67

CHAPTER 3
ALIPHATIC COMPOUNDS II
Aim & Goal : Aliphatic compounds are open-chain or acyclic
compounds, and the name aliphatic arises from the fact that the first
compounds of this class to be studied were the fatty acids. The term aliphatic is
now reserved for any compound that has an open-chain structure. In this
chapter, reactions concerning carboxylic acid, amines and amides are
presented. The exercises given are required to make self-study and self-
assessment.
3.1 Carboxylic Acids (Monocarboxylic Acids)
Carboxylic acids are organic compounds containing carboxyl group
(-COOH). The functional group of a carboxylic acid is called carboxyl group.
Since the group contains a carbonyl ( C=O) and hydroxyl group (-OH), it is
called as a carboxyl group.

–COOH (or) –CO2H

a carboxyl group a carboxyl group 3 D view of acetic acid

(abbreviated forms)

The carbon atom of a carboxyl group is surrounded by three groups,

making it sp2 hybridized and trigonal planar, with bond angles 119°. In a
carboxylic acid, the bond length of C=O bond is shorter than that of C–O bond.
The acids are known as mono-, di-, tri-, or poly carboxylic acids
according to the number of carboxyl groups present in the molecule. The
molecular formula of monocarboxylic acid is C nH2nO2. In these compounds, the
carboxyl group can attach to hydrogen (H-COOH), or an alkyl group (R-
COOH), or an aryl group (Ar-COOH).

General formula: H-COOH (or) R-COOH Ar-COOH

Aliphatic carboxylic acids Aromatic carboxylic acids

Carboxylic acids with long, unbranched chains of carbon atoms are

called fatty acids because they are formed from fats by a hydrolysis reaction
called saponification. Examples of fatty acids are palmitic acid, stearic acid,
and oleic acid.
3.1.1 Sources of Carboxylic Acids
Many simple carboxylic acids are found in nature. Formic acid is found
in ants, bees, and other stinging insects; its name comes from formica, which is
 68

Latin word for “ant.” Acetic acid is the sour-tasting component of vinegar. The
name comes from Latin word acetum, meaning “vinegar.” Propionic acid is the
smallest acid that shows some of the characteristics of the larger fatty acids; its
name comes from the Greek words pro meaning “the first” and pion meaning
“fat”. Butyric acid is found in rancid butter; the Latin word for “butter” is
butyrum. Caproic acid is found in goat’s milk. Caper is the Latin word for
“goat.” Latic acid gives sour taste to milk.

3.1.2 Nomenclature
IUPAC Names
In IUPAC system, the longest chain carrying the carboxyl group is
considered as the parent structure, and is named by replacing the –e ending of
the corresponding alkane with -oic acid. When substituents are present, their
locations are indicated by numbers. Numbering of carbon chain always begins
at the carboxyl group. Carboxyl groups, like the aldehyde groups, are always at
the end of a chain, so the carboxyl carbon atom is always assigned number 1.
For example:

CH3CH=CHCOOH C6H5 CH2CH2COOH

2-Butenoic acid 2-Methylbutanoic acid 3-Phenylpropanoic acid

Common Names
Most simple carboxylic acids have the common names that are widely
used than their IUPAC names. Their common (trivial) names are often derived
from a Greek or Latin word that indicates the original source. The common
names are ended by the suffix -ic acid. Branched chain acids and substituted
acids are named as derivatives of the straight chain acids. To indicate the
position of substituents, the Greek letters, α-, β-, γ-, δ-, etc., are used. The
carbon adjacent to the carboxyl group is called the α-carbon. The α-carbon in
common system is numbered C-2 in the IUPAC system. The names and
structure of some monocarboxylic acid are shown in Table 3.1.

IUPAC system: Start numbering here

5 4 3 2 1

C-C-C-C-C-C-C-COOH

δ γ βα

Common system: Start lettering here

 69

Table 3.1 Names and Structures of Some Monocarboxylic Acids

Formula Common names IUPAC names
(suffix -ic acid) (suffix -oic acid)
HCOOH Formic acid Methanoic acid
CH3 COOH Acetic acid Ethanoic acid
CH3CH2 COOH Propionic acid Propanoic acid
CH3CH2CH2 COOH Butyric acid Butanoic acid
CH3 (CH2)3 COOH Valeric acid Pentanoic acid
CH3 (CH2)4 COOH Caproic acid Hexanoic acid
CH3 CH(OH) COOH Latic acid 2-Hydroxypropanoic acid
C6H5 COOH Benzoic acid Benzoic acid
CH3 (CH2)14 COOH Palmitic acid Hexadecanoic acid
CH3 (CH2)16 COOH Stearic acid Octadecanoic acid
The name of salt of a carboxylic acid consists of the name of the cation
(sodium, calcium, etc.) followed by the name of acid with the ending –ic acid
changed into –ate.
CH3COONa sodium acetate
HCOONH4 ammonium formate

3.1.3 Preparation of Carboxylic Acids

(1) Oxidation of Primary Alcohols
Carboxylic acids are obtained by the oxidation of primary (1º) alcohols
with a strong oxidizing agent such as potassium permanganate or chromic acid.
KMnO4 (or)
  
RCH2-OH K2Cr2O7, H2SO4 R-COOH
1° alcohol carboxylic acid

isobutyl alcohol isobutyric acid

(2) Oxidation of Aldehydes

Aldehydes can be oxidized to carboxylic acids with a number of
oxidizing agents.
 70

(3) Side-chain Oxidation of Alkyl Benzenes

Alkyl benzenes having at least one benzylic C-H bond can be oxidized
to benzoic acid. So the structure of alkyl benzenes must be Ar-CH 3 or Ar-CH2R
or Ar-CHR2.
KMnO4 (or)
Ar – R    Ar – COOH
K2Cr2O7, H2SO4
alkyl benzene benzoic acid
KMnO4 (or)
  
Cl CH3 K2Cr2O7, H2SO4 Cl COOH

p-chlorotoluene p-chlorobenzoic acid

(4) Hydrolysis of Nitriles (Alkyl / Aryl cyanides)

Carboxylic acids can be prepared by hydrolysis of nitriles with acid or
alkali. Nitriles are compounds containing a cyano group ( C N ). Notice that
the carboxylic acid produced in this two-step reaction has one more carbon
atom than the starting haloalkane.

R-X R- C N R-COOH + NH3

(or)Ar-X (or) Ar- C N acid or base (or) Ar-COOH
haloalkane nitrile carboxylic acid
(one more carbon atom)

C4H9–Br C4H9–CN C4H9–COO¯ + NH3

H+

n-butyl bromide n-valeronitrile n-C4H9–COOH + NH4+

n-valeric acid (or)
pentanoic acid

(5) Carboxylation of Grignard Reagents

Grignard reagents react with carbon dioxide to form carboxylate salts,
which on treatment with a strong aqueous acid solution. This reaction is called
a carboxylation reaction because a carboxylic acid functional group adds to an
organic compound. In this reaction carboxylic acid formed have one more
carbon atom than the starting haloalkane.

R-X M R-MgX CO2 RCOOMgX RCOOH

haloalkaneg grignard reagents carboxylic acid
(or Ar-X) (or Ar-COOH)
(one more carbon atom)
 71

2-chloro-2-methyl butane 2,2-dimethyl butanoic acid

3.1.4 Physical Properties of Carboxylic Acids

(1) Smell and state: The first three members are colourless, pungent
smelling liquids. The acids from C4 to C9 are colourless oily liquids smelling
like goat's butter, while the higher members are colourless and odourless waxy
solids.
(2) Solubility: The first four members are very soluble in water. The
solubility of higher members falls rapidly with increase in molecular weight.
Acids from C10 onward are insoluble in water. Fatty acids are readily soluble in
less polar solvents like alcohol, ether etc.
(3) Specific gravity: The specific gravity decreases gradually from 1.22
for formic acid to 0.85 for stearic acid. Only the first two members are heavier
than water.
(4) Volatility: The lower members are much less volatile than is to be
expected from their molecular weight. For example, n-pentane (mol. wt. 72)
boils at 36 °C while propionic acid (mol. wt. 72) boils at 141°C. This is due to
the formation of intermolecular hydrogen bonding that give dimers. Unlike
other acids formic acid shows an exceptional behavior. It exists as a dimer in
vapour state, but a polymer in liquid and solid state.

Intermolecular
hydrogen bonds

Carboxylic acid dimer

(5). Melting and boiling points: The melting points of normal fatty
acids show oscillation from one member to the next. The melting point of an
acid with even number of carbon atoms is higher than that of an acid with odd
number of carbon atoms preceding or following it. This is due to closer packing
of molecules in the solid state. The boiling point increases with increase in
molecular weight.
(6). Acid strength: The strength of an acid is expressed in terms of
dissociation constant (Ka) or more conveniently by the negative logarithm (pKa)
of dissociation constant (Ka). The larger the Ka value the greater is the strength
of an acid. The smaller pKa value indicates the stronger acid. Formic acid is the
strongest of all fatty acids.
 72

In aqueous solution a carboxylic acid exists in equilibrium with the

carboxylate anion and the hydronium ion.
RCOOH + H2O RCOO¯ + H3O+
At equilibrium, the concentrations of the components are related by the
following equilibrium expression.

Keq =

Ka = , pKa = – log Ka

Since the concentration of water remains constant, Keq × [H2O] = Ka.

This new constant, Ka, is called the acidity constant.
The pKa values of unsubstituted aliphatic carboxylic acids are in the
range of 4 to5. So they are stronger than alcohols (pKa ~ 16) but weaker than
mineral acids such as HCl (pKa ~ –7) or H2SO4 (pKa ~ –9).
The acidities (pKa values) of saturated aliphatic carboxylic acids are
increased by the presence of electron-withdrawing substituents on the α-carbon
atom. The acidity of acetic acid is greatly increased by replacing one or more
hydrogen atom by halogen atom or nitrile group. All the monohaloacetic acids
are about 100 times more acidic than acetic acid. Multiple halogen substitution
increases the acidity even more trichloroacetic acid is 7000 times more acidic
than acetic acid.
3.1.5 Chemical Properties of Carboxylic Acids
The characteristic chemical behavior of carboxylic acids is mainly due
to their functional group, carboxyl, -COOH group. This group is made up of
carbonyl group (C=O) and a hydroxyl group (-OH).
(A) Reactions due to Carboxyl Group
(1) Reactions Involving Proton
Like other acids, carboxylic acids undergo ionization into proton and the
acid anion but the degree of ionization is small as compared to that of inorganic
acids. Carboxylic acids react as Bronsted-Lowry acids, that is, as proton
donors.
RCOOH RCOO¯ + H+
Salt Formation
Carboxylic acids combine with strong electropositive metals, metal
oxides, carbonates, alkalis, and ammonia etc., to form salts.
2RCOOH + Zn (RCOO)2 Zn + H2
2RCOOH + ZnO (RCOO)2 Zn + H2O
2RCOOH + Na2CO3 2RCOONa + H2O + CO2
RCOOH + NaOH RCOONa + H2O

RCOOH + NH3 RCOONH4

 73

2 CH3COOH + Zn (CH3COO)2 Zn + H2
acetic acid zinc acetate
(2) Reactions Involving Hydroxyl Group
(a) Conversion into Acid Chlorides

C2H5COOH + SOCl2 reflux C2H5COCl + SO2 + HCl

propionic acid thionyl chloride propionyl chloride
50ºC
3CH3COOH + PCl3 3 CH3COCl + H3PO3
acetic acid acetyl chloride

C6H5COOH + PCl5 100ºC C6H5COCl + POCl3 + HCl

benzoic acid benzoyl chloride

(b) Conversion into Esters (Fischer Esterification)

In the presence of an acid catalyst, carboxylic acids and alcohols react
to form esters. This reaction is called the Fischer esterification. It is an
equilibrium process but can be driven to favor the ester by removing
the water that is formed.

carboxylic acid alcohol ester

Reactivity of alcohol (R'OH): 1º > 2º > 3º

acetic acid benzyl alcohol benzyl acetate

(c) Conversion into Amides

(d) Dehydration
Carboxylic acids yield acid anhydride when heated with a dehydrating
agent. (e.g., phosphorus pentoxide)
 74

P2O5
R-CO-OH + HO-OC-R   RCO-O-COR + H2O
carboxylic acid P2O5 acid anhydride
CH3-CO-OH + HO-OC-CH3   CH3-CO-O-CO-CH3 + H2O
acetic acid acetic acid acetic anhydride

(3) Reactions Involving Carbonyl Group

Reduction of Carboxylic Acids
Carboxylic acids are reduced to primary alcohols by the powerful reducing
agent, lithium aluminum hydride. In this reaction carbonyl group is reduced to
methyleneOgroup (-CH2-).
LiAlH4
R-C-OH RCH2OH

carboxylic
O
acid primary alcohol
LiAlH4
CH3-C-OH CH3CH2OH

acetic acid ethyl alcohol

(B) Reactions due to Alkyl group
α-Halogenation of Aliphatic Acids (Hell-Volhard-Zelinsky Reaction)

carboxylic acid α-halo carboxylic acid

CH3COOH ClCH2COOH Cl2CHCOOH Cl3C-COOH acetic

acid chloro dichloro trichloro
acetic acid acetic acid acetic acid

3.2 Functional Derivatives of Carboxylic Acids

Acid halides, acid anhydrides, esters, and amides are all called
functional derivatives of carboxylic acids because they are closely related to
carboxylic acid and to each other. These carboxylic acid derivatives are formed
by replacing the –OH of a carboxyl group by –Cl, –OCOR, –NH 2, or –OR'
group. They all contain the acyl group, (R–C=O). An acyl group is a carbonyl
group ( C=O) attached to an alkyl or aryl group.

carboxylic acid carboxylic acid derivatives

acid chloride acid anhydride ester amide

 75

Loss of water from two molecules of a carboxylic acid results in acid

anhydride. “Anhydride” means “without water”.

-H2O
+ an acid anhydride

3.3 Esters
Esters are compounds containing the –COOR functional group.General
formula: R-COOR´ where R and R´ may be the same or different. An ester
has an OR´ group in place of the OH group of a carboxylic acid. Esters are
substances obtained by the interaction of an alcohol with an acid; inorganic or
organic. Esters of inorganic acids are called as inorganic esters e.g., ethyl
nitrite, whereas, those of organic acids are known as organic esters eg., ethyl
acetate.

3 D view of an ester

3.3.1 Sources of Esters

of an ester
Many esters are widely distributed in nature in plants, fruits, flowers etc.
Many of the fragrance of flowers and fruits are due to esters. Volatile esters are
often used in the preparation of perfumes and artificial flavorings.(Table 3.2)

Table 3.2 Name and Characteristic Odour of Some Ester

Formula Name Odour

CH3COOCH2CH2CH(CH3)2 isoamyl acetate banana
CH3CH2CH2COOCH2CH3 ethyl butanoate mango
CH3CH2CH(CH3)COOCH3 methyl 2-methylbutanoate pineapple
CH3CH2CH2COO(CH2)4CH3 n-amyl butanoate apricot
CH3COO(CH2)7CH3 n-octyl acetate orange
CH3CH2CH2COOCH3 methy butanoate apple
C6H4(OH)(COOCH3) methyl salicylate oil of wintergreen
CH3COOCH2 C6H5 benzyl acetate jasmine
Fats and oils are naturally occurring mixtures of glycerol triesters. They
are esters of higher fatty acids such as stearic, palmitic, oleic acids etc. with
glycerol (CH2OH-CHOH-CH2OH). Fats are solids at room temperature; oils
are liquids. The long unbranched chain of carboxylic acids obtained from fats
and oils by hydrolysis are known as fatty acids.
Waxes are mixtures of esters made up of long-chain unbranched
alcohols and carboxylic acids that contain an even number of carbon atoms.
 76

Waxes generally contain a total of between 40 and 72 carbon atoms. Many of

the commercial products that we use to protect and beautify cars, floors, and
furniture are waxes. In nature, waxes are found on the surfaces of stems and
leaves of plants, where they protect the plant from loss of moisture and attack
by harmful insects.

3.3.2 Nomenclature
Esters are usually called by their common names. In naming an ester,
the name of the alkyl group (R) attached to the carboxyl oxygen is stated first,
followed by the name of the acid, with “ic acid” replaced by “ate.” Cyclic
esters are called lactones.(Table 3.3)

acyl group

Table 3.3 Common and IUPAC Name of Some Ester

Formula Common names IUPAC names
H-COOCH3 methyl formate methyl methanoate
CH3-COOCH3 methyl acetate methyl ethanoate
CH3-COOCH2CH3 ethyl acetate ethyl ethanoate
CH3CH2-COOCH3 methyl propionate methyl propanoate
CH3CH2-COOC6H5 phenyl propionate phenyl propanoate
C6H5-COOCH2CH3 ethyl benzoate ethyl benzoate

3.3.3 Preparation of Esters

(1) From Carboxylic Acids (Fischer Esterification)
In the presence of an acid catalyst, alcohols and carboxylic acids react to
form ester and water. This reaction is called the Fischer esterification.
O O
H2SO4
R-C-OH + R'-OH R-C-OR' + H2O
carboxylic acid alcohol ester
The ease of esterification of alcohols and carboxylic acids are as
follows:
1° alcohol > 2° alcohol > 3° alcohol
Normal chain carboxylic acid > branched chain carboxylic acid
O O
H2SO4
CH3-C-OH + C2H5-OH CH3-C-OC2H5 + H2O

acetic acid ethyl alcohol ethyl acetate

 77

(2) From Acid Chlorides

O O
pyridine
R-C-Cl + R'-OH R-C-OR' + HCl
acid chloride alcohol ester
O O
pyridine
CH3-C-Cl + C2H5-OH CH3-C-OC2H5 + HCl
acetyl chloride ethyl alcohol ethyl acetate
(3) From Acid Anhydrides
O O O O
pyridine
R-C O-CR + R'OH R-C-OR' + R-C-OH

acid anhydride alcohol ester

O O O O
pyridine
CH3 -C-O- C-CH3 + C2H5-OH CH3-C-OC2 H5 + CH3-C-OH

acetic an hydride ethyl alcohol ethyl acetate acetic acid

3.3.4 Physical Properties of Esters

1. Smell and state: Esters are colourless liquids or solids with fruity or
flowery odour. Most simple esters are pleasant smelling substances. They are
responsible for the flavor and fragrance of most fruits and flowers. Many of the
artificial fruit flavor are used in cakes, candies and ice cream. The
characteristic odours of many fruits are due to low molecular weight esters.
2. Solubility: The esters of low molecular weight are fairly soluble in
water, but solubility rapidly decreases with increasing molecular weight. All
esters are soluble in most organic solvents such as benzene, ether etc. Esters of
low molecular weight are excellent solvents for non-polar compounds. Ethyl
acetate is an excellent solvent.
3. Melting and boiling points: Esters are moderately polar, with dipole
moments 1.5 to 2.0 D. Dipole-dipole attractive forces give esters higher boiling
points than hydrocarbons of similar shape and molecular weight. However,
ester molecules cannot form hydrogen bonds to each other because they lack
hydroxyl groups. Consequently, esters have lower melting and boiling points
than alcohols or carboxylic acids of comparable molecular weight. The boiling
points of normal-chain esters are higher than those of branched-chain isomers.
CH3 OH
CH3CHCH2CH3 CH3CHCH2CH3
2-Methyl butane Methyl acetate 2-Butanol
mol wt. 72, bp. 28C mol wt. 74, bp. 57C mol wt. 74, bp. 99C
 78

3.3.5 Chemical Properties of Esters

(1) Hydrolysis of Esters
With boiling water esters undergo slow hydrolysis into alcohol and acid.
However, in the presence of acids or alkalis hydrolysis takes place more
readily. Acid hydrolysis is reversible, so it is slower than alkaline hydrolysis,
which is irreversible.
(a) Acid Hydrolysis of Esters
The hydrolysis of esters in dilute aqueous acid is the reverse of the
Fischer esterification.
O O
H2SO4
R-C-OR' + H2O R-C-OH + R'OH
ester carboxylic acid alcohol
O O
H2SO4
CH3-C-OCH2CH3 + H2 O CH3-C-OH + CH3CH2OH

ethyl acetate acetic acid ethyl alcohol

(b) Alkaline Hydrolysis of Esters (Saponification)

During alkaline hydrolysis sodium or potassium salts of the acids are
obtained. Since alkali salts of higher fatty acids (stearic, palmitic acid etc.) are
soaps, alkaline hydrolysis of esters is called saponification which means “soap
making”.
O O
H2O
R-C-OR' + NaOH R-C-ONa + R'OH

ester sodium carboxylate

O O
H2O
CH3-C-OC2H+5 + NaOH CH3-C-ONa + C2H5OH

ethyl acetate sodium acetate

(2) Reaction with Ammonia and Amines
Esters react with ammonia and amines to form 1°, 2°, or 3° amides.
Methyl and ethyl esters are the most reactive.
O O
R-C-OR' + NH3 R-C-NH2 + R'OH

Ester ammonia 1° amide

 79

O O
CH3-C-OC2H5 + NH3 CH3-C-NH2 + C2H5OH
ethyl acetate acetamide ethyl alcohol
(3) Alcoholysis of an Esters
When an ester is refluxed with excess amount of alcohol in the presence
of a little acid or sodium alkoxide as a catalyst, a partial change of alcohol
residue takes place. This splitting of ester by alcohol is the trans-esterification.
O O
acid
R-C-OR' + R''OH R-C-OR'' + R'OH
or base

ester alcohol
O O
H2SO4
CH3-C-OH + C2H5-OH CH3-C-OC2H5 + H2O

acetic acid ethyl alcohol ethyl acetate

(4) Reduction with Lithium Aluminium Hydride
Lithium aluminium hydride cleaves esters to yield two different
alcohols. O
1. LiAlH4
R-C-OR' 2. H2O
RCH2OH + R'OH
ester 1° alcohol alcohol
COOCH3 CH2OH
1. LiAlH4
2. H2O + CH3OH

methyl benzoate benzyl alcohol methanol

(5) Reduction with Hydrogen (Adkin’s Method)
Hydrogen gas at 100-300 atmospheres and in the presence of copper
chromate at 200-300°C reduces an ester to alcohols. This method is known as
Adkin’s method. O
Cu-chromite
R-C-OR' + 2H2 RCH2OH + R'OH
100-300 atm
ester 200-300 C alcohol

3.4 Amides
Amides are classified as 1°, 2°, or 3° depending on the number of
carbon atoms directly bonded to the nitrogen atom.
 80

General formula:

1° Amides 2° Amides 3° Amides 3D view of an amide

3.4.1 Nomenclature
All 1° amides are named by replacing the –ic acid of common name or
–oic acid of IUPAC name with the suffix –amide. e.g.,

CH3-CO-NH2 (derived from acetic acid) acetamide

C6H5-CO-NH2 (derived from benzoic acid) benzamide

Naming 2° and 3° amides requires two parts:

(1) Name the alkyl group (or groups) bonded to the N atom of the amide.
Use the prefix "N" preceding the name of each alkyl group to show that it is
bonded to a nitrogen atom. This becomes the first part of the name.

(2) For 3º amides, use the prefix di- if the two alkyl groups on N are the
same. If the two alkyl groups are different, alphabetize their names. One "N-" is
needed for each alkyl group, even if both R groups are identical.

(3) Name the acyl group (R–C=O) derived from carboxylic acid by
replacing the –ic acid or –oic acid ending by the suffix –amide. e.g.,
H-CO-NHCH2CH3 (derived from formic acid) N-ethylformamide
C6H5-CO-N(CH3)2 (derived from benzoic acid) N,N-dimethylbenzamide

3.4.2 Preparation of Amides

The direct conversion of a carboxylic acid to amide with ammonia or
amine is very difficult. This is because carboxylic acids are strong organic
acids and ammonia and amines are bases, so they undergo acid-base reactions
to form ammonium salt before any substitution occurs. In the laboratory amides
are prepared by the reaction of ammonia with acid chlorides or acid
anhydrides.
Preparation from Acid Anhydride
 81

3.4.3 Physical Properties of Amides

1. Melting and boiling points: Intermolecular forces, especially hydrogen
bonding, are considered when comparing the boiling points of compounds. For
example, there is strong hydrogen bonding in acetamide. So it has higher
boiling point than the compounds of nearly the same molecular weight, 2-
methyl propene and acetone which have no hydrogen bonding.
The number of substituents on nitrogen determines how many hydrogen
bonds are possible. For example, N,N-dimethylacetamide lacks N-H bonds and
so it has lower melting and boiling points than N-methylacetamide with one
N-H bond. Then N-methylacetamide has lower melting and boiling points than
acetamide with two N-H bond.
2. Acidity of amides: Because nitrogen is less electronegative than oxygen,
the N-H group of an amide is a weaker acid than the O-H of a carboxylic acid.

3.4.4 Chemical Properties of Amides

(1) Hydrolysis of Amides
Amides are hydrolyzed in acid or base to form carboxylic acids or
carboxylate anions.
O O
H+
R-C-NR'2 + H2O R-C-OH + R'2NH2
(R = H or alkyl) carboxylic acid

amide carboxylate anion

In acid, the by-product amine is protonated as an ammonium ion,

whereas in base, a neutral amine is formed.

O O
H+
CH3-C-NH2 + H2O CH3-C-OH + NH4

acetamide acetic acid

O O
OH-
CH3-C-NH2 + H2O CH3-C-O- + NH3

acetamide acetate
 82

(2) Hoffmann Degradation of Amides

Hoffmann degradation of amides yield amines containing one less
carbon atom than the starting material.
KOBr
R-CO-NH2 
 R-NH2 + CO32–
amide 1° amine
(one less carbon atom)
KOBr
CH3(CH2)4CONH2 
 CH3(CH2)4NH2
hexamide n-pentyl amine

3.5 Amines (Monoamines)

Introduction
Amines are organic nitrogen compounds, formed by replacing one, two
or all three hydrogen atoms of ammonia (NH 3) with alkyl (R-) or aryl (Ar-)
groups. Amines are classified as primary (1°), secondary (2°) or tertiary (3°),
according to the number of groups attached to the nitrogen atom.
General formula: R N H R N H R N R''
H R' R'

1° amine 2° amine 3°amine

Quarternary ammonium compounds may be considered as tetra-alkyl
derivatives of ammonium salts obtained by the replacement of all four
hydrogen atoms by alkyl groups. e.g., (CH3)4N+Cl-
3.5.1 Structure and Bonding
An amine nitrogen atom is surrounded by three atoms and one
nonbonded electron pair, making this N atom sp3 hybridized and trigonal
pyramidal, with bond angles of approximately 109.5°. Because nitrogen is
much more electronegative than carbon or hydrogen, the C-N and N-H bonds
are all polar.
Ammonium ion (NH4+), which is the conjugate acid of ammonia, also
forms organic derivatives. One, two, three, or all four hydrogen atoms of the
ammonium ion can be replaced by any combination of alkyl or aryl groups.
Compounds in which all four hydrogen atoms of the ammonium ion are
replaced with organic groups are called quaternary ammonium salts. The
nitrogen atom of all substituted ammonium ions carries a positive charge.

3.5.2 Sources of Amines

A great many simple and complex amines occur in nature. Naturally
occurring amines found in plants are called alkaloids. Caffeine is a bitter
alkaloid found in coffee, tea, cola beverages, and chocolate. The antimalarial
drug quinine is another medicinally useful alkaloid found in the bark of
Cinchona tree. Nicotine is highly toxic alkaloid isolated from tobacco. Other
 83

alkaloids, morphine and codeine extracted from the poppy were found to
relieve pain.
Other physiologically active amines can be found in humans and other
animals. These compounds are not classified as alkaloids because they are not
isolated from plants. Serotonin stimulates the contraction of smooth nucleus
and causes vasoconstriction. Histamines is released from body tissue in allergic
reaction.
Aromatic amines are generally very toxic; they are readily absorbed
through the skin, often with fatal results.

3.5.3 Nomenclature
Common names are obtained by citing the names of the alkyl
substituents attached to nitrogen (in alphabetical order) and following these by
the suffix –amine. The name of amine is written in one word.
In IUPAC name, primary amines can be named by finding the longest
continuous carbon chain bonded to the nitrogen atom (as the parent amine
chain) and changing the –e ending of the parent alkane to the suffix –amine.
Then usual rules are used for numbering the chain and naming the substituent.
Symmetrical secondary and tertiary amines are named by adding the prefix di-
or tri- to the name of the alkyl group. Unsymmetrically substituted secondary
or tertiary amines are named as N-substituted primary amines using the
following procedure. The use of letter N indicates that the alkyl groups are
attached to the nitrogen atom and not the carbon atom of the parent alkyl chain.
The names of the alkyl groups bonded to the nitrogen atom are listed
alphabetically.
Aromatic amines in which nitrogen is attached directly to an aromatic
ring are generally named as derivatives of aniline, the simplest aromatic amine.
(Table 3.4)

Table 3.4 Common and IUPAC Name of Some Amines

Formula (type of amine) Common names IUPAC names
(alkyl amine) (alkane alkan amine)
CH3NH2 (1°) methylamine methanamine
(CH3)2NH (2º) dimethylamine
(CH3)3N (3º) trimethylamine
C2H5-NH-CH3 (2º) ethylmethylamine N-methylethanamine
CH3
CH3CH-NH-CH3 (2º) methylisopropylamine N-methyl-2-propanamine
CH3
CH3CHCH2CH2CH2NH2 (1°) 4-methyl-1-pentanamine
CH3
CH3CH2CH2-N-CH2CH3(3º) ethylmethylpropylamine N-ethyl-N-methyl-1-
propanamine
NH2 (1°) aniline
 84

NH-CH2CH3 (2º) N-ethylaniline

N-(CH3)2 (3º) N,N-dimethylaniline

3.5.4 Preparation of Amines

(1) Reduction of Nitro Compounds
Aliphatic or aromatic nitro compounds can be reduced to primary
amines by using metal/H+ (or) H2/catalyst.
R–NO2 (or) Ar–NO2 R– NH2 (or) Ar–NH2
nitro compound 1º amine
Fe, HCl
CH3CH2CH2-NO2 
 CH3CH2CH2-NH2
(or) H2, Pt
1-nitropropane n-propylamine
(2) Reaction of Halides with Ammonia or Amines (Ammonolysis of
Halides)
Many organic halogen compounds are converted into amines by
treatment with aqueous or alcoholic solutions of ammonia.

NH3 R–NH2 R 2N R3N

1º amine 2º amine 3º amine quaternary
ammonium
salt
C2H5Cl NH3
 C2H5-NH2 CH3Cl

  C2H5-NH-CH3
ethyl chloride ethylamine (1º) ethylmethylamine (2º)
(3) Reductive Amination
The catalytic chemical reduction of aldehydes and ketones in the
presence of ammonia or an amine will give any class of amine.

acetone iso-propylamine (1º)

CH3CHO + (CH3)2NH + H2 CH3CH2-N(CH3)2
acetaldehyde dimethylamine (2º) dimethylethylamine (3º)

(4) Reduction of Nitriles

 85

Synthesis via reduction of nitrile has the special feature of increasing the
length of a carbon chain, producing a primary amine that has one more carbon
atom than the alkyl halides from which the nitrile was made.
RX RCR-NN N: RCH-NH2
alkyl halide nitrile 1º amine (one more carbon)
CH3 Br CH3-CR-N
N N: CH3CH2NH2
methyl bromide methyl cyanide ethylamine (1º)
(5) Hoffmann Degradation of Amides
As a method of synthesis of amines the Hoffmann degradation of
amides has the special feature of yielding a product containing one less carbon
atom than the starting material.

R-CO-NH2 R-NH2 + CO32–

amide 1° amine (one less carbon atom)
CH3(CH2)4 -CONH2 CH3(CH2)4NH2
hexa amide n-pentylamine
3.5.5 Physical Properties
(1) Smell and state: Amines are unpleasant smelling compounds.
Lower molecular weight amines smell much like ammonia, while higher
molecular weight amines have a distinct fishy odour. Lower members are
combustible gases at ordinary temperature; the members from C 3 to C11 are
volatile liquids, while higher members are solids.
(2) Solubility: Amines of three classes are capable forming
hydrogen bonds with water. As a result, the lower members (amines containing
5 or fewer carbon atoms) are quite soluble in water. But the solubility decreases
with increase in molecular weight because the nonpolar alkyl portion is too
large to dissolve in the polar water solvent. Amines are soluble in less polar
solvents like ether, alcohol, benzene, etc.
(3) Melting and boiling points: Amines have higher boiling points than
non-polar compounds (alkanes, ethers, haloalkanes) of the same molecular
weight. This is because amines are polar compounds and they exhibit dipole-
dipole interactions due to the presence of the polar C-N and N-H bonds.
Besides that, primary and secondary amines, except for tertiary amines, can
form intermolecular hydrogen bonding due to the presence of N-H bonds.
Amines have lower boiling point than alcohols or carboxylic acids.
Because nitrogen is less electronegative than oxygen, intermolecular hydrogen
bonds between N and H in amines are weaker than those between O and H in
alcohols. Thus amines have lower boiling points than alcohols.
The boiling points of amines of the same molecular weight decrease in
the order 1° > 2° > 3° amines. This is because 1° and 2° amines can form
intermolecular hydrogen bonding while 3°amines cannot.
(4) Basicity: The basic character of amines is due to the presence of a
lone pair of electrons on nitrogen atom. Amines are more basic than most other
 86

organic compounds such as alcohols, ethers, or water. Thus amines can form
salts with acids such as HCl.
Like ammonia, amines are converted into their salts by aqueous mineral
acids.The basic strength of an amine can be measured by basicity constant Kb.
The larger the value of Kb (the smaller the value of pKb), the stronger is the
base. When an amine is dissolved in water, equilibrium is established.
For the reaction:
RNH2 + H2O RNH3+ + OH¯

Kb = , pKb = – log Kb

The basicity of amines is related to structure. Any factor that increases

the electron density on the N atom increases the basicity of an amine. An
electron donating group pushes electrons towards nitrogen and makes the
nitrogen available for sharing with an acid. Any factor that decreases the
electron density on the N atom decreases the basicity of an amine. An electron
withdrawing group pulls electrons away from nitrogen and thus makes the
nitrogen available for sharing with an acid. Aliphatic amines are more basic
than NH3 because of the electron donating effect of the alkyl group. Aromatic
amines are weaker base than ammonia because of the electron withdrawing
effect of the aryl group.

3.5.6 Reaction of Amines

(1) Salt Formation
Amines have the basic properties and they combine with acids to give
salts.
RNH2 +
R2NH +
R3N +

dimethylamine dimethyl ammonium nitrate

(2) Reaction with Alkyl Halides (Alkylation)

All amines react with alkyl halides. Amines of the next higher class are
formed and finally quaternary ammonium salts are produced. Quaternary
ammonium salts have the formula, R4N+X- .

1º amine 2º amine 3º amine quaternary ammonium salt

 87

n-propylamine methyl- dimethyl- trimethyl

n-propylamine n-propylamine n-propylammonium
(1º) (2º) (3º) iodide (4º)

(3) Reaction with Acid Chloride (Acylation)

The 1º and 2º amines can react with acid chlorides to form substituted
amides.

(1º amine) R-NH2 R'CONHR (N-substituted amide)

(2º amine) R2-NH R'CONR2 (N,N-disubstituted amide)
(3º amine) R3-N no reaction
CH3-NH2 + CH3CO-Cl CH3CONHCH3 + HCl
methylamine N-methylacetamide

(4) Hofmann Elimination

The Hofmann elimination converts an amine into an amide.

CH3 CH Ag O AgAgO O

2Ag2OAg22O2 Ag2O
CH3-CH-CH 3CH
CH
CHI3 3-CH-CH
3CH
2excess CH
3 CHCHCH3-CH-CH
3-CH-CH
32-CH-CH
3-CH-CH
CH
22 223  CHCH -CH-CH
3CH
CH
CH33-CH-CH
CH
-CH-CH 222 
32-CH-CH
3-CH-CH
3-CH-CH 2 2

CH 
3-CH CH3CH
CH 3-CH
-CH
2
CHCH
CH CH
-CH
-CH CH2
2 2 CH
33-CH-CH 2 2 C
excessexcessexcess
excess HHN(CH
N(CH
excess )2 H N(CH )
H N(CHH )N(CH) ) H N(CH
H )
N(CH )
H NH2 H N(CH 3
3 2 3 2 2 )33 2 HH N(CH
H
N(CH )
3 2N(CH
3 ) 2 )
3 2
33 22 3 2 + H O
2
H N(CH 3) 2

I¯ ¯OH +N(CH3)3
+ AgI
Propylamine quaternary ammonium salts

(5) Reaction with Nitrous Acid

Nitrous acid, HNO2, unstable acid formed from NaNO2 and a strong acid
like HCl, reacts with 1º alkylamine or arylamine to form diazonium salts
(RN2+Cl-). This reaction is called diazotization.
NaNO
R-NH2 
 
HCl
2 R-N N: Cl¯
1º amine alkyl diazonium salt
NaNO
NH2 Cl¯ 
 
HCl
2
N = N:Cl¯

aniline aryl diazonium salt

Separation of Mixture of Amines

The mixture of 1º, 2º and 3º amines along with the quaternary
ammonium salt is distilled with potassium hydroxide, when amines distil over
leaving behind the non-volatile quaternary salt. The mixture of amines (1º, 2º
and 3º), obtained as distillate, is separated by Hinsberg's method.
 88

Hinsberg's Method
The mixture of 1º, 2º and 3º amines is treated with benzene sulphonyl
chloride and shaken with 5 % potassium hydroxide solution. A 1º amine yields
a clear solution, from which, upon acidification, an insoluble material
separates. A 2º amine yields an insoluble compound, which is unaffected by
acid. A 3º amine does not react with Hinsberg's reagent (benzene sulphonyl
chloride) and so remains as an unreacted insoluble amine, which dissolves
upon acidification of the mixture.

Notes:1º, 2º and 3º amines can also be distinguished by using Hinsberg's

method.
 89

Exercises
1. Give an acceptable IUPAC name for each of the following carboxylic acids.
(a) (CH3)2CHCH2CH2COOH (c) H2C=CH(CH2)5COOH
(b) CH3CH2 COOH (d) COOH
Cl
2. Give the structural formula and IUPAC name for each of the following
compounds.
(a) calcium propionate (d) p-hydroxybenzoic acid
(b) isovaleric acid (e) α,β-dimethylcaproic acid
(c) trimethyl acetic acid (f) isopropyl 3-methylbutanoate
3. Arrange each of the following compounds in order of increasing acidity.
(a) acetic acid, ethanol, formic acid
(b) benzene, benzoic acid, benzyl alcohol
(c) sulfuric acid, 1-butyne, butanoic acid
4. Which acid of each pair shown here would you expect to be stronger?

5. Which carboxylic acid would you expect to be stronger, A or B?

COOH COOH
or
O2N
A B
6. Starting from acetic acid how would you prepare each of the following
compounds?
(a) acetyl chloride (b) acetamide (c) acetic anhydride (d) ethyl alcohol
7. What ester is formed when propanoic acid (CH 3CH2COOH) is treated with
methanol (CH3OH) in the presence of H2SO4?
8. What products are formed when ethyl propanoate (CH3CH2CO2CH2CH3) is
hydrolyzed with water in the presence of H2SO4?
9. Write equations for the reactions that would prepare the following carboxylic
acids from the starting materials indicated.
(a) 3-methylbutanoic acid from an alcohol
(b) 2-methylbutanoic acid from 2-chlorobutane
(c) pentanoic acid from an aldehyde
10. Propose methods for preparing butanoic acid from each of the following
compounds:
(a) 1-butanol (b) butanal (c) 1-propanol (d) 2-propanol
 90

11. Show how butanoic acid may be converted to each of the following
compounds:
(a) butanoyl chloride (b) 1-butanol (c) 2-bromobutanoic acid
12. Methyl salicylate is the major component of the oil of wintergreen. What
carboxylic acid and alcohol are needed to synthesize methyl salicylate by
Fischer esterification?
COOCH3
Methyl salicylate
OH
13. Identify A and B in the following two-step sequence that synthesizes benzyl
benzoate from benzyl alcohol. Benzyl benzoate is a component of jasmine
oil.
CH2OH A COOH B CO2CH2
benzyl alcohol benzyl benzoate
14.Write equations for the reaction of propanoic acid with each of the
following reagents:
(a) KOH / H2O (b) 1-Propanol / acid catalyst (c) LiAlH4
15. Give the structure corresponding to each name.
(a) propionic anhydride (d) α-chlorobutyryl chloride
(b) isopropyl formate (e) cyclohexyl propanoate
(c) vinyl acetate (f) N-cyclopentylpentanamide
16.Draw structures and give names of nine isomeric esters of formula C5H10O2.
17. Explain the boiling point of CH3-CO-NH2 (221° C) is significantly higher
than the boiling point of CH3-CO-N(CH3)2 (166° C) , even though the later
compound has a higher molecular weight and more surface area.
18. Amide is less acidic than carboxylic acid. Explain why.
19.What reagents would you use to convert methyl propanoate into the
following compounds?
(a) iso-propyl propanoate (c) N-ethylpropanamide
(b) propanoic acid (d) sodium propanoate
20.What product would be obtained when ethyl butanoate is treated with each
of the following reagent? With some reagents, no reaction occurs.
(a) SOCl2 (b) H3O+ (c) H2O, ¯OH (d) NH3 (e) CH3CH2-NH2
21. How would you prepare acetamide from (a) acetic anhydride (b) ethyl
acetate?
22. Write an equation for the preparation of the following amides from the
indicated carboxylic acid derivatives:
O
CH -C-NH2
3
(a) (CH3)2 CH from an acid chloride
 91
O
CH3-C-NH-CH3
(b) from an acid anhydride
O
CH -C-NH2
3
(c) H (CH3)2 from a methyl ester
23. Draw the products formed when phenylacetamide (C6H5CH2-CO-NH2) is
treated with each reagent. (a) H3O+ (b) H2O, ¯OH
24. Draw a structure corresponding to each name.
(a) sec-butylamine (c) diphenylamine
(b) N-methylpentylamine (d) N,N-dimethylethanamine
25.How many isomers of amines are known for the molecular formula C 3H9N?
Write their structural formulae and name them. Classify these isomers as
primary, secondary or tertiary amines.
26. Draw structures, give names, and classify as primary, secondary, or tertiary:
(a) the eight isomeric amines of formula C4H11N
(b) the five isomeric amines of formula C7H9N that contain a benzene ring
27. How is methylamine prepared from (a) methyl alcohol (b) formaldehyde
(c) acetamide?
28. What are quarternary ammonium compounds? Give example.
29. Show how n-propylamine could be prepared from each of the following:
(a) n-propyl bromide (c) propionaldehyde
(b) n-butyramide (d) 1-nitro propane
30. Describe the one general method for the preparation of primary, secondary
and tertiary amines.
31. How would you prepare 1-pentanamine from each of the following starting
materials and any other organic or inorganic reagents needed?
(a) 1-bromopentane (b) pentanamide (c) pentanal
32. How would you prepare benzylamine from each of the following
compound?
(a) C6H5 CH2 Br (b) C6H5 CONH2
33. How would you convert CH3CH2 CH2 CH2NH2 into each of the following
compounds?
(a) CH3 (CH2)3NH CH2 C6H5 (c) [CH3 (CH2)3N(CH2)3 ]+I-
(b) CH3 CH2 CH= CH2 (d) CH3 (CH2)3NH CO C6H5
34. What products are formed when N-ethylaniline C6H5 NH CH2 CH3 is treated
with each reagents?
(a) HCl (c) CH3I (excess) (e)CH3CH2COCl
(b) NaNO2 and HCl (d) CH3I (excess), followed by Ag2O and heat
35. How will you distinguish between a primary, secondary, and tertiary
amine?
36. How will you separate primary, secondary, and tertiary amines from their
mixture by Hinsberg's method?
37. Arrange the following sets of compounds in order of increasing basicity.
(a) aniline, ammonia, methylamine (b) aniline, ammonia, cyclohexylamine
(c) acetic acid, ethylamine, aniline (d) acetic acid, aniline, p-nitroaniline
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 92

Prescribed Text
Whitten, K.W., Davis, R.E., Peck, M. L. and Stanley, G. G., (2010),
"Chemistry", 9th Ed., Brooks/Cole, Cengage Learning, Canada.

Reference Text
Bruice, P. Y., (2004), “Organic Chemistry”, 4th Ed., Prentice Hall, Inc., A
Simon & Schuster Company, New Jersey.
Morrison, R., T., and Boyd, R., N., 1992, “Organic Chemistry”, 6 th Ed.,
Prentice Hall, Inc., A Simon & Schuster Company, New Jersey.
Tewari, K. S., Vishloi, N. K., Mehrotra, S. N., 1998, A Textbook of Organic
Chemistry, 2nd Revised Edition, Vikas Publishing House PVT LTD.,
New Delhi.

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