12C12

Aldehydes, Ketones
and
Carboxylic Acids
 The world of tastes and
fragrances

Acetone Acetic Acid

Vanillin Benzaldehyde
 Aldehyde Ketone Carboxylic Acid

Acid Anhydride Acyl halide Ester Amide

 12C12.1

Preparation of
Aldehydes and Ketones
12C12.1 Preparation of Aldehydes and Ketones

Learning Objectives

Nomenclature of Aldehydes and Ketones

Preparation of Aldehydes

Preparation of Ketones
 12C12.1

CV 1

Nomenclature of
Aldehydes and Ketones
 Common Names of Aldehydes

Acetaldehyde Benzaldehyde Salicyldehyde

 IUPAC Names of Aldehydes
Suffix -al

Ethanal Pent-2-enal Cyclohexanecarbaldehyde

2-Hydroxybenzaldehyde 4-Hydroxy-3-methoxybenzaldehyde
 Common Names of Ketones

Acetone Acetophenone Benzophenone

 IUPAC Names of Ketones
Suffix -one

Propanone 1-Phenylpropan-1-one 3-Methylcyclopentanone

5-Bromo-4-methyloctan-2-one
 ConcepTest

Ready for Challenge

Q. Write the IUPAC names of following compounds:
a. b. c.

Pause the video

Time duration: 3 minutes
Q. Write the IUPAC names of following compounds:
Sol.

a. b. c.
4 2
3 1
5 2
6 3 2 1 3 1
5 4
4

2-Methylhexan-3-one 3-Methyl-4-phenylbutan-1-al 4-Methyl-3-oxopentan-1-al

 12C12.1

CV 2

Preparation of Aldehydes-I
 Preparation of Aldehydes
1. From Acyl chlorides:

Rosenmund Reaction
Mechanism:

Pd-Complex
 Preparation of Aldehydes
Example:

Propanoyl chloride Propanal

Benzoyl chloride Benzaldehyde

 Preparation of Aldehydes
2. From Nitriles and Esters:

Stephens Reactions
Mechanism:

Carbanion
 Preparation of Aldehydes
2. From Nitriles and Esters:

Stephens Reactions
Mechanism:

Carbanion

Imine
• Carbanions are highly unstable
• Acid-base reaction
 Preparation of Aldehydes
2. From Nitriles and Esters:

Stephens Reactions
Mechanism:

• Acid-base reaction
 Preparation of Aldehydes
2. From Nitriles and Esters:

Stephens Reactions
Mechanism:

H H H

Aldehyde
 Preparation of Aldehydes
2. From Nitriles and Esters: Stephens Reactions

Imine Aldehyde

• Esters are also reduced to aldehydes with DIBAL-H

 Preparation of Aldehydes

Examples:

Benzonitrile Benzaldehyde

Methylpropanoate Propanal
 Preparation of Aldehydes
3. From Alcohols:

Examples:
 ConcepTest

Ready for Challenge

Q. How will you bring about the following conversions:
a. Propylchloride to Butanal
b. Ethene to Ethanal

Pause the video

Time duration: 3 minutes
 Q. How will you bring about the following conversions:
a. Propylchloride to Butanal
b. Ethene to Ethanal
Sol.
a. Propylchloride to Butanal

Nucleophilic Substitution Stephen Reaction

b. Ethene to Ethanal

Acidic Hydrolysis Controlled Oxidation

 12C12.1

CV 3

Preparation of Aldehydes-II
 Preparation of Aldehydes
4. From Hydrocarbons:
a. Reductive Ozonolysis of Alkenes

Mechanism:

Molo-ozonoid
Ozonoid
 Preparation of Aldehydes
4. From Hydrocarbons:
a. Reductive Ozonolysis of Alkenes

Mechanism:

+ + ZnO

Ozonoid Aldehydes
 Preparation of Aldehydes
Examples:

2-Butene Ethanal

2-Pentene Propanal Ethanal

 Preparation of Aldehydes
4. From Hydrocarbons:
b. Etard Reaction
| |

Toluene Benzaldehyde
Mechanism:

| | |

Chromium Complex
 Preparation of Aldehydes
4. From Hydrocarbons:
c. Gatterman-Koch Reaction
|

Mechanism:

Slow Fast

Proton Transfer Aromaticity regained

 Preparation of Aldehydes
4. From Hydrocarbons:

d. Side Chain Chlorination followed by Hydrolysis:

| | |

Benzal chloride

This is the commercial method for the preparation of Benzaldehyde.

