Carboxylic Acid Derivatives

 Acid derivative is a derivative of carboxylic acid which is obtained by replacing –OH

group of carboxylic acid by another reactive atom or group of atoms.
O - OH O
R – C – OH R–C–X
+X

Derivatives of Acetic Acid

+ Cl O
CH3 – C – Cl (acetyl chloride)
+ NH2 O
O CH3 – C – NH2 (acetamide)
CH3 – C – OH + O – C2H5 O
CH3 – C – O – C2H5 (ethyl acetate – ester)
O

+ O – C – CH3 O O
CH3 – C – O – C – CH3 (acetic anhydride)

I) Acetyl Chloride
 Chemical formula: CH3COCl
O
 Functional group: – C – Cl
 Common name: Acetyl chloride
–e
 IUPAC name: Alkane Alkanoyl chloride
+ oyl chloride

 Ethynoyl chloride
 Preparation

From glacial acetic acid:

i) With PCl5 and PCl3

O O

CH3 – C – OH + PCl5 CH3 – C – Cl + POCl3 + HCl

Acetyl chloride

O O

3CH3 – C – OH + PCl3 3CH3 – C – Cl + H3PO4

ii) With SOCl2 (Thionyl chloride)
O
CH3 – C – OH + SOCl2 CH3COCl + SO2 + HCl
Acetyl chloride
 Preparation of acetyl chloride from acetic acid with SOCl 2 is the best method because
by-products formed are in gaseous state and can escape easily.

Physical Properties

 It is a colourless liquid with pungent smell.

 It boils at 52 0C (lower than parent acid).
 It is insoluble in water due to absence of hydrogen bond but soluble in alcohol, ether
and ester.
 It fumes in moist air due to formation of HCl gas.
CH3COCl + H2O CH3COOH + HCl (gas)

Chemical Properties (Nucleophilic Addition-Elimination Reaction

 Acetyl chloride is the most reactive derivative of acetic acid. This is because in acetyl
chloride the carbonyl carbon atom is bonded to highly electronegative chlorine atom.
 Due to negative I effect (-I effect) or electron withdrawing of Cl atom, the electron
density on carbonyl carbon is reduced and it can be easily attacked by a nucleophile.
 Acylation:
The replacement of hydrogen atom of certain group such as OH, NH 2, NH – R, etc by
acyl group (R – CO) is called acylation. When acylation is carried out with acetyl
chloride, the process is known as acetylation.

i) Hydrolysis of acetyl chloride:

O O
CH3 – C – Cl + H2O CH3 – C – OH + HCl
Acetic acid
Mechanism: 1) Addition of Nu
O O–
CH3 – C – Cl + H – O – H CH3 – C – Cl
O+ – H
H
2) Elimination of Cl–
O– O
CH3 – C – Cl CH3 – C + Cl
O+– H O+ – H
H H
3) Elimination of proton (H+)
O O
CH3 – C + Cl CH3 – C + Cl
O+– H OH
H
 ii) Reaction with ethyl alcohol (alcoholysis):
O O
CH3 – C – Cl + HO – C2H5 CH3 – C – O – C2H5 + HCl
Ethyl acetate (ester)
(ethyl ethanoate)

iii) Reaction with ammonia (ammonolysis):

O O
CH3 – C – Cl + HNH2 CH3 – C – NH2 + HCl
Acetamide

iv) Reaction with ethyl amine:

O O
CH3 – C – Cl + HNHC2H5 CH3 – C – NHC2H5 + HCl
Ethyl acetamide

II) Ethyl Acetate (Ester)

O
 Chemical formula: CH3– C – O – C2H5 (CH3COOC2H5)
 Common name: Name of alkyl group + Name of parent acid – ic acid + ate
Eg: CH3COOC2H5 Ethyl acetate
 IUPAC name: Name of alkyl group + Name of parent acid (IUPAC) – ic acid + ate
Alkyl alkanoate
Eg: CH3COOC2H5 Ethyl ethanoate

Preparation

From glacial acetic acid:

conc. H2SO4

CH3COOH + C2H5OH CH3COOC2H5 + H2O

 Physical Properties

 It is a colourless liquid with pleasant smell with boiling point lower than parent acid.
 It is soluble in water, alcohol and ether.
 It is neutral to litmus.

Chemical Properties

Hydrolysis of ethyl acetate:

 It is catalysed by both mineral acids as well as alkalis.

i) In Acidic Medium:
O H+ O
CH3 – C – O – C2H5 + H2O CH3 – C – OH + C2H5OH
ii) In Basic Medium:
O
CH3 – C – O – C2H5 + NaOH CH3COONa + C2H5OH
Sodium Ethyl
ethanoate alcohol

 Since alkali (sodium or potassium) salts of higher carboxylic acid (fatty acid) are
soaps. The alkaline hydrolysis of ester is called saponification.

Fats

Fats and Oils:

 Are obtained from plants and animals.

 Fats and oils are esters of higher fatty acids and glycerol.
 The esters are called glycerides.
Fats:

 Are glycerides of saturated fatty acids with high molecular masses.

 Are solid at room temperature.
O
CH2O – C – C17H35
CH2OH O
CHOH + 3C17H35COOH CHO – C – C17H35 + 3H2O
CH2OH Steric acid O
CH2O – C – C17H35
Glyceryl stearate
(Tristearin-fat)

Saturated fat:

 A fat in which fatty acids, all have single bonds.

Unsaturated fat:

 A fat or fatty acid containing one or more double bond.

 Liquid at body temperature.

Oils:

 Are glycerides of unsaturated fatty acids with low molecular mass.

 Are liquid at room temperature.
Eg: O
CH2O – C – C17H33
CH2OH O
CHOH + 3C17H33COOH CHO – C – C17H33 + 3H2O
CH2OH Oelic acid O
Glycerol CH2O – C – C17H33
Glyceryl oclate
(Trioelin-oil)
Health Risk of Saturated Fats:

 Consumption of saturated fats, the cholesterol level increases which causes blockage
in arteries, which increases the risk of heart diseases and stroke (or cardiovascular
disfunction).

Biodiesel:

 Is diesel fuel made from vegetable oils, animal fats or recycled restaurant grease.
 It is safe, biodegradable and produces less air pollutants than petroleum based diesel.

Preparation / Manufacture of Biodiesel:

 The conversion of vegetable oil into biodiesel is done by a reaction called trans-
esterification reaction.
 In this reaction vegetable oil is treated with alcohols containing short chain and low
molecular weight in presence of base as a catalyst.
C16H32COOH NaOH / KOH CH2OH
C16H31COOH + 3CH3OH 3C16H33COOH + CHOH
C16H32COOH catalyst CH2OH

Uses of Esters:

 It is used as a solvent for oils, fats, resins, etc.

 It is used in perfumery for making artificial flavours and essences.
 It is used in the treatment of skin diseases.
 It is used in the preparation of acetoacetic water.

III) Acetic Anhydride

O O
CH3 – C – O – C – CH3
 Chemical formula:
O O O
CH3 – C – O – C – CH3 CH3 – C O
2
  Functional group:

O O
–C–O–C– anhydride

 Common name: Replacing acid of parent acid with anhydride.

– acid
Acetic acid Acetic anhydride
+ anhydride (common name)
 IUPAC name: Alkanoic anhydride

CH3COOCOCH3 Ethanoic anhydride

Preparation

By dehydration of acetic acid:

 When acetic acid is heated with strong dehydrating agent P 2O5, acetic anhydride is
obtained.
O O P2O5 O O
CH3 – C – OH + H – O – C – CH3 CH3 – C – O – C – CH3 + H2O
Acetic anhydride
OR

P2O5 O O
2CH3COOH CH3 – C – O – C – CH3 + H2O

Physical Properties

 It is colourless liquid with vinegar smell.

 It is soluble in water.
 Its boiling point is 139 0C.
 Chemical Properties

 Acetic anhydride is less reactive than acetyl chloride. This is because the electron
deficiency at carbonyl carbon in acetic anhydride is decreased by oxygen atom and
the attack by nucleophile becomes difficult.
O O O O
CH3 – C – O – C – CH3 CH3 – C δ+ + CH3 – C δ–

i) Reaction with water (Hydrolysis).

O O
CH3 – C – O – C – CH3 + H2O 2CH3COOH

ii) Reaction with ethyl alcohol (Alcoholysis).

O O O
CH3 – C+ – O– – C – CH3 + H+ O– C2H5 CH3 – C – O – C2H5 + CH3COOH

iii) Reaction with ammonia (Ammonolysis).

O O O
CH3 – C+ – O– – C – CH3 + H+ N– CH2 CH3 – C – NH2 + CH3COOH
Acetamide

iv) Reaction with ethylamine.

O O O
CH3 – C+ – O– – C – CH3 + H+ N– HC2H5 CH3 – C – NHC2H5 + CH3COOH
Ethyl acetamide
 Manufacture of Aspirin (Acetyl salicyclic acid)

 Aspirin is acetyl salicyclic acid prepared by heating salicyclic acid with acetyl
chloride or acetic anhydride in presence of phosphoric acid.

COOH COOH O
OH O O H3PO4 O – C – CH3
+ CH3 – C – O – C – CH3 + CH3COOH

Salicyclic (Aspirin)
acid

 Aspirin reduces fever and is also used as pain killer.

 Advantages of acetic anhydride over acetyl chloride in production of aspirin:
1) Reaction with acetyl chloride is very fast and difficult to control while with acetic
anhydride it is slower and controllable.
2) It is less dangerous with acetic anhydride since no HCl is produced.
3) It is cheaper reagent.

IV) Acetamides
 Amides are the derivatives of carboxylic acids in which the –OH group is replaced by
–NH2, -NHR, NR2 groups.
 It is also referred as acid amides.
 Chemical formula: CH3CONH2

 Molecular formula: C2H5ON

 Structural formula:
O
CH3 – C – NH2
 Functional group: O
C – NH2 (amide)
 Common name: Replace ic acid by amide.
Eg: Acetic acid – ic acid + amide = Acetamide
 IUPAC name: Replace oic acid by amide.
Eg: Ethanoic acid – oic acid + amide = Ethanamide (Alkamide)

Preparation

i) From acetic acid.

CH3COOH + NH3 CH3CONH2 + H2O

ii) From acetyl chloride Is the most common method.

CH3COCl + NH3 CH3CONH2 + HCl

iii) From acetic anhydride.

CH3COOCOCH3 + NH3 CH3CONH2 + CH3COOH

iv) Heating ammonium acetate in presence of glacial acetic acid.

glacial acetic acid
CH3COONH4 CH3CONH2 + H2O

Physical Properties

 It is a colourless crystalline solid.

 Soluble in water and alcohol.
 It is a good solvent for organic and inorganic substances.
 Chemical Properties

i) Hydrolysis.
O O
CH3 – C – NH2 CH3 – C+ + N–H2
O
CH3 – C – NH2 + H2O CH3COOH + NH3 (slow reaction)
a) In acidic medium
O
CH3 – C – NH2 + H2O + HCl (aq) CH3COOH + NH4Cl (fast)
b) In alkaline medium
O
CH3 – C – NH2 + H2O + NaOH (aq) CH3COONa + NH3 (very fast)

ii) Reduction.
 When treated with LiAlH4 or sodium and alcohol, amides are reduced to primary
amines.
O LiAlH4

R – C – NH2 + 4H R – CH2 – NH2 + H2O

or Na / C2H5OH
Eg:
O LiAlH4

CH3 – C – NH2 + 4H CH3CH2NH2 + H2O

Na / C2H5OH Ethanamine or
ethyl amine

iii) Hoffman’s degradation reaction (Hoffman’s bromamide reaction).

O
– C – NH2 – NH2 (primary amine) Degradation
  In this reaction, amides are treated with bromine water and aqueous solution of KOH
or NaOH to form primary amines which will have one carbon atom less than their
parent amides.
 As the reaction involves the decrease in the number of carbon atoms, it is also called
as Hoffman’s degradation reaction.
 This reaction is used to decrease the number of carbon atoms in the chain.

O
R – C – NH2 + Br2 + NaOH R – NH2 + Na2CO3 + 2NaBr + 2H2O
O
CH3 – C – NH2 + Br2 + NaOH CH3 – NH2 + Na2CO3 + 2NaBr + 2H2O
Methyl amine

O
CH3–CH2–C–NH2+Br2+NaOH CH3–CH2–NH2+ Na2CO3+2NaBr+2H2O
Ethyl amine

Significance of Amides

 Amides are used for the preparation of primary amines.

 Certain amides such as dimethyl-formamide (DMF) and dimethyl acetamide (DMA)
are used as solvents for polar and non-polar compounds.
 Amide is used as high temperature solvent.
 Amide is used as an intermediate in the degradation of ethyl amine (or ethyl alcohol)
to methyl amine (to methyl alcohol).
 Amide is used as a reagent for identifying acetic acid.