CARBOXYLIC ACIDS AND THEIR

DERIVATIVES
 CLASSIFICATION

Depending on the number of –COOH groups they

are classified as;
1. Monocarboxylic acids: containing one -COOH
group
2. Dicarboxylic acids: containing two -COOH groups
and so on.
3. Fatty acids: Aliphatic monocarboxylic acids are
commonly called fatty acids because higher
members are obtained by the hydrolysis of oils and
fats.
Note: Fatty acids can be saturated or unsaturated
Physical Properties
1. Acids upto C-10 are liquids with unpleasant
odours. The higher members are colourless waxy
solids.
2. Boiling points of acids increase regularly with
molecular weight and higher than alcohols(of
comparable molecular mass) due to formation of
dimer through H-bonding
3. Carboxylic acids having one to four carbon atoms
are completely miscible with water. Solubility
decreases with molar mass
Dimer Of Carboxylic Acid Molecule
Dimer Of Carboxylic Acid Molecule
There are strong hydrogen bonds between two
carboxylic acid molecules resulting in to dimers.
They are referred to as dimers because two
molecules behave as a single molecule following
the gas laws.
Dimers have boiling point than alphatic carboxylic
acid because the form strong hydrogen bonds.
(Double the number of hydrogen bond in alphatic
carboxylic acids).
Question

 With a reason identify the compound with the

highest boiling point.

a) b)
IUPAC System

 In the IUPAC system, aliphatic carboxylic acids are named

by replacing the ending –e in the name of the
corresponding alkane with –oic acid.
 Generally the carboxylic carbon is numbered oe and it
position needs not to be indicated.
 For naming compounds containing more than one carboxyl
group. The alkyl chain is numbered and the number of
carboxyl groups are indicated by adding the prefix,
dicarboxylic acid, tricarboxylic acid, etc. to the name of
parent alkyl chain.
 Monocarboxylic acids are called alkanoic acids
IUPAC System
3. Derived System

• Acids are regarded as alkyl derivatives of acetic

acid eg
Names and Structures of Some Carboxylic Acids

Structure Common name IUPAC name

HCOOH Formic acid Methanoic acid
CH3COOH Acetic acid Ethanoic acid
CH3CH2COOH Propionic acid Propanoic acid
CH3CH2CH2COOH Butyric acid Butanoic acid
(CH3)2CHCOOH Isobutyric acid 2-Methylpropanoic acid
HOOC-COOH Oxalic acid Ethanedioic acid
HOOC -CH2-COOH Malonic acid Propanedioic acid
HOOC -(CH2)2-COOH Succinic acid Butanedioic acid
ISOMERISM

 Carboxylic acids exhibit both Chain, Positional

isomerism and Functional group isomerism.
• C6H12O2 represent
ISOMERISM
1. Positional isomerism
 In this case isomers have the same molecular formula but differ
in the position of a functional group on the carbon chain.
1. Chain Isomerism
 It arises when two or more compounds have similar molecular
formula but different carbon skeletons
3. Functional Isomerism
 It arises when two or more compounds have the same
molecular formula but different functional group. e.g., C3H6O
represents an aldehyde and as a ketone
ISOMERISM

2, 3 - dimethyl butanoic acid

3, 3 - dimethyl butanoic acid

2, 2 - dimethyl butanoic acid

FUNCTIONAL ISOMERISM
2. Common System

• HCOOH, Formic acid

• CH3COOH, Acetic acid,
• C3H7COOH, Butyric acid
ACIDITY OF CARBOXYLIC ACIDS

The carboxylic acids on ionization produce

carboxylate ion which is stabilized by resonance.
ACIDITY OF CARBOXYLIC
ACIDS
Electrons releasing alkyl groups decrease the
acidity. Hence lower members are more acidic than
higher members e.g.

As the size of alkyl group increases the ionic

character of O-H bond decreases
 ACIDITY OF CARBOXYLIC
ACIDS..
Carboxylic acids give H+ ions to solution just like
mineral acids.
They behave in similar manner with mineral acids
e.g theyreact with bases to give salt and water.
Carboxylic acid have a pH below 7 but slightly
above 3 due to partial ionization.
 ACIDITY OF CARBOXYLIC
ACIDS
 Electrons withdrawing substituents increase the
acidity by increasing the ionic character of –OH
bond by inductive effect and dispersing the
negative charge of anion formed.
 ACIDITY OF CARBOXYLIC
ACIDS
The strength of the acid is expressed in terms of the
dissociation constant (Ka), also called acidity
constant. A stronger acid has higher Ka but lesser
pKa value (pKa = -log Ka).
The electron releasing substituents (ERGs) decrease
the acidic strength of the carboxylic acids by
destabilizing the carboxylate ion.
Example of ERGs: Alcohols (-OH), Ethers (-OR), Alkyl
groups (e.g., -CH3), Amine groups (-NH2 or -NR2)
 ACIDITY OF CARBOXYLIC
ACIDS
• The electron withdrawing substituents such as
halogen atoms (X), nitro (NO2) group increase the
acidic strength by decreasing the magnitude of the
negative charge on the carboxylate anion and thus
stabilizing it. Therefor the release of H+ ion
becomes easy.
 ACIDITY OF CARBOXYLIC
ACIDS
• Acidic strength order

Electon withdrawing effect decreases in the order : F > C1 > Br >

I.
 Test for Acidity
Reactions with metals and alkalies.

Above reactions are used to detect the presence of

carboxyl group in organic compound.
PREPARATION OF
CARBOXYLIC ACID
1. Oxidation of primary alcohols and aldehydes
with acid K2Cr2O7 or KMnO4
Primary alcohols are readily oxidized to carboxylic
acids with common oxidizing agents such as
potassium permanganate in neutral, acidic or
alkaline media or by potassium dichromate
(K2Cr2O7) and chromium trioxide in acidic media.
PREPARATION OF CARBOXYLIC
ACID..
2. From aldehydes:
 Oxidation of aldehydes in presence of mild oxidizing
agents like Tollen’s reagent (ammoniacal silver
nitrate solution) or Fehling reagent forms carboxylic
acids.
PREPARATION OF CARBOXYLIC
ACID
3. From alkylbenzenes: Aromatic carboxylic acids
can be prepared by vigorous oxidation of alkyl
benzenes with chromic (H2CrO4) acid or acidic or
alkaline potassium permanganate (KMnO4) to
give benzoic acid.
PREPARATION OF CARBOXYLIC
ACID
4. Oxidation of alkenes: Suitably substituted
alkenes are oxidized to carboxylic acids on
oxidation with acidic potassium permanganate or
acidic potassium dichromate.
PREPARATION OF CARBOXYLIC
ACID
5. Hydrolysis of Nitriles: hydrolysis of nitriles in
presence of dilute acids or bases forms amide
which on further hydrolysis gives carboxylic acid.
PREPARATION OF CARBOXYLIC
ACID
6. From Grignard reagent: Carboxylic acids can be
prepared from Grignard reagents through a
process called carboxylation. This involves
reacting the Grignard reagent with carbon dioxide
(CO2), followed by acidification to produce the
desired carboxylic acid.
PREPARATION OF CARBOXYLIC
ACID
7. Hydrolysis of an ester: with alkali or
acid

 Alkaline hydrolysis of an ester is known as

saponification
8. Hydrolysis of acid chloride: with
alkali or acid.
PREPARATION OF CARBOXYLIC
ACID
9. Hydrolysis of amides: with alkali or
acid

10.Hydrolysis of anhydrides: with alkali

or acid
Chemical Reaction Of Carboxylic
Acids
1. Reactions with Mineral acids:
 Carboxylic acids on heating with mineral acids such
as or with give corresponding anhydride.
Chemical Reaction Of
Carboxylic Acids
2. Esterification:
 Carboxylic acids are esterified with alcohols in the
presence of a mineral acid such as concentrated
H2SO4 as a catalyst.
Chemical Reaction Of
Carboxylic Acids
Chemical Reaction Of
Carboxylic Acids
3. Reaction with PCl5, PCl3 and SOCl2
 Carboxylic acids react with the above to form acyl
chlorides.
Chemical Reaction Of
Carboxylic Acids
4. Reaction with ammonia (NH3): Carboxylic acids
react with ammonia to give ammonium salt
which on further heating at high temperature
gives amides.
Chemical Reaction Of
Carboxylic Acids
5. Reduction:-Carboxylic acids are reduced to
alcohols in presence of LiAlH4 or B2H6.

6. Decarboxylation:-Sodium or potassium salts of

carboxylic acids on heating with soda lime (NaOH
+ CaO in ratio of 3:1) gives hydrocarbons which
contain one carbon less than the parent acid.
Chemical Reaction Of
Carboxylic Acids
7. Electrophilic Aromatic susbstitution reactions-
Aromatic carboxylic acids undergo electrophilic
aromatic substitution reactions. Carboxyl group in
benzoic acid is electron withdrawing group and is
meta directing.
Chemical Reaction Of
Carboxylic Acids

Note:
Carboxylic acids do not undergo Friedel-Craft’s
reaction (Acylation and Alkylation) because the
carboxylic group is deactivating and the catalyst
AlCl3(anhy.) gets bonded to the carboxyl group.
Chemical Reaction Of
Carboxylic Acids
Other examples;
 Uses of Carboxylic Acids

1. Formic acid is used in rubber, textile, dyeing, leather and

electroplating industries.
2. Used as a reducing agents.
3. Ethanoic acid is used as a solvent and as vinegar in the
food industry.
4. Benzoic acid and its salts are used as urinary antiseptics.
5. Benzoic acid is also used in the preparation of esters and
in perfumery.
6. Higher fatty acids are used for the manufacture of soaps
and detergents.
DERIVATIVES OF CARBOXYLIC ACIDS

 These are obtained when -OH group of carboxylic

acids is replaced by Cl, NH2, OR’ and OCOR and
are called respectively acid chlorides, acid amides,
esters and acid anhydrides.
 ACID CHLORIDES
General Formula:

Acid halide (X = Cl, Br, I)

Nomenclature
Replace the terminal ‘e’ with ‘oyl’ and name halide
e.g. Ethanoly chloride
Nomenclature Of Acid
Chlorides..
IUPAC named Alkanoyl Chloride
 Physical Properties
1. Appearance- Lower acyl chlorides are colourless
liquids with a strong odour.
2. Solubility- They dissolve in organic solvents like
alcohol, ether, and chloroform.
3. Acid Chlorides are polar in nature, still insoluble
in water due to absence of hydrogen bonding
which is also the reason of their having low B.p.
than carboxylic acids.
 Methods Of Preparation

1. From Carboxylic acids

Methods Of Preparation

2. From Salts Of Carboxylic Axids (Industrial

method)
Chemical Reactions of
Acid Chlorides
Acid halides react readily with various nucleophiles
via nucleophilic acyl substitution, a reaction
mechanism where a halogen atom (e.g., Cl, Br, I) is
replaced by another group.
Some of the reactions;
1. Hydrolysis: Reaction with water (H₂O) leads to
the formation of carboxylic acids.
2. Alcoholysis: Reaction with alcohols (ROH)
produces esters.
Chemical Reactions of
Acid Chlorides
Some of the reactions
3. Amide Synthesis: Reaction with ammonia (NH₃) or
amines (RNH₂) generates amides.
4. Anhydride Formation: Reaction with carboxylic
acids (RCOOH) yields acid anhydrides.
5. Ketone Synthesis: Reaction with Grignard reagents
(RMgX) produces ketones.
6. Reduction: Reaction with lithium aluminum hydride
(LiAlH₄) results in primary alcohols.
Chemical Reactions of
Acid Chlorides
Uses of Acid Chlorides

1. As acylating agent e.g in Friedel-Craft’s acylation

reaction
2. Synthesis of ketones by reacting with
organometallic reagents like Grignard reagents
and organolithium compound
3. Syntheis of carboxylic acids: Acid chlorides can be
hydrolyzed to produce carboxylic acids.
4. Synthesis of Alcohols: They can be reduced to
alcohols using lithium aluminum hydride (LiAlH4)
or reacted with Grignard reagent.
5. Synthesis of Plastics and Polymers.
AMIDES

• General formula
 Nomenclature
 The IUPAC and common names of amides are
derived from the parent carboxylic acid, by
replacing the suffix “oic acid” and “ic acid,”
respectively, with “amide.
IUPAC name Alkanamide
Formula, Common name, IUPAC name
HCONH2, Formamide, Methanamide
CH3CONH2, Acetamide, Ethanamide
Nomenclature

Benzamide

Questions: Draw the structure for;

a) N- methyleheptanamide
b) N,N-dimethylbenzamide
c) N-methyl-2-bromopropanamine
 Physical Properties

1. Except formamide, amides are colourless,

crystalline solids.
2. Lower members are soluble in water and alcohol.
3. Their m.pts are higher due to hydrogen bonding
 Methods of Preparation

Reacting Carboxylic Acids and NH3

Reacting Acid Chlorides and NH3

Reacting Acid Anhydides and NH3

 Methods of Preparation

Hydrolysis of Nitriles

Reacting Esters and NH3

Chemical Reactions of
Acid Amides
1. Hydrolysis:
Acidic Conditions:
• Amides react with water in the presence of acid to
yield a carboxylic acid and an ammonium salt
(NH4+).
Basic Conditions:
• Amides react with water in the presence of base to
yield a carboxylic acid and ammonia (NH3) or an
amine.
Chemical Reactions of
Acid Amides
2. Reduction
 LiAlH4: Amides can be reduced by LiAlH4, forming primary
amines.
2. Dehydration
 Formation of Nitriles: Amides can be dehydrated to form
nitriles, which are compounds containing a carbon triple
bond to a nitrogen (R-CN).
2. Hofmann Degradation
 Conversion to Primary Amines: In the Hofmann degradation,
an amide is treated with bromine and a base to produce a
primary amine with one less carbon atom.
Chemical Reactions of
Acid Amides
USES

