Chapter 19 : Amines 19.1 : Introduction 19.

2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.1 Introduction
Amines are organic derivatives of
ammonia, NH3

Classification of Amines
Primary amines H N H

Secondary amines H N R'

Tertiary amines R'' N R'

R
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.1 Classify the following amines:

i. CH3CH2CH2NH2 1°
ii. CH3CH2 N H
2° Aliphatic amines
CH3
iii. CH3CH2 N CH3
3°
CH3
iv. N CH3
2°
H
v. NH2 1° Aromatic amines
vi. N CH3
3°
CH2CH3
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2 IUPAC Nomenclature

In primary amines, the suffix ‘amine’
replaces the ‘e’ in the name of the parent
alkane
i. CH3CH2CH2NH2 propaneamine
e
3 2 1

Secondary and tertiary amines are named

as N-substituted derivatives of primary
amines
2°
ii. CH3CH2 N H
2 1 N-methylethanea
emine
CH3
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2 Examples:
Structure IUPAC Name
CH3NH2 Methanamine
CH3CH(NH2)CH3 2-propanamine
NH2
Cyclopentanamine

CH3CH2CHCH2CH3 N-methylpentanamine
NHCH3

CH3 N-ethyl-N-methyl
CH3CH2 N CH2CH3
ethanamine
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2 IUPAC Nomenclature

When multiple functional groups are
present and the –NH2 group does not
take priority, it is named as an “amino”
substituent
Examples:
NH2CH2COOH 2-aminoethanoic acid
2 1

H 2N 4
1 OH
3 2 2,4-diaminophenol
NH2
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2 IUPAC Nomenclature

Aromatic amines are named as
derivatives of aniline

N-ethyl-N-methylaniline
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.2 Common Name

Most primary amines are named as
alkylamines

Structure IUPAC Name

CH3NH2 methylamine
CH3CH2NH2 ethylamine
CH3CH2CH2NH2 propylamine
CH3NHCH3 dimethylamine
CH3NHCH2CH3 methylethylamine
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 (i) Boiling Point

Boiling point Both primary and secondary amines
can form intermolecular hydrogen
Solubility bonds.
CH3 CH3
Basicity H HCH3
CH3
CH3N NCH H N CH3
CH3 N H CH3 NN CH
CH3
3
3
CH3 H
H
no hydrogen bond
hydrogen bonds hydrogen bonds

1° amines 3° amines 2° amines

Tertiary amines cannot form hydrogen
bonds to each other.
Examples:
The table below compares the boiling points of isomeric
amines.
Amines Class Relative Boliling
molecular points/oC
mass
CH3CH2CH2NH2 1° 59 49
CH3CH2-NH-CH3 2° 59 37
CH3 3° 59 4
|
CH3-N-CH3

Boiling Point : CH3CH2CH2NH2 > CH3CH2NH(CH3) > (CH3)3N

 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 (i) Boiling Point

Boiling point Amines have higher boiling points than
alkanes or haloalkanes of similar relative
Solubility molecular mass due to intermolecular
hydrogen bonding Example
Basicity
Amines have lower boiling points than
alcohols or carboxylic acids of
comparable molecular weight because
H- bond in RNH2 is weaker than the
H- bond in ROH and RCOOH
(Nitrogen is less electronegative than the
Oxygen)
Examples: The table below compares the boiling points of organic
compounds of comparable relative molecular mass.
Amines Type Relative Boliling
molecular mass points/oC
CH3CH2CH2CH3 Alkane 58 -0.5
butane
CH3CH2Cl Haloalkane 64.5 12.5
chloroethane
CH3CH2CH2NH2 Amine 59 48.6
1-propanamine
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 (i) Boiling Point

Boiling point Amines have higher boiling points than
alkanes or haloalkanes of similar relative
Solubility molecular mass due to intermolecular
hydrogen bonding Example
Basicity
Amines have lower boiling points than
alcohols or carboxylic acids of
comparable molecular weight because
H- bond in RNH2 is weaker than the
H- bond in ROH and RCOOH
(Nitrogen is less electronegative than the
Oxygen) Example
Examples: The table below compares the boiling points of organic
compounds of comparable relative molecular mass.
Amines Type Relative Boiling
molecular mass points/oC
CH3CH2CH2CH3 Alkane 58 -0.5
butane
CH3CH2Cl Haloalkane 64.5 12.5
chloroethane
CH3CH2CH2NH2
CH3CH2CH2NH2 Amine 59 48.6
1-propanamine
1-propanamine
CH3CH2CH2OH Alcohol 60 97.2
1-propanol
CH3COOH Carboxylic 60 118
ethanoic acid acid

Boiling Point : Carboxylic acid > Alcohol > Amine >

Haloalkane > Alkane
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 (ii) Solubility

Boiling point All amines including tertiary amines,
are capable of forming hydrogen
Solubility bonds with water molecules. Thus
Basicity simple amines (amines of fewer than
5 carbons) are generally water
soluble and dissolve to form basic
aqueous solutions
 Comparison the solubility between 1°,2° and 3°amine
R N
TheHsolubilityR : N3°H< 2 ° < 1R° N R
H R R
o
1 Increasing2osolubility 3o
O H O H
O H
H H
H
R N H O H R N H O H
H H R H R N R
O H R
H : hydrogen bonds
3 hydrogen bonds 2 hydrogen bonds 1 hydrogen bond
per a 1° amine per a 2° amine per a 3° amine
molecule molecule molecule
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Basicity
 An amine is a nucleophile (a Lewis base)
base
Boiling point
because its lone pair of non-bonding
Solubility electrons on nitrogen
H H
Basicity + -
H N + H OH H N H + OH

H H
Ammonia Ammonium ion
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Basicity – (i) Inductive effect

 An alkyl group is electron donating
Boiling point group, and it stabilises the
Solubility alkylammonium ion by dispersing its
positive charge
Basicity H H
+ -
R N + H OH R N H + OH

H H
1° Amine alkylammonium ion
Stabilised by the
alkyl group Stronger base
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 H H
+ -
R N + H OH R N H + OH
Boiling point
H H
Solubility
1° Amine alkylammonium ion
Basicity R R
+
R N + H OH R N H + OH

H H
2° Amine alkylammonium ion

Strength as a base : Methyl, 1°, 2°

Increasing
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Basicity – (ii) Resonance effect

 Aromatic amines (e.g., aniline) are
Boiling point
weaker bases than the corresponding
Solubility aliphatic and cyclic amines

Basicity Example:
NH2 NH2

Cyclohexylamine Aniline
pKb = 3.36 pKb = 9.42
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.3 Basicity – (ii) Resonance effect

Aromatic amines are less basic
Boiling point The lone pair electrons of nitrogen atom
are delocalised and overlapped with the
Solubility
aromatic ring π electrons system make it
Basicity less available for bonding to H+
NH2
NH2 NH2 NH2

arylamines are stabilised due to the 4

resonance structures
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 Reduction of nitro compounds

Reduction of  Aromatic amines can be prepared by
nitro compound reduction of nitro compounds using
Zn/H+ or SnCl2/H+
Reduction of
nitriles
Zn/H+ or
Reduction of NO2 NH2
amides SnCl2/H+
nitrobenzene Aniline
anline
Hoffmann’s
degradation of
amides
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 Reduction of nitriles

Reduction of  Nitriles are reduced to primary amines
nitro compound by H2 / catalyst, LiAlH4 / H+ or
NaBH4 / H+.
Reduction of
H2
nitriles R C N RCH2NH2
catalyst (Pt, Ni, Pd)
Reduction of
amides Example :
Hoffmann’s OH 1. LiAlH 4 OH
degradation of
+
amides CN 2. H CH2NH2
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 Reduction of amides

Reduction of  Reduction of an amide using LiAlH4 / H+
nitro compound or NaBH4 / H+ can yield a primary,
secondary, or tertiary amine
Reduction of depending on the type of amide used
nitriles
O 1. LiAlH4 H
Reduction of
R C NH 2 2. H + R C NH 2 + H2O
amides
H
Hoffmann’s
degradation of
amides
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 Example :
Reduction of i.
O H
1. LiAlH4
nitro compound CH3 C NH2 CH3 C NH2 + H2O
+
2. H
Reduction of H
Ethanamide
nitriles Ethanamine
(2o amide)
(1o amine)
Reduction of
amides ii.
O CH3 1. NaBH4
H CH
3
+ CH3 C NH + H2O
Hoffmann’s CH3 C NH 2. H
H
degradation of
N-methylethanamine
amides N-methylethanamide
(2o amine)
(2o amide)
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 Hoffmann’s degradation of amides

Reduction of  On warming a primary amide with bromine
nitro compound in solution of NaOH, a primary amine is
formed.
Reduction of
 This reaction is used to synthesise
nitriles
primary alkyl and aryl amines.
Reduction of O Br2 , NaOH 2-
RNH2 + CO3
amides R C NH2 H 2O
Hoffmann’s amide amine
degradation of  The elimination of carbonyl group is
amides shortening the length of carbon chain by
one carbon atom.
atom
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.4 Example :
Reduction of CONH2 NH2
nitro compound
Br2, OH-
Reduction of + CO32-
nitriles H2O
Reduction of
amides
Hoffmann’s
degradation of
amides
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with acyl chlorides

Reaction with :  1° and 2° amines are acylated to form
N-substituted amides
Acyl chloride H O H O
RNH3 Cl -
+
+
Acid anhydride 2 R N H + Cl C CH3 R N C CH3
1o amine 2o amide
Benzenesulphonyl
chloride
O
Nitrous acid R R O
-
+ R2NH+2 Cl
2 R N H + Cl C CH3 R N C CH3
Bromine water 3o amide
2o amine

Formation of dye  3° amines are not acylated because they

do not have a H atom attached to N atom.
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with acid anhydride

Reaction with :  1° and 2° amines are acylated to form
N-substituted amides
Acyl chloride H O O H O
R N H + CH3 C O C CH 3 R N C CH3
Acid anhydride
1o amine acid anhydride 2o amide
Benzenesulphonyl
chloride + CH3COO H

R O O R O
Nitrous acid
R N H + CH3 C O C CH 3 R N C CH3
Bromine water 2o amine acid anhydride 3o amide
+ CH3COO H

Formation of dye  3° amines are not acylated because they

do not have a H atom attached to N atom.
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with benzenesulphonyl chloride

Reaction with :
Hinsberg’s test
Acyl chloride  This reaction is used to differentiate
Acid anhydride between 1°, 2° and 3° amines.
Benzenesulphonyl
chloride

Nitrous acid
Bromine water

Formation of dye
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 1° amines
Reaction with :  Benzenesulphonyl chloride reacts with a
1° amine to form a white precipitate
Acyl chloride (N-substituted sulphonamides)Acidic hydrogen
Acid anhydride H O H O
-
OH
Benzenesulphonyl R-N-H
+
Cl-S- R-N -S-
chloride (-HCl)
1o amine O O
N-substituted
Nitrous acid Na O benzenesulphonamides
Bromine water R-N -S- (precipitate)
 N-substituted sulphonamides have an
O
acidic hydrogen, N-H.NaOH
Formation of dye water soluble salt
 Therefore, it dissolve in aqueous NaOH.
(clear solution)
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 2° amines
Reaction with :  Benzenesulphonyl chloride reacts with a
2° amines to form a white precipitate
Acyl chloride (N,N-disubstituted sulphonamide)
R' O R' O
Acid anhydride -
OH
Benzenesulphonyl R-N-H
+
Cl-S- R-N -S-
chloride (-HCl)
o O
2 amine O
N,N-disubstituted
Nitrous acid
benzenesulphonamides
Bromine water (precipitate)
 N,N-disubstituted sulphonamides do not
No reaction
have an acidic hydrogen, N-H.NaOH
Formation of dye  Therefore, it dissolve in aqueous NaOH.
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 3° amines
Reaction with :  3° amine do not gives visible reaction
with benzenesulphonyl chloride
Acyl chloride
Summary of Hinsberg’s test:
Acid anhydride
NaOH
Benzenesulphonyl 1° amines  white precipitate  clear
chloride solution
NaOH
Nitrous acid 2° amines  white precipitate  do not
dissolved
Bromine water
3° amines  do not give any visible
Formation of dye change
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Reaction with nitrous acid (NaNO2 + HCl)

