∞ 3·75
CH3COOH 289.6 391 ∞ 4·76

CHEMISTRY 323
 MODULE - 7 Aldehydes, Ketones and Carboxylic Acids
Chemistry of Organic
Compounds CH3CH 2 COOH 252 414 ∞ 4·87

CH3CH 2 CH 2 COOH 267 437 ∞ 4·82

CH3CH 2 CH 2 CH 2 COOH 239 460 4·97 4·81

ClCH 2 COOH 336 462 very soluble 2·86

Cl2 CHCOOH 283.8 465 very soluble 1·48

Notes
Cl3CCOOH 329.3 471 very soluble 0·70

C6 H5 COOH 295 523 0·34 4·19

p-CH3C6 H 4 COOH 450 548 0·03 4·36

p-ClC6 H 4 COOH 515 0.009 3.98

p − NO2 C6 H 4 COOH 515 0.03 3.41

Do not worry about the pK a values listed in the last column of the table. We
will refer to them when we discuss the acidic nature of carboxylic acids in the
following section.

27.2.4 Acidity of Carboxylic Acids

Carboxylic acids are acidic in nature. They dissociate in water according to
following equilibrium to give a proton and the carboxylate ion.
O O
–
R C O H + H2O R C O + H 2O +
Carboxylic acid Carboxylate ion

The pKa values of some carboxylic acids are given in the last column of Table
27.2. Remember that the lower pKa indicates greater acidity. If you compare
these pKa value with those of alcohols, you will note that the carboxylic acids
are much more acidic than alcohols. This can be explained on the basis of the
anion formed as a result of ionisation. The carboxylate ion obtained by the
dissociation of carboxylic acids can be represented as a resonance hybrid of the
following two structures:
–
: :

O O:
R C R C
: :

: O– O
Resonance structures of Carboxylate Ion

These structures show that the negative charge is delocalised over two oxygen
atoms. Thus, the carboxylate ion gets stabilised. The greater stability of
carboxylate ion facilitates the release of proton from the –COOH group.

324 CHEMISTRY
Aldehydes, Ketones and Carboxylic Acids MODULE - 7
Chemistry of Organic
–
If you compare this situation with the alkoxide ion (RO ) obtained by the Compounds
dissociation of an alcohol molecule, you will see that no such resonance
stabilisation is possible in the alkoxide ion.
Let us now analyse the acid strength of different acids and correlate them with
their structure. If we examine the first five acids listed in table 27.2, we find
that their pKa values keep on increasing which means that as we go down, their
acid strength decreases. Since the alkyl groups are electron releasing in nature, Notes
they make the release of H+ difficult and hence decrease the acidity. Thus,
ethanoic acid is less acidic than methanoic acid. Therefore, we can say that the
electron-donating substitutents decrease the acidity of carboxylic acids.
Let us next see what will be the effect of electron withdrawing substituents such
as halogens and nitro-group on the acidity. The comparison of pKa values of
ethanoic acid (4·76) and chloroethanoic acid (2·86) suggests that chloroethanoic
acid is a stronger acid than ethanoic acid. The chloro substituent has −I effect
and pulls the electrons towards itself which facilitates the release of H+ ions.
You can also see below that as the number of halogen groups increases in the
carboxylic acid, its acidity increases. This is because they make the release of
H+ ion more and more easy.
N N Cl Cl

H C COOH < Cl C COOH < Cl C COOH < Cl C COOH

H H H Cl
Ethanoic acid Chloroethanoic acid Dichloroethanoic acid Trichloroethanoic acid
pKa 4.76 2.86 1.48 0.70

Acidity increases

Since the inductive effect decreases with increase in the distance of the group
in the carbon chain, 2-chlorobutanoic acid (pKa 2·86) is more acidic than 3-
chlorobutanoic acid (pKa 4.05) which is in turn more acidic than 4-chlorobutanoic
acid (pKa 4.50).
Cl Cl Cl

CH3CH3CHCOOH > CH3CHCH2COOH > CH2CH2CH2COOH

2-Chlorobutanoic acid 3-Chlorobutanoic acid 4-Chlorobutanoic acid

Acidity increases
(or decreases in the revenue order)

27.2.5 Reactions of Carboxylic Acids

Let us now study the reactions given by carboxylic acids.

CHEMISTRY 325
 MODULE - 7 Aldehydes, Ketones and Carboxylic Acids
Chemistry of Organic
Compounds 1. Formation of Salts
Carboxylic acids are completely deprotonated by strong bases such as metal
hydroxides to give salts.
O O
–
CH3C O H + NaOH CH3C O Na+ + H2O
Ethanoic acid Sodium ethanoate
Notes
It will be interesting to know that soaps are sodium salts of long chain carboxylic
acids which are called fatty acids.
O O
–
CH3(CH2)16 C OH + NaOH CH3(CH2)16 C O Na+ + H2O
Stearic acid Sodium stearate (soap)

Caboxylic acids are also deprotonated by the weak bases such as sodium
bicarbonate. In this reaction, they form sodium salt of the acid, carbon dioxide
and water.

O O
–
R C O H + NaHCO3 R C O Na+ + H2O + CO2 ­

This reaction is also used as a test for carboxylic acids in the laboratory. The
liberation of CO2 in the form of bubbles on treatment with NaHCO3 indicates
a carboxyl functional group in the compound.
This test is not given by phenols since they are weaker acids than the carboxylic
acids. Hence, the two categories of compounds can be distinguished on the basis
of the above test.

2. Reduction of Carboxylic Acids

Carboxylic acids are reduced to primary alcohols by lithium aluminium hydride
(LiAlH 4 ) .

CH2COOH CH2CH2OH
1. LiAlH4
+
2. H3O

Phenylethanoic acid 2-Phenylethanol

3. Hell-Volhard-Zelinski Reaction
Similar to aldehydes and ketones, carboxylic acids undergo halogenation at α -
carbon atom using Br2 (or Cl2 ) in the presence of phosphorus or phosphorus
trihalide.

326 CHEMISTRY
Aldehydes, Ketones and Carboxylic Acids MODULE - 7
Chemistry of Organic
Br Compounds
1. Br,2P
CH3CH2CH2COOH 2. HO2
CH3CH2CHCOOH
Butanoic acid 2 - Bromobutanoic acid

α -Haloacids so obtained are useful intermediates in the synthesis of other

organic compounds.
Notes
4. Synthesis of Acid Derivatives
This is one of the very important reactions of carboxylic acids. The nucleophilic
addition to the carboxyl carbon of the carboxylic acids is followed by elimination
of the leaving group leading to a substitution product. If you remember the
reactions of aldehydes and ketones, the addition of nucleophile is followed by
addition of the proton to give an addition product.
In case of carboxylic acids, since the substitution takes place at the acyl carbon
atom as shown below. It is also known as nucleophilic acyl substitution.

O O
– –
R C X + :Nu R C Nu + X

Here, X = OH in case of the carboxylic acids and Nu − can be a halide ion,

O
R¢ or − NH 2
– –
O C R, O group leading, respectively to carboxyl acid halides,
anhydrides, esters or amides as the substitution products which are known
as derivatives of carboxylic acids because they are derived from carboxylic
acids.

O O O

R C X R C O C R
Carboxylic acid O Carboxylic acid anhydride
halide
R C OH
Carboxylic acid
O O
R C O R¢ R C NH2
Ester Amide

(i) Formation of Acid Chlorides

Carboxylic acids react with SOCl2 , PCl3 or PCl5 to give carboxylic acid chlorides
also known as acyl chlorides, as shown below :

CHEMISTRY 327
 MODULE - 7 Aldehydes, Ketones and Carboxylic Acids
Chemistry of Organic
Compounds O O
R C OH + SOClR2 C Cl + SO2­ + HCl ­
Carboxylic Thionyl an acid
acid chloride chloride

O O
Notes R C OH + PCl3 3R C Cl + H3 PO3
Phosphorus
trichloride

O O

R C OH + PCl5 R C Cl + POCl3 + HCl

Phosphorus
pentachloride

(ii) Formation of Acid Anhydrides

O O
P2O5
2 RCOOH - H2O
RC O C R
aCarboxylicacid an Acid Anhydride

O O
P2O5
2 CH3COOH CH3 C O C CH3
- H2O
Ethanoicanhydride

Since the carboxylic acid anhydrides are formally derived from carboxylic acids
by loss of water, their names are derived from the corresponding acids by using
the word anhydride in place of the acid. As the anhydride formed in the above
reaction is derived from ethanoic acid, it is called ethanoic anhydride.
This method is used for the preparation of symmetrical anhydrides.
Carboxylic acid also react with acyl chlorides in the presence of pyridine to give
carboxylic acid anhydrides.
O O
D
CH 3CH2CH2COH + ClCCH2CH2CH3 Pyridine
Butanoic acid Butanoyl chloride
O O

CH 3CH2CH2C - O - C - CH2CH2CH3
Butanoicanhydride
We can prepare unsymmetrical anhydrides by this method.
Cylic anhydrides are obtained by the dehydration of dicarboxylic acids at higher
temperature.

328 CHEMISTRY
Aldehydes, Ketones and Carboxylic Acids MODULE - 7
Chemistry of Organic
O Compounds
COOH C
H 2C H 2C
573 K
O
–H2O
H 2C H 2C
COOH C
Butanedioic acid O
(Succinic acid)
Butanedioic anhydride Notes
(Succinic anhydride)

(iii) Formation of Esters

Carboxylic acids react with alcohols to form esters.
O O
+
H
R C OH + R ¢OH R C OR¢ + HO2
Carboxylic Alcohol Ester
acid

Note that the acid catalysed esterification is an equilibrium reaction. The

equilibrium can be shifted to the right side towards products it we are able to
remove water or the ester from the reaction mixture. Also if we use excess of
one reagent, then the equilibrium shifts towards the right side to give the ester.
Normally, we take excess of alcohol and use it as a solvent to carry out
esterification.

O O
H 2SO4 , Δ
CH3 C OH + CH3OH CH3COCH3
–H2O
Ethanoic acid Methanol Methyl ethanoate

Esters are named as alkyl alkanoates. The alkyl part comes from the alcohol
while the alkanoate portion is derived from the carboxylic acid. Therefore, the
above ester is called methyl ethanoate because it is obtained from methyl
alcohol and ethanoic acid.

Esters can also be prepared by the reaction of acid chlorides or acids

anhydrides with alcohols. Thus, we can see that these acid derivatives can be
converted to one-another.

O O

C Cl COCH2CH3

Pyridine
+ CH3CH2OH + HCl

Benzoyl chloride Ethanol Ethyl benzoate

CHEMISTRY 329
 MODULE - 7 Aldehydes, Ketones and Carboxylic Acids
Chemistry of Organic
Compounds
CH2OH
O O O
Pyridine
CH3C O C CH3 + CH3 C O CH2 + CH3 COOH
Ethanoic Benzyl ethanoate Ethanoic acid
anhydride Benzyl alcohol

(iv) Formation of Amides

Notes
Carboxylic acids react with ammonia or amines to give amides. The reaction
involves the formation of an ammonium carboxylate salt as an intermediate
which on heating gives amide.
O O O
|| || - + D
||
R - C - OH + : NH3 R C - O N H4 R - C - NH 2 + H 2 O
Carboxylic Ammonium anAmide
acid carboxylate

O O
|| ||
R C OH + R ¢NH 2 R C NHR ¢ + HO 2
Carboxylic Primary Amide
acid amine (Substituted)

Amides can also be obtained by the reaction of ammonia or amines with

carboxylic acid halides, anhydrides and esters.
O O
|| ||
NaOH
CH3 C Cl + CH3 NH 2 ¾¾¾¾® CH3 C NH CH3
Ethanoyl N - Methylethanamide
chloride

O O
|| 273-278K
||
ClCH 2 C OC2 H5 +NH3 ¾¾¾¾¾® ClCH 2 C NH 2 + C2 H 5 OH
Ethylchloroethanoate Chloroethanamide Ethanol

Thus, we can make one carboxylic acid derivative from another. Generally, the
less reactive acid (acyl) derivatives can be prepared from the more reactive
ones.
The order of reactivity of various carboxylic acid derivatives is as follows :
Acid chloride > Acid anhydride > Ester > Amide

330 CHEMISTRY
Aldehydes, Ketones and Carboxylic Acids MODULE - 7
Chemistry of Organic
Thus, acid chlorides are the most reactive ones whereas the amides are the least Compounds
reactive.
Since the least reactive derivative can be prepared from the more reactive ones,
we can summarise which derivative can be prepared from which other one in
the following way:
Anhydride
Acid chloride Ester Acid chloride Anhydride Notes

Amide Ester
Acid chloride

Anhydride

Of course, these derivatives can be synthesised from the carboxylic acids as

well.

INTEXT QUESTIONS 27.2

1. Match the following compounds given in column I and their classes given
in column II:
Column I Column II

(i) CH3COOH (a) Carboxylic acid halide

(ii) CH3CONH 2 (b) Carboxylic acid
(iii) CH3COOCH3 (c) Carboxylic acid anhydride
(iv) CH3COCl (d) Carboxylic acid amide
(v) CH3COOCOCH 2 Cl (e) Ester
2. Arrange the following acids in the increasing order of their solubility in
water:
CH3COOH, CH3 (CH 2 )3COOH p-ClC6 H 4 COOH

3. Which one of the following will be most acidic and why ?

Butanoic acid, 2-Chlorobutanoic acid, 3-Chlorobutanoic acid, 4-
Chlorobutanoic acid
4. Give the products of the following reactions :
(i) NaCN
(i) BrCH 2 CH 3 ⎯⎯⎯⎯→
+
(ii) H3O

CHEMISTRY 331
 MODULE - 7 Aldehydes, Ketones and Carboxylic Acids
Chemistry of Organic
Compounds
CH3
(i) KMnO4 , –OH, D
(ii)
(ii) H3O+

(iii) CH 3COOH + PCl3 ⎯⎯

→
Notes 5. Why are carboxylic acids more acidic than alcohols ?

WHAT YOU HAVE LEANT

In this lesson, you have learnt that
z Aldehydes and ketones constitute the carbonyl compounds. Aldehydes are
known as alkanals whereas ketones are called alkanones.
z Aldehydes and ketones can be prepared by oxidation of alcohols, ozonolysis
of alkenes, hydration of alkynes and Friedel–Craft’s acylation.
z Carbonyl group is polar in nature and carbonyl-carbon is susceptible to
nucleophilic attack. Thus, aldehydes and ketones undergo nucleophilic
addition reactions with many reagents. They also exhibit condensation
reactions.
z Since the α -hydrogen is acidic in nature, aldehydes and ketones show
specefic reactions at α -carbon atom such as halogenation and aldol
condensation.
z Carboxylic acids are an important class of compounds.
z The methods of preparation of carboxylic acids being oxidation of alkenes,
aldehydes and ketones and alkylbenzene, hydrolysis of nitriles and carbonation
of Grignard reagents.
z The molecules of carboxylic acids show hydrogen bonding and can exist as
dimers.
z Carboxylic acids are acidic in nature. Their acidity is affected by various
factors including the nature of substituents attached to the carbon chain
bearing the carboxylic group.
z Carboxylic acids form salts with strong bases such as metal hydroxides. They
undergo halogenation at α -carbon atom and can be reduced to primary
alcohols using LiAIH 4 .
z Carboxylic acids gives rise to a number of carboxylic acid derivatives such
as carboxylic acid halides, anhydrides, esters and amides by nucleophilic acyl
substitution reactions. They can be prepared from one another as shown
below :

332 CHEMISTRY
Aldehydes, Ketones and Carboxylic Acids MODULE - 7
Chemistry of Organic
Compounds
Carboxylic Acid Acid chloride Anhydride

Ester

Amide
Notes

TERMINAL EXERCISE
1. Write the structural formulae and IUPAC names of the compounds containing
a carbonyl functional group and having the molecular formula C3H 6 O.
2. How can you prepare primary, secondary or tertiary alcohols using aldehydes
or ketones?
3. Write the mechanism of addition of HCN to propanone.
4. What is Tollen’s Test?
5. Explain keto-enol tautomerism.
6. What is haloform reaction?
7. How will you test a carboxylic acid in the laboratory?
8. Which reagent can reduce a carboxylic acid to a primary alcohol?
9. What are carboxylic acid anhydrides ? Give their method of preparation from
carboxylic acids.
10. Which carboxylic acid derivative is most reactive?
(a) Acid amide (b) Ester (c) Acid halide (d) Acid anhydride

ANSWERS TO INTEXT QUESTIONS

27.1
1. (i) aldehyde, Ethanal
(ii) ketone, Butan-2-one
(iii) ketone, 1-Phenylethanone
(iv) aldehyde, Propanal

CHEMISTRY 333
 MODULE - 7 Aldehydes, Ketones and Carboxylic Acids
Chemistry of Organic
Compounds
2. Using hydration with Hg 2+ , H + .

3. Because they have one alkyl group whereas a ketone has two alkyl group.
Hence, the carbonyl carbon in aldehydes is more positive.
Also, the two alkyl groups lead to more crowding in ketones.

Notes OH OR ¢¢ R¢
| | |
4. (i) R C CN (ii) R C R ¢¢¢ (iii) R C R ¢¢
| | |
R¢ OR ¢ OH

5. By Wolff- Kishner reduction or Clemmensen reduction.

6. The product formed by the condensation of two aldehyde molecules having
α-hydrogen atom. Aldol contains both an aldehyde and an alcohol functional
group.

CHO COOH CH2OH

cone NaOH
7. + ,
H+

27.2
1. (i). (b) (ii). (d) (iii). (e) (iv). (a) (v) e
2. p – CIC6H4COOH < CH3(CH2)3COOH < CH3COOH
3. 2-Chlorobutanoic acid, because of maximum –I effect of –Cl at 2 – position.

COOH

4. (i) HOOCCH 2 CH3 , (ii) ,

(iii) 3CH3COCl + H3PO3

5. Because of resonance stabilization of carboxylate anion. The alkoxide ion

cannot stabilize by resonance.

334 CHEMISTRY