1. Pharmaceuticals:
 Many drugs, including paracetamol, penicillin, and LSD, are
amides.
2. Polymers and Materials:
 Amides are key components in polymers like nylons,
aramids, and Kevlar, which are known for their strength and
durability.
3. Solvents
• Low molecular weight amides, such as dimethylformamide,
are used as solvents in various chemical processes.
ESTERS

 Esters are organic compound that reacts with water

to produce alcohols as well as organic/inorganic
acids.
• General formula
Nomeclature
• Esters are named as if the alkyl chain from the
alcohol is a substituent.
• When naming esters you prefix the alkyl group from
the originated alcohol and then add the suffix name
of the original acid but replacing the ‘oic’ with
‘oate’
Nomeclature

• Formula, Common name, IUPAC name

Ethyl acetate, ethyl ethanoate

Methyl acetate, methyl ethanoate

Question
1. Draw the structure of the following compounds;
a) Ethyl butanoate
b) Ethyl-3-butenoate
2. Give the product for the reaction below:
(CH3CO)2O + H2O 
 Methods of Preparation

1. Reaction between Aid chlorides and alcohols

2. Reacting carboxylic acids and alcohols

3. Reacting acid anhydrides with alcohols

 Physical Properties

1. They have a pleasant smell

2. Lower members are liquids and higher solids
3. They are sparingly soluble in water soluble in
alcohol and ether.
4. Esters are highly volatile and are highly
flammable.
Chemical Reactions Of
Ester
Uses Of Esters
1. The main use of esters is for flavorings and
perfumes/artificial essences .
2. They can also be used in the chemicals industry as
solvents.
3. Pharmaceuticals: Esters are important building blocks
in the synthesis of many pharmaceutical drugs.
4. Agrochemicals: Some esters are used in the
production of pesticides and herbicides.
5. Pigments: Certain esters are used in the production of
dyes and pigments.
 ACID ANHYDRIDE
• General formula
Physical Properties

1. Appearance: Colorless liquids (lower aliphatic

anhydrides) or colorless solids (higher aliphatic
and aromatic anhydrides).
2. Odor: Pungent, often described as vinegar-like.
3. Boiling Point: Higher than their parent acids due
to stronger intermolecular forces.
4. Solubility: Soluble in organic solvents, but react
with water to form the parent acid. For example,
acetic anhydride reacts with water to produce
acetic acid.
Nomeclature
Symmetrical anhydrides are formed from a
mixture of two identical carboxylic acids and are
named by changing the suffix “acid” with
“anhydride”.
If the originating acid is the same then you add the
name only once.
For example, the IUPAC name ethanoic anhydride
is derived from ethanoic acid, and the common
name, acetic anhydride, is obtained from acetic
acid.
Nomeclature..
• Question drwn the structure for:
a) Ethanoic methanoic anhydride
b) Ethanoic anhydride
Nomeclature

Formula, Common name, IUPAC name

Acetic anhydride, Ethanoic anhydride

Propionic anhydride, Propanoic anhydride

Methods of Preparation
Chemical reactions of anhydrides
 USES

1. Acid anhydrides are also used as plasticizers for PVC

and other plastics
2. Acid anhydrides are key reactants in the synthesis of
esters,
3. Aspirin- Acetic anhydride is a key ingredient in the
synthesis of aspirin (acetylsalicylic acid)
4. Production of various pharmaceuticals, industrial
chemicals and perfumes
5. Protecting Groups- Acid anhydrides can also be used as
protecting groups in organic synthesis to safeguard
sensitive groups during reactions
IMIDES
mides are chemical compounds characterized by
having a nitrogen atom bonded to two carbonyl
groups (C=O).
Imides are monoacyl derivatives of amides or
lactams.

Amoxicillin
Lactams ring
Nomenclature
Uses
1. Used as valuable intermediates in organic
synthesis.
2. synthesis Used in biologically active compounds
like drugs, fungicides and herbicides.
3. Synhtesis of polmers.
NITRILES
Nitriles are organic compounds characterized by
the presence of a cyano functional group (C≡N).
They are also known as cyano compounds and
have the general formula R-C≡N, where R
represents an organic group.
Nomenclature
NITRILES..
Polarity:
• Due to the electronegative nitrogen atom, nitriles
are highly polar molecules.
Reactions:
• Nitriles can undergo hydrolysis to form carboxylic
acids.
Nitrile Reactions
Applications

 Nitriles are used in various applications, including

the production of nitrile rubber, synthetic textiles,
and polymers