Reaction with :  Nitrous acid (HNO2) is a weak and unstable
Acyl chloride acid.
 It is always prepared in situ, by treating
Acid anhydride
cold sodium nitrite (NaNO2) with an
Benzenesulphonyl aqueous solution of a cold dilute
chloride
hydrochloride acid (-5°C).
Nitrous acid  Nitrous acid reacts with all classes of
amines
Bromine water
Nitrous acid test can be used to distinguish:
• 1° aliphatic and 1° aromatic amines
Formation of dye • 1° and 2° aliphatic amines
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 1° amines (Aliphatic)

Reaction with :  Primary aliphatic amines react with
nitrous acid to yield highly unstable
Acyl chloride aliphatic diazonium salts
Acid anhydride H
NaNO2, HX -N2
+
+ -
R-N-H [ R-N NX ] R +
X
Benzenesulphonyl o
-5 to 0 C
chloride o aliphatic carbocation
1 amine diazonium salt
Nitrous acid (unstable)

Bromine water Observation :

Formation of gas bubbles C=C +
ROH +
RX
Formation of dye (N2)
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 1° amines (Aromatic)

Reaction with :  Primary arylamines react with nitrous
acid to give arenediazonium salts
Acyl chloride
Acid anhydride NH2 N2+Cl

Benzenesulphonyl NaNO2, HCl

chloride + NaCl + H2O
cold
Nitrous acid arenediazonium salt
Bromine water

Formation of dye
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 1° aliphatic amines and 2° aliphatic amines

Reaction with : Primary Form a mixture of alkenes,
aliphatic alcohols, alkyl halides and
Acyl chloride
amines nitrogen gas.
Acid anhydride Secondary Form secondary N-
Benzenesulphonyl aliphatic nitrosamines as yellow oil,
chloride amines which is stable under the
Nitrous acid reaction conditions.

Bromine water

Formation of dye
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Identification
Reaction with bromine water
test
Reaction with : Aniline reacts with aqueous bromine to
yield white precipitates
Acyl chloride
NH2 group is an activating and ortho-
Acid anhydride para directors group
Benzenesulphonyl NH2 NH2
chloride
3Br2(aq) Br Br
Nitrous acid
room temperature + 3HBr
Bromine water
Br
(2,4,6-tribromoaniline)
Formation of dye
Observation: White precipitate formed
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 Formation of dye

Reaction with : Primary arylamines react with nitrous acid
to give arenediazonium salts which are
Acyl chloride stable at 0 C
Acid anhydride
Arenediazonium salts also undergo coupling
Benzenesulphonyl reaction with aromatic compounds with
chloride strong electron donating group, such as –OH
Nitrous acid and –NR2 at the para position to yield azo
compounds
Bromine water
Azo compounds are usually intensely
coloured and relatively inexpensive
Formation of dye compounds, they are used as dyes
 Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5
Reaction with :

Acyl chloride OH
N=N OH

Acid anhydride (orange)

+
-
Benzenesulphonyl N N: X CH3
CH3
chloride
N CH3 N=N N CH3
Nitrous acid (yellow)

Bromine water

Formation of dye