 12C12.1

CV 4

Preparation of Ketones
 Preparation of Ketones
1. From Acyl chlorides:

Acyl Chloride Dialkylcadmium Cadmium chloride

Mechanism:
Dialkylcadmium
 Preparation of Ketones
1. From Acyl chlorides:

Acyl Chloride Dialkylcadmium Cadmium chloride

Mechanism:

Example:

Ethanoylchloride Ethanemagnesiumchloride Butan-2-one

 Preparation of Ketones
2. From Nitriles and Esters:

Mechanism:

Similarly, Esters react with Grignard’s reagent followed by hydrolysis to

produce ketones:

Methylbutanoate 1-Phenylbutanone
 Preparation of Ketones
3. From Benzene and its derivatives:

Friedel-Crafts Acylation Reaction

Example:

Toluene p-substituted o-substituted

(Major product) (Minor product)
 Preparation of Ketones
4. From Alcohols:

Examples:

Prop-2-ol Propanone
Summary
Preparation of Aldehydes Preparation of Ketones

| |
 12C12.1 Preparation of Aldehydes and Ketones

Reference Questions

NCERT In-Text Questions: 12.1, 12.2

NCERT Exercise Questions: 12.2, 12.3, 12.4, 12.5

Workbook Questions: 2, 6, 7
 12C12.2

Properties of
Aldehydes and Ketones
 12C12.2 Properties of Aldehydes and Ketones

Learning Objectives

Physical Properties of Aldehydes and Ketones

Nucleophilic Addition Reactions

Reduction of Aldehydes and Ketones

Oxidation of Aldehydes and Ketones

 12C12.2

CV 1

Physical Properties of
Aldehydes and Ketones
 Physical Properties of Aldehydes and
Ketones
• Methanal is a gas at room temperature whereas Ethanal is a volatile

liquid.

• Ketones up to carbon number 13 are volatile liquids.

• Higher members of both aldehydes and Ketones are solids.

• Lower aldehydes have unpleasant smell whereas ketones and higher

aldehydes have fruity smells.

Physical Properties of Aldehydes and
Ketones
Structure of Carbonyl Group
p-orbitals

Polar bond

Nucleophiles prefer
to attack
 12C12.2

CV 2

Nucleophilic Addition Reactions-I

 Nucleophilic Addition Reactions

C O
Trigonal Planar
Nucleophilic Addition Reactions

C O
Nucleophilic Addition Reactions

Nu
 Nucleophilic Addition Reactions

Tetrahedral C

Nu
Counter part of attacking
agent or proton from
water
Nucleophilic Addition Reactions

C
H

Nu

Nucleophilic Addition Product

 Nucleophilic Addition Reactions

• Aldehydes are generally more reactive than ketones in nucleophilic

addition reactions.

Less hindrance More hindrance

More electron Less electron

deficiency at carbon deficiency at carbon
 Nucleophilic Addition Reactions
a. Addition of hydrogen cyanide (HCN):

Cyanohydrin
2-Hdroxycarboxylic acid

2-Hdroxy amine
 Nucleophilic Addition Reactions

Hydrogensulphite addition
compound (crystalline)
• Due to steric hindrance rate of reaction in case of ketones is very
slow.
• Used for separation and purification of aldehydes.
 Nucleophilic Addition Reactions
c. Addition of Grignard Reagents:
 ConcepTest

Ready for challenge

Q. Arrange the following compounds in increasing order of their
reactivity in nucleophilic addition reactions.
(i) Ethanal, Propanal, Propanone, Butanone.
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
Hint: Consider steric effect and electronic effect.

Pause the video

Time duration: 2 minutes
Q. Arrange the following compounds in increasing order of their
reactivity in nucleophilic addition reactions.
(i) Ethanal, Propanal, Propanone, Butanone.
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde, Acetophenone.
Hint: Consider steric effect and electronic effect.

