Amines

13

BASIC
CONCEPTSL

1. Introduction
AIkyl or aryl derivatives of ammonia are regarded as amines. These are obtained by replacing one or more
hydrogen atoms by alkyl or aryl groups. Amines are classified as primary, secondary or tertiary depending
upon whether one, two or three atoms of hydrogen have been replaced by alkyl or aryl groups.

H
-

NH +CH3
CH NH +CH3 (CH) NH (CH3)3N
Methylamine Dimethylamine +CH3
Trimethylamine
I°(Primary) 2°(Secondary) 3°(Tertiary)
Thus, characteristic functional groups for 1, 2° or 3° amines are:

-NH2 -NH -N
Primary Second1ry Tertiary
Amines are said to be 'simple' when all the alkyl or aryl groups are the same, and 'mixed' when they are
different.
There is another class of compounds wherein all the four hydrogen atoms of an ammonium salt have been
replaced by alkyl or aryl groups. Such compounds are named as quaternary ammonium salts.
4H
[NH,'X HR INRI'X
Tetra alkylammoniunm halide

Unshared
Structure of Amines electron
pair
LIke ammonia, nitrogen atom of amines is trivalent and carries
an unshared pair of electrons. Nitrogen orbitals in amines
ire therefore sp' hybridised and the geometry of amines is

Pyramidal. Each of the three sp' hybridised orbitals of nitrogen -CH3

erlap with orbitals of hydrogen or carbon depending upon -CH
Composition of the amines. The fourth orbital of nitrogen
in allaamines contains an unshared pair of electrons. Due to the
sence of unshared pair of electrons. the angle C-N-E, CH3
reEis C or H) is less than 109.5°; for instance, it is 108 108°

Case of trimethylamine as shown in Fig. 13.1 alongside.

3. Nomenclature Trimethylamine
Fig. 13.1: Pyramidal
n the these are
named as
named alkylamine but in the IUPAC system,
y s t e m , amines are as
alkanamine (replacing 'e' of alkane with amine).
CHg-CH-CH-NH2 CHs
oCHN
2-Phenyl propanamine (19 N-Benzyl-N-ethyl benzenamine

Amines 525
 Table 13.1: Nomenclature of Some Amines
Common Name Structural Formula IUPAC Name
Ethyl amine
CH-CH-NH Ethanamine

CH3
Isopropyl amine CH-CH-NH2 Propan-2-amine
Ethyl methyl amine CH-CH-NH-CH3 N-Methylethanamine
CH5
N. N-Diethylbutylamine
CHs-N-CH2-CH-CH2-CH3 N, N-Diethylbutan-1- amine
Allylamine CH-CH-CH-NH, Prop-2-en-1-amine
Hexamethylenediamine HN-(CH,)6-NH2 Hexane-1, 6-diamine

NH2
Aniline
Benzenamine or Aniline

o-Toluidine
NH2
-CH3 2-Methylaniline

N, N-Dimethylaniline
H,C-N-CH3
N, N-Dimethylbenzenamine

Preparation of Amines: Amines are prepared by the following methods:

(a) Reduction of nitro compounds:
Ni
R-NO +3H2 R-NH2 +
1° amine
2H20

CH3-CH2-NO2 + 6[H] Fe/HCI (conc.)

Nitroethane or CