Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

CHEMISTRY OF CARBOXYLIC ACID AND THEIR DERIVATIVES

Organic compounds which contain the carboxyl functional group (-COOH) are called the
carboxylic acids. The general formula of carboxylic acid is CnH2n+1+COOH.
O

R C OH or RCOOH or RCO2H
O

The name carboxyl is derived from CARBonyl C and hydrOXYL OH because in the CARBOXYL
group these two groups are directly bonded to each other.
O
CARBonyl C OH hydrOXYL
functional group functional group

CARBOXYL functional group

Classification of carboxylic acid

Carboxylic Acids are classified as,
i) Aliphatic Carboxylic acids.
ii) Aromatic Carboxylic acids.
1. Mono carboxylic Acids containing one – COOH
2. Dicarboxylic Acids containing two – COOH
3. Tricarboxylic Acids containing three – COOH
4. Polycarboxylic Acids containing more than two – COOH
The long chain monocarboxylic acids are commonly known as fatty acids because many of them
are obtained by hydrolysis of animal fats or vegetable source oils.
Preparation of Carboxylic Acids: -
Carboxylic acids are prepared by the following methods.
1. Oxidation of Primary Alcohols or Aldehydes: -
Primary alcohols or aldehydes undergo oxidation with a mixture of potassium dichromate and
Sulphuric acid to form carboxylic acids. The alcohols are first oxidized to aldehydes and then to
carboxylic acids.
O O
H2 [O]
R C OH
[O]
R C H R C OH

2. Hydrolysis of Nitrites or Alkyl cyanides: -

The alkyl cyanides when are hydrolyzed they produce carboxylic acids.
O

H2 O
R C N R C OH + NH3
H
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

H2O
H3C C N H3 C C OH + NH3
H

3. Hydrolysis of Esters: -
When an ester is boiled with concentrated aqueous NaOH solution sodium salt of the acid is
formed. On treatment will dilute HCl produces corresponding acid.
O O

NaOH
H3C C OC2H5 H3C C ONa + C2H5OH
Heat

O O

H 3C C ONa + HCl H 3C C OH + NaCl

4. From Grignard Reagent and CO2: -

Grignard reagent (RMgX) react with CO2 to form addition product that can be hydrolyzed to
carboxylic acid.
CH3 O

H2O
O C O + CH3MgI O C OMgI H3C C OH + MgI(OH)
H+

5. Carboxylation of Alkenes (Koch Reaction): -

When an alkene is heated with carbon monoxide and steam under pressure with phosphoric
acid at 400oC carboxylic acid are formed.
CH3

H3PO4
H3C C CH2 + CO + H2O H3C C COOH
H 400oC H

6. Oxidation of Alkyl Benzene: -

Alkyl benzene an oxidation with potassium permanganate yield carboxylic acid.
CH3 COOH

O
Benzoic acid
KMnO4

7. Decarboxylation of Dicarboxylic Acids: -

Two carboxyl group attached to the same carbon atom are unstable to heat and a molecule of
CO2 is lost.
COOH H2
Heat
R CH R C COOH + CO2
COOH
COOH
H2C Heat
H3 C COOH + CO2
COOH
COOH Heat
H COOH + CO2
COOH

8. From Hydrolysis of Trihalogen Compounds: -

Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

When Trihalogen compound are heated with KOH solution carboxylic acids are formed.
OH
R CCl3 + 3H2O KOH Heat
R C OH RCOOH + H2O
-3HCl
OH
OH
KOH Heat
C6H5 CCl3 + 3H2O C6 H5 C OH C6H5COOH + H2O
-3HCl
OH
9. From Amides: -
When amides are heated in the presence of acid carboxylic acid is formed.

CONH2 COOH

H2O
+ NH3
H
Benzoic acid

Physical Properties: -
1. Lower carboxylic acids (up to C10) are liquids. Higher members are wax like solid and almost
odourless.
2. Lower carboxylic acids have disagreeable odour while higher acids are odourless.
3. Melting points of carboxylic acids increases irregularly with increase in molecular weight.
4. Boiling points of carboxylic acids are higher than those of alcohols of same molecular weight.
5. The first four members are completely soluble in water due to hydrogen bonding and solubility
decreases with increase in molecular weight.
6. Carboxylic acids are polar due to the carboxylic group.
7. The IR spectrum shows that O−H stretching at 2500 – 3300cm-1 and C=O stretching at 1710 –
1720cm-1.
Chemical Properties of Carboxylic Acids: -
Carboxylic acids are acidic in nature and lose a proton readily because the carboxylic ion is
formed by ionization and is stabilized by the resonance.
RCOOH RCOO + H+
O O O
R C R C  R C
O O O
This stability can be explained based on its molecular structure. The carbon atom of carboxylic
ion is sp2 hybridized it is bonded to each oxygen atom by a 𝜎-bond. The unused carbon p orbital
overlaps with p-orbitals of both oxygen atoms to form a stable delocalized molecular orbital.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

 Delocalized Molecular orbital

O
nd
bo


 bond
R C

bo
nd

1. Salt Formation: -
Carboxylic acids react with hydroxides carbonate and bicarbonate to form corresponding salts.
O O

H3C C OH + NaOH H3 C C ONa + H2O

O O

2 H3C C OH + Na2CO3 2 H3C C ONa + H2O + CO2

2. Formation of Acid Halides: -

Carboxylic acids react with phosphorous halides or Thionyl chloride (SOCl2) to form acid halides
O O

H3C C OH + SOCl2 H3C C Cl + HCl + SO2

3. Formation of Amides: -
Carboxylic acids react with ammonia to give salts which on heating yields amides.
O O O

H3C C OH + NH3 H3 C C ONH4 H3C C NH2 + H2O

4. Formation of Esters: -
Carboxylic acids react with alcohols in the presence of strong acid like H2SO4 or HCl to form
esters.
O O

HCl
H3C C OH + HOC2H5 H3C C OC2H5 + H2O

5. Formation of Anhydrides: -
Carboxylic acids undergo dehydration with P2O5 to form acid anhydride.
O O O O
P2O5
H3C C OH + HO C CH3  H3C C O C CH3 + H2O
Acetic anhydride
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

6. Reduction: -
Carboxylic acids undergo reduction with Lithium aluminum hydride to give primary alcohols.
O
LiAlH4 H2
R C OH R C OH
Ether
7. 𝜶-Halogenation {Hell Volhard-Zetnisky (HVZ)} Reaction: -
Carboxylic acids having 𝛼-hydrogen treated with Cl2 or Br2 in the presence of phosphorous
undergo 𝛼-halogenation by replacing 𝛼-hydrogen.
Cl
H2
R C COOH + Cl2 R C COOH + HCl
H
Cl
H2
H3C C COOH + Cl2 H3C C COOH + HCl
H
8. Decarboxylation: -
Carboxylic acids salts lose carbon dioxide to form hydrocarbon in the presence of soda lime and
heat.
O

NaOH/CaO
R C ONa R H + Na2CO3
Heat
Alkane
O

NaOH/CaO
H3 C C ONa H3C H + Na2CO3
Heat
Methane
9. Ring Substitution: -
Aromatic carboxylic acids undergo electrophilic substitution reaction and substitution at ring
takes place in the presence of Lewis acid and as carboxylic group is ring deactivator so meta
substitution takes place.
COOH COOH

FeBr3
+ Br2 + HBr

Br
Carboxylic Acids Derivatives: -
Compounds of carboxylic acids in which H or OH of carboxyl group are replaced by other atom
or group of atoms are called carboxylic acid derivatives.
The most common and important derivatives of carboxylic acids are,
1. Acid or Acyl Halides.
2. Anhydrides.
3. Esters.
4. Amides.
1. Acid Halides (Acyl Halides): -
O

R C X
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

Acid halides are the derivatives of acids in which the –OH functional group of carboxyl
functional group has been replaced by a halogen atom.
O O

- OH
R C OH R C X
+X
Acid halides are also called acyl halides. The acyl groups.
O

R CO or R C
The acid chlorides are the most important of all the acid halides.
Preparation: -
Acid chlorides are prepared from appropriate carboxylic acid. Some methods are given below.
1. By Acid and Thionyl Chloride: -
When carboxylic acids are treated with Thionyl chloride, acid chloride is formed.
O O

R C OH + SOCl2 R C Cl + HCl + SO2

H3C C OH + SOCl2 H3C C Cl + HCl + SO2

O O
2. By Acid and Phosphorous Trichloride: -
When a carboxylic acid is treated with PCl3 , acid chloride is formed.
O O

R C OH + PCl3 R C Cl + H3PO3

H3 C C OH + PCl3 H3C C Cl + H3PO3

O O
3. By Acid and Phosphorous Penta Chloride: -
When phosphorous penta-chloride is reacted with carboxylic acid than acid chloride is formed.
O O

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

H3 C C OH + PCl3 H3C C Cl + POCl3 + HCl

O O
It is possible to prepare acid bromides and iodides by reaction analogous to those used in the
preparation of chlorides. However, in comparison to the chlorides they are seldom used.
Physical Properties: -
1. All simple acid chlorides are colorless liquids of lower boiling points than corresponding acid.
2. They have sharp pungent smell and are Lachrymators (tear producing).
3. They emit pale yellow fumes of hydrogen chloride when exposed in air because their reaction
with water vapors.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

4. They are insoluble in water but slowly dissolve in it because of hydrolysis.

5. The C O stretching band in IR spectrum occurs at frequency range in 1789 – 1850cm-1.
Chemical Properties of Acid Chlorides: -
The acid halides (chlorides) undergo the following reactions.
1. Hydrolysis: -
They react with water when the chlorine atom is displaced by OH group to reform the original
organic acid.
O O

H3C C Cl + H2O H3C C OH + HCl

2. Alcoholysis: -
Esters are formed when acid chlorides react with alcohols.
O O

R C Cl + HOC2H5 H 3C C OC2H5 + HCl

3. Reaction with Ammonia: -
Acid chlorides react with ammonia resulting in the formation of amides.
O O

R C Cl + HNH2 H3C C NH2 + HCl

NH3 + HCl NH4Cl

4. Friedel Craft Reactions: -

Acid chlorides undergo Friedel crafts acylation resulting in the formation of ketone when
reacted with benzene in the presence of Lewis acid (AlCl3).
O
O
AlCl3 C CH3
+ H3C C Cl
+ HCl

5. Reduction: -
Acid chloride reduced when reacted with hydrogen in the presence of poisoned palladium
catalyst.
O O
Pd
H3C C Cl + H2 H3C C H + HCl
BaSO4
2. Acid Anhydrides: -
The compounds derived by less of water molecules between two molecules of a carboxylic acid
are called acid anhydrides or simply Anhydrides.
O O

R C O C R or CO O CO
O O O O

H3C C O C CH3 C2H5 C O C C2H5

Acetic or Ethanoic anhydride Propanoic anhydride
Anhydrides derived from two molecules of different acids are called mixed anhydrides.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

Preparation of Anhydrides: -
Acid anhydrides may be prepared.
1. Reaction of Acid Halides and Carboxylic Acid: -
When acid halides are reacted with a carboxylic acid in pyridine, acid anhydride is formed.
O O O O

C5H5N
R C Cl + HO C R R C O C R + HCl

O O O O

C5H5N
H3C C Cl + HO C CH3 H3C C O C CH3 + HCl

Acetic or Ethanoic anhydride

2. By Reaction of Acid Halide with a Salt of Carboxylic Acid: -

When acid salt is reacted with acid halides acid anhydride is formed.
O O O O

R C Cl + NaO C R R C O C R + NaCl

O O O O

H3C C Cl +NaO C CH3 H3C C O C CH3 + NaCl

Acetic or Ethanoic anhydride
3. Cyclic Anhydrides: -
When dicarboxylic acid salts are heated a cyclic acid, anhydride is formed.
O

COOH
200oC C
O + H 2O
COOH C

Phthalic Anhydride
Physical Properties: -
1. The lower simple anhydrides are colorless liquid with a sharp pungent smell.
2. They are insoluble in water due to lack of hydrogen bonding.
3. They have higher boiling points than the acid from which they are derived.
4. The IR spectrum shows C=O stretching bond 1800 – 1850 and 1740 – 1790cm-1.
5. They are hydrolyzed by water to give corresponding acids.
Chemical Properties: -
The acid anhydrides undergo the following reactions.
1. Hydrolysis: -
Hydrolysis of acid anhydrides gives carboxylic acids.
O O O O
H3C C O C CH3 + H2O H3C C OH + HO C CH3
2. Reaction with Alcohols: -
Alcohols give Esters when reacted with acid anhydride.
O O O O
H3C C O C CH3 + HOC2H5 H3C C OC2H5 + HO C CH3
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

3. Reaction with Ammonia: -

Acid anhydrides when reacted with ammonia give amides.
O O O O
H3C C O C CH3 + HNH2 H3C C NH2 + HO C CH
3
4. Reaction with Amines: -
When acid anhydrides are treated with amines substituted amides are formed.
O O O O

H3 C C O C CH3 + HNHR H3C C NHR + HO C CH3

N-Alkyl acetamide

5. Friedel Crafts Reactions: -

The reaction of benzene with anhydride in the presence of AlCl3 give ketones.
O
O O O
C CH3
H3C C O C CH3 + + HO C CH3

Esters
These organic compounds in which the – OH group of carboxyl group is replaced by – OR(alkoxy)
group are called Esters.
O

R C O R or RCOOR
They are also called carboxylic esters. Many esters occur in flowers and fruits which owe their
fragrance to these compounds.
Preparations: -
Some important methods of esters preparation are given below.
1. By Fisher Esterification: -
When a mixture of carboxylic acid and an alcohol is heated in the presence of concentrated
H2SO4 as catalyst.
O O

H2SO4
R C OH + HO R R C O R + H2O

O O

H2SO4
H3C C OH + HO CH3 H3C C O CH3 + H2O

2. By Acid Chlorides and Alcohol Reaction: -

When acid chlorides react with alcohol in the presence of pyridine give esters in acidic medium.
O O

H2SO4
R C Cl + HO R R C O R + HCl
3. From acid Anhydrides: -
Acid anhydrides react with alcohols to form ester.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

O O O

R C O C R + HO R R C OR + RCOOH

4. From alkyl Halide: -

When carboxylate salts and alkyl halides react, ester is formed.
O O

R C ONa + X R R C OR + NaX
5. From Diazo-methane: -
When a carboxylic acid react with Diazo-methane than methyl ester is formed.
O O

R C OH + CH2N2 R C OCH3 + N2

Physical Properties of Esters: -

1. Lower carboxylic esters are neutral colorless liquids having fruit odour.
2. The boiling points of lower ester are lower than corresponding carboxylic acid.
3. They are generally insoluble in water and soluble in most organic compounds.
4. Many esters are excellent solvent for other organic substances.
5. The IR spectrum shows characteristic C O stretching at 1735cm-1 frequency range.
Chemical Properties of Esters: -
Some important chemical properties of ester are given below.
1. Hydrolysis: -
The hydrolysis of ester on heating gives alcohols and carboxylic acid in the presence of acid.
O O

H+
H3C C OC2H5 + H2O H3C C OH + C2H5OH
2. Trans esterification: -
Esters react with other alcohols under acidic or basic conditions to give new esters. This reaction
is called trans esterification because ester is converted into another ester.
O O

H+
R C OR' + HO R" H3C C OR" + R'OH
excess
3. Reaction with Ammonia: -
Esters react with ammonia often in a solvent such as ethanol to give amides.
O O
H+
R C OR' + H NH2 R C NH2 + R'OH
4. Reduction: -
Esters undergo reduction with LiAlH4 to form primary alcohols.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

O O

LiAlH4
R C OR' R C OLi + R'OLi

O
H2O H2
R C OLi + R'OLi R C OH + R'OH
H+
5. Reaction with Grignard Reagent: -
Ester react with Grignard reagents to form ketones which at once react with another molecule
of the Grignard reagent to yield a tertiary alcohol.
O OMgX

R C OR' + R'MgX R C OR'

OMgX O

H2O
R C OR' R C R' + MgX(OR')
H+
R

O OMgX

R C R' + R"MgX R C R'

R"
OMgX OH

H2O
R C R' R C R' + MgX(OH)
H+

R" R"

Amides: -
Those organic compounds in which – OH group of COOH group have been replaced by an amino
group (−NH2) are called Amides or acid amides. The general formula of amides is,
O

R C NH2 or RCONH2

Preparation of Amides: -
Some methods of amides preparation are given as,
1. By the Action of Ammonia on Acid Chlorides: -
When ammonia is reacted with acid chloride amides are formed.
O O

R C Cl + 2NH3 H3 C C NH2 + NH4Cl

2. By Reaction of Ammonia and anhydrides: -

Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

When ammonia is treated with acid anhydrides, amides and acids are formed.
O O O O

H3C C O C CH3 + HNH2 H3C C NH2 + HO C CH3

3. From Ammonium Carboxylates: -

When ammonium carboxylates are heated amide is formed.
O O

H3C C ONH4 R C NH2 + H2O

Physical Properties of Amides: -

1. Almost all amides are white, odourless crystalline solids.
2. They have sharp melting points that are due to intermolecular hydrogen bonding.
3. Simple amides up to six carbons are vary soluble in water and solubility decreases as number
of carbon increases.
4. They are soluble in organic solvent.
5. IR spectrum shows C O stretching at 1680cm-1.

Chemical Properties of Amides: -

Amides are the least reactive in acid derivatives due to resonance stability.

O O

R C NH2 R C NH2+

Some important chemical properties are,

1. Hydrolysis: -
Amides are hydrolyzed in acid on prolonged heating.
O O


R C NH2 + H2O + HCl R C OH + NH4Cl

2. Reduction: -
Amides are reduced to amines on reacting with Lithium Aluminum hydride.
O

LiAlH4 H2
H3C C NH2 H3C C NH2

3. Reaction with Nitrous Acid: -

Amides on treatment with nitrous acid form carboxylic acid.
O O

H3C C NH2 + O N OH H3 C C OH + N2 + H2O

4. Dehydration with P2O5: -

When amides are heated with a strong dehydrating agent such as phosphorous penta-oxide
give alkyl nitrites.
Muhammad Hussain Sabir Naqshbandi (Gold medallist) Assistant Professor (Govt: Boys Degree College Pishin)

H3C C NH2 + P O H3C C N + H2O

2 5
5. Hofmann’s Degradation of Amides: -
Treatment of an amide with bromine and sodium hydroxide solution produce primary
ammonia.
O

R C NH2 + Br2 + 4NaOH R NH2 + 2NaBr + Na2CO3 + 2H2O

O

H3C C NH2 + Br2 + 4NaOH H3C NH2 + 2NaBr + Na2CO3 + 2H2O