Sol.
(i) >

Ethanal > Propanal > Propanone > Butanone

(ii)

+M/+I -M/-I

p-Nitrobenzaldehyde > Benzaldehyde > p-Tolualdehyde > Acetophenone

 ConcepTest

Ready for Challenge

Q. Identify the final product of following reaction:

Pause the video

Time duration: 3 minutes
Q. Identify the final product of following reaction:

Sol.

Cyclic ether
2-Methyltetrahydrofuran
 ConcepTest

Ready for Challenge

Q. Ethereal solution of an organic compound ‘A’ when heated with
magnesium gave ‘B’ on treatment with ethanal followed by acid
hydrolysis gave 2‐propanol. Identify the compound ‘A’. What is ‘B’
known as?

Pause the video

Time duration: 2 minutes
Q. Ethereal solution of an organic compound ‘A’ when heated with
magnesium gave ‘B’ on treatment with ethanal followed by acid
hydrolysis gave 2‐propanol. Identify the compound ‘A’. What is ‘B’
known as?
Sol.

Grignard’s reagents are formed when alkyl bromide is treated with Mg

A B
Methylbromide Methylmagnesiumbromide
 12C12.2

CV 3

Nucleophilic Addition Reactions-II

 Nucleophilic Addition Reactions
d. Addition of Alcohols:

Hemiacetal Acetal

gem-dialkoxy compound

• Dry hydrogen chloride protonates the oxygen of the carbonyl group.

• Similarly ketones react with alcohols to give ketals.
• Acetals/ketals are hydrolysed with aqueous mineral acids to yield
corresponding aldehydes and ketones respectively,
 Nucleophilic Addition Reactions
d. Addition of Alcohols:
• Acetals/ketals are less reactive towards oxidation/reduction, Hence
these are used as protecting group for carbonyl compounds.

• Ethylene glycol is
commonly used as
protecting reagent.
 Nucleophilic Addition Reactions
d. Reaction with Ammonia and its derivatives:

Imine
 Nucleophilic Addition Reactions

i. Reaction with amine:

Amine Substituted imine

(Schiff’s base)
ii. Reaction with Hydroxylamine:

Hydroxylamine Oxime
 Nucleophilic Addition Reactions
iii. Reaction with Hydrazine:

Hydrazine Hydrazone

iv. Reaction with Phenylhydrazine:

Phenylhydrazine Phenylhydrazone
 Nucleophilic Addition Reactions
v. Reaction with 2,4-Dinitrophenylhydrazine:

2,4-Dinitrophenylhydrazine 2,4-Dinitrophenylhydrazone
Orange-red precipitate
• Used for test of the carbonyl group, also know as 2,4-DNP Test
 Nucleophilic Addition Reactions
vi. Reaction with Semicarbazide:

Semicarbazide Semicarbazone
1 2 3

Q. Why does N-1 attack on the carbonyl group not N-2 or N-3?
Pause the video
Time duration: 2 minutes
Sol.
1 2 3 1 2 3
 12C12.2

CV 4

Reduction of Aldehydes and

Ketones
 Reduction of Aldehydes and Ketones
1. Reduction to alcohols

• Aldehydes form 1° alcohols

• Ketones form 2° alcohols
 Reduction of Aldehydes and Ketones
Example:

Pent-1-ol

Pent-3-enal

Pent-3-en-1-ol
 Reduction of Aldehydes and Ketones
2. Reduction to hydrocarbons

a. Clemmensen Reduction
Zinc amalgam and HCl are used
 Clemmensen Reduction
Mechanism:

• Reaction occurs at zinc surface

• Zinc being a metal has tendency to donate electrons

• Clemmensen reduction is not applicable to keto alcohols,

unsaturated cyclic ketones as these contain acid sensitive groups.
 Reduction of Aldehydes and Ketones
b. Wolff-Kishner Reduction

Mechanism:

Carbanion
 Reduction of Aldehydes and Ketones
b. Wolff-Kishner Reduction

Mechanism:
 12C12.2

CV 5

Oxidation of Aldehydes and

Ketones
 Oxidation of Aldehydes and Ketones

• Ketones are generally oxidised under vigorous conditions, i.e. strong

oxidising agents and at elevated temperatures.

• Popoff's Rule according to which carbonyl group of the

unsymmetrical ketone remains with the smaller alkyl group
preferentially.
 Oxidation of Aldehydes and Ketones
• Mild oxidising agents like tollen’s reagent and fehling solution can
oxidise only aldehydes, hence used for the test of aldehydes.
a. Tollen’s Test (Silver Mirror Test)
Ammonical solution of Silver Nitrate

Tollen’s Reagent

Silver Mirror

• Both aliphatic and aromatic aldehydes give Tollen’s Test.

 Oxidation of Aldehydes and Ketones
b. Fehling Solution

Deep Blue complex

Red-Brown

• Aromatic aldehydes do not respond to this test.

12C12.2

PSV 1
Sol.
Aldehyde or Ketone
A

Tollen’s test Ketone

Pentan-2-one Pentan-3-one
Sol.

Propanoic Acid

Ethanoic Acid

Kolbe’s Butane
Sodiumpropanoate
Electrolysis D

• On Kolbe’s electrolysis salts of acids give alkanes

 ConcepTest

Ready for Challenge

 Pause the video
Time duration: 3 minutes
 Oxidation
Sol.
A
B
Reduction A is Ketone

• Ketone on reduction give 2° Alcohol. So B is 2-Propanol

B C 2-Bromopropane D Propene
Summary
• The boiling points of aldehydes and ketones are higher than the
hydrocarbons and ethers of comparable molecular masses.

• Reaction with ammonia

• Catalytic Reduction
Summary
• Clemmensen Reduction • Wolff-Kishner Reduction

• Oxidation Reaction

• Tollen’s Test

Silver Mirror
• Fehling Solution Test

Red-Brown
 12C12.2 Properties of Aldehydes and Ketones

Reference Questions

NCERT In-Text Questions: 12.4, 12.5

NCERT Exercise Questions: 12.1, 12.5, 12.8, 12.18 (i & ii), 12.13 (i), 12.12 (i)

Workbook Questions: 4, 14, 20

 O

H
C
H
R C

H
 O
Hyperconjugation

H
C
H
R C

H
 O
Hyperconjugation

H
C
H
R C

H
Hyperconjugation

C H

R
Enolate ion

H
 O
Hyperconjugation

H
C
H
R C

H
 O

H
C
H
R C
+I
Less Acidic

H
• Aldehydes are more acidic than Ketones
Iodoform Reaction

Iodoform
Mechanism:

Enolate ion
Iodoform Reaction

Iodoform
Mechanism:

Enolate ion
Iodoform Reaction

Iodoform
(Yellow Precipitate)
12C12.3

PSV 1
Q. Give simple chemical tests to distinguish between the following pairs
of compounds.
(i) Propanal and Propanone
(ii) Pentan-2-one and Pentan-3-one
Sol.

Yellow ppt.

(ii) By iodoform test

Yellow ppt.
Pentan-2-one is a methyl ketone thus it responds to this test while
Pentan-3-one not being a methyl ketone does not respond to this test
 12C12.3

CV 2

Aldol Condensation
 Aldol Condensation

Aldol

Mechanism:
 Aldol Condensation

Aldol
Mechanism:

Aldol
 Aldol Condensation
• Aldols on heating undergo condensation to form unsaturated carbonyl
compounds

Trick to form direct aldol condensation product

Aldol condensation product

Cross-Aldol Condensation

Self condensation products

 Cross-Aldol Condensation

Self condensation products

Cross condensation products

• In case of cross-aldol, self condensation products are formed in major

quantity.
12C12.3

PSV 2
Q.
Major Product

Which of the following will the major product of above reaction:

A. B. C. D.
Q.
Major Product

Sol. Option D is correct

1 2 Option D is correct

More Stable

More acidic

Less Stable

Less acidic
 ConcepTest

Ready for Challenge

Q.
Major Product

A) B)

C) Both will be formed in equal amount.

D) Need more information to predict major product.

Pause the video

Time duration: 3 minutes
Q.
Major Product

Sol.

More stable Less stable

1 2

Option A is correct
 12C12.3

CV 3

Cannizzaro Reaction
 Cannizzaro Reaction

Alcohol Carboxylic Acid

Mechanism
 Cannizzaro Reaction

Alcohol Carboxylic Acid

Mechanism

Benzyl alcohol Benzoic acid

• Usually, less hindered aldehyde gives oxidised product.

Q. During crossed-cannizzaro reaction less hindered aldehyde gives
oxidised product. Explain why?

Pause the video

Time duration: 2 minutes
Q. During crossed-cannizzaro reaction less hindered aldehyde gives
oxidised product. Explain why?

Sol.
 Electrophilic Aromatic Substitution Reaction

• m-position is relatively less electron deficient hence electrophile

prefer m-position
 ConcepTest

Ready for challenge

Q. How will you bring about the following conversions in not more
than two steps?
(i) Propanone to Propene
(ii) Benzaldehyde to 3-Phenylpropan-1-ol

Pause the video

Time duration: 2 minutes
Q. How will you bring about the following conversions in not more
than two steps?
(i) Propanone to Propene
(ii) Benzaldehyde to 3-Phenylpropan-1-ol

Sol
.
(i)

(ii)

Aldol condensation
 12C12.3

CV 4

Uses of Aldehydes and Ketones

 Uses of Aldehyde and Ketone
Aldehydes and ketones are used as
Biological specimen preservative
Solvent

To prepare Bakelite Urea-Formaldehyde glues

 Uses of Aldehyde and Ketone
Acetaldehyde is used primarily as a starting material in the manufacture
Acetic acid Ethyl acetate
Vinyl acetate

Polymers Drugs
 Uses of Aldehyde and Ketone
Benzaldehyde is used in
Dye
Perfumery industries
industries

Many aldehydes and ketones like butyraldehyde, vanillin, acetophenone,

camphor etc. are well known for their odours and flavours
Summary
Iodoform Reaction:

Aldol Condensation:

Cannizzaro Reaction:

Electrophilic Aromatic Substitution Reaction:

Reference Questions

NCERT Exercise Questions: 12.7, 12.10, 12.13, 12.15 (i to vii), 12.16 (i, ii,iii), 12.1

Workbook Questions: 13, 19

 12C12.4

Carboxylic Acid
&
It’s Preparation
 12C12.4 Carboxylic Acid & It’s Preparation

Learning Objectives

Nomenclature of Carboxylic Acids

Preparation of Carboxylic Acids-I

Preparation of Carboxylic Acids-II

 12C12.4

CV 1

Nomenclature of Carboxylic Acids

 Nomenclature of Carboxylic Acids
Common Names

Formic Acid Acetic Acid Butyric Acid Valeric Acid

Ant sting Vinegar Butter

Valerian Plant
Ant: Formica Vinegar: Acetum Butter: Butyrum
 Nomenclature of Carboxylic Acids
IUPAC Names
Suffix- oic acid

Methanoic acid Ethanoic acid Butanoic acid Pentanoic acid

2-Aminobutanoic acid 2,4-Dimethyl-3-

oxopentanoic acid 3-Isopropylbenzoic acid
4-Bromo-2-chlorobenzoic acid
 Nomenclature of Carboxylic Acids

Malonic acid Succinic acid

Oxalic Acid
Ethanedioic acid Propane-1,3-dioic acid Butane-1,4-dioic acid

Gluteric acid Adepic acid

Pentane-1,5-dioic acid Hexane-1,6-dioic acid

Propane-1,2,3-tricarboxylic acid
 ConcepTest

Ready for challenge

Q. Draw the structures of following compounds:
a) 4-Methoxy-2-isopropylpentanoic acid
b) 3,5-Dihydroxybenzoic acid
c) 3-Ethyl-6-oxohexanoic acid

Pause the video

Time duration: 2 minutes
Q. Draw the structures of following compounds:
a) 4-Methoxy-2-isopropylpentanoic acid
b) 3,5-Dihydroxybenzoic acid
c) 3-Ethyl-6-oxohexanoic acid
Sol. a) 4-Methoxy-2-isopropylpentanoic acid

OH
Q. Draw the structures of following compounds:
a) 4-Methoxy-2-isopropylpentanoic acid
b) 3,5-Dihydroxybenzoic acid
c) 3-Ethyl-6-oxohexanoic acid
Sol. b) 3,5-Dihydroxybenzoic acid c) 3-Ethyl-6-oxohexanoic acid

O OH OH

O
O
HO OH
 12C12.4

CV 2

Preparation of Carboxylic Acids-I

 Preparation of Carboxylic Acids
1. From Primary Alcohols and Aldehydes

Example:

• Carboxylic acids are also prepared from aldehydes by the use of mild
oxidising agents like Tollen’s reagent or Fehling solution.
 Preparation of Carboxylic Acids
2. From Alkylbenzenes

• Primary and secondary alkyl groups are oxidised in this manner while
tertiary group is not affected.
 Preparation of Carboxylic Acids
3. From Nitriles and Amides

Mechanism Amide Carboxylic acid

| || |

Amide || |
 Preparation of Carboxylic Acids
3. From Nitriles and Amides

Mechanism

| |
|| | || | || | ||

Example:

Ethane nitrile Ethanamide Ethanoic acid

 12C12.4

CV 3

Preparation of Carboxylic Acids-II

 Preparation of Carboxylic Acids
4. From Acyl halides, Acid Anhydrides and Esters:
Acidic Hydrolysis

Examples:

Ethyl benzoate Benzoic acid Ethanol

• Basic hydrolysis gives alcohol and carboxylate ion.

 Preparation of Carboxylic Acids
5. From Grignard Reagents

Mechanism:

|| ||

• Step up reaction as number of C-atom increases in product.

Example:

Ethane magnesium chloride Propanoic acid

 Preparation of Carboxylic Acids
6. From Alkenes and Alkynes

• C-atom with double bond must have atleast one hydrogen atom.

Example:

• In case of unsymmetrical alkenes two carboxylic acids are formed.

 Preparation of Carboxylic Acids
6. From Alkenes and Alkynes
b. Oxidative Ozonolysis

Example:

2-Butene Ethanoic acid

12C12.4

PSV 1
Q. Show how each of the following compounds can be converted to
benzoic acid.
(i) Ethylbenzene
(ii) Acetophenone
(iii) Bromobenzene
(iv) Phenylethene (Styrene)
Sol (i) Benzoic acid from Ethylbenzene
.

(ii) Benzoic acid from Acetophenone

(iii) Benzoic acid from Bromobenzene

(iv) Benzoic acid from Phenylethene (Styrene)

Summary
Carboxylic Acid & It’s Preparation
 12C12.4 Carboxylic Acid & It’s Preparation

Reference Questions

NCERT In-Text Questions: 12.6

NCERT Exercise Questions: 12.14, 12.17 (i & ix)

Workbook Questions: 17 (i), 18 (i & ii)

 12C12.5

Properties of Carboxylic
Acids
 12C12.5 Properties of Carboxylic Acids
Learning Objectives

Physical Properties of Carboxylic Acids

Acidic Nature of Carboxylic Acids

Reactions involving Breaking of C-OH bond

Reactions involving –COOH Group

Substitution Reaction of Carboxylic Acids

Uses of Carboxylic Acids

 12C12.5

CV 1

Physical Properties of Carboxylic

Acids
 Physical Properties of Carboxylic
Acids
• Lower fatty acids upto C-1O are colourless liquids but the higher ones
are colourless waxy solids.
• First 3 members have a sharp pungent odour, C-4-C-9, have an odour
of rancid butter whereas higher members do not possess any smell.
• Lower members are highly soluble in water but the solubility
decreases with the rise of molecular mass.
• Boiling points of carboxylic acids are higher than those of alcohols of
same molecular mass due to the intermolecular H-bonding.
 Structure of Carboxylic Acids

120°

Note: B.L. mentioned is for formic acid, it varies with the attached alkyl
group and substituents.
12C12.5

PSV 1
 O O O O
O OH O OH
H H
O
H
OH
O
A B C H
D
Sol
.

`
 O O O O
O OH O OH H
Sol
H
O
.

H
OH
O
A B C H
D

Ortho effect
Sterically Inhibited Resonance

O OH O O
(SIR-effect)

H
OH O
H
Steric Hindrance

D A B <
< < C
 ConcepTest
Ready for challenge
Q. Arrange following molecule in increasing order of their acidity:

A B C D

Pause the video

Time duration: 1 minute
Q. Arrange following molecule in increasing order of their acidity:

A B C D
Sol
.

Order of acidic nature:

A< C B D
< <
 12C12.5

CV 2

Acidic Nature of Carboxylic Acids

Acidic Nature of Carboxylic Acids

Less Acidic More Acidic

 Acidic Nature of Carboxylic Acids
Reactions due to Acidity of Carboxylic Acids

Example:

Example:
 Acidic Nature of Carboxylic Acids
Reactions due to Acidity of Carboxylic Acids

Example:
 12C12.5

CV 3

Reactions involving Breaking of

C-OH Bond
 Reactions involving Breaking of C-OH
1. Formation of Anhydride Bond

Acid Anhydride
Mechanism:

• O-atom on carbonyl carbon is nucleophilic due –ve charge in its

resonating structure
 Reactions involving Breaking of C-OH
Bond

• We can also obtain acid anhydrides by heating sodium salt of acid

with acid chloride.
Note: Anhydride of formic acid cannot be obtained by this method.
 Reactions involving Breaking of C-OH
2. Esterification Bond
 Reactions involving Breaking of C-OH
Bond
3. Reaction with Phosphorus Chlorides or Thionyl Chlorides:

Mechanism: Acid Chloride

Acid Chloride
 Reactions involving Breaking of C-OH
4. Reaction with Ammonia: Bond

Ammonium Salt Amide

• Acid-Base Reaction.
• Heated at High Temperature.
Example:

Benzoic acid Benzamide

 ConcepTest

Ready for challenge

Q. Identify A,B and C in following reaction:

Pause the video

Time duration: 2 minutes
Q. Identify A,B and C in following reaction:

Sol.

Phthalic Acid

|
• Phthalimide is used to prepare primary amines. Phthalimide

|
 12C12.5

CV 4

Reactions involving –COOH Group

 Reduction of –COOH Group

Primary Alcohol
Example:

Propanoic acid Propanol

 Decarboxylation Reaction

Alkane
Soda Lime Process
Mechanism:

Alkane

• Carbanion is formed as intermediate.

• Step down reaction as number of C-atoms in product decreases.
 Decarboxylation Reaction
Example:

Ethanoic Acid Methane

Benzoic Acid Benzene

 Kolbe’s Electrolysis
Anode Cathode

Alkane
Mechanism:
At Anode:

Acid Salt Solution

 Kolbe’s Electrolysis
Anode Cathode

Alkane
Mechanism:
At Anode:

Acid Salt Solution

Alkane

• Alkyl radicals undergo dimerisation to form alkane.

• Alkane has twice the number of carbon atoms present in the alkyl
group of the acid.
 Kolbe’s Electrolysis
Anode Cathode

Mechanism: Alkane

At Anode:

Acid Salt Solution

Alkane
At Cathode:
 12C12.5

CV 5

Substitution Reactions of
Carboxylic Acids
 Substitution Reaction of Carboxylic
Acids
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Hell-Volhard-Zelinsky Reaction
Mechanism:

Tautomerisation
 Substitution Reaction of Carboxylic
Acids
|

Hell-Volhard-Zelinsky Reaction
Mechanism:

Tautomerisation
 Substitution Reaction of Carboxylic
2. Electrophilic Aromatic Substitution
AcidsReaction:

• m-position is relatively less electron deficient hence electrophile

prefer m-position
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Q. How will you convert Benzoic acid to m- Nitrobenzyl alcohol in not
more than three steps?

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Q. How will you convert Benzoic acid to m- Nitrobenzyl alcohol in not
more than three steps?
 12C12.5

CV 6

Uses of Carboxylic Acid

 Uses of Carboxylic Acid
• Methanoic acid is used in
Rubber industries Leather industries Electroplating industries

Dye industries Textile industries

 Uses of Carboxylic Acid
• Ethanoic acid is used as
Solvent Vinegar

• Sodium benzoate is used as a food preservative

• Higher fatty acids are used for the manufacture
Detergent
Soaps

• Esters of benzoic acid are used in perfume industry

Summary
• Carboxylic acids are weaker than mineral acids, but they are stronger
acids than alcohols and simple phenols.

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 12C12.5 Properties of Carboxylic Acids

Reference Questions

NCERT In-Text Questions: 12.7, 12.8

NCERT Exercise Questions: 12.10, 12.12, 12.16, 12.19 (i to viii), 12.19, 12.20

Workbook Questions: 15, 16 (i), 17

12C12.1

PSV 1
12C12.1

PSV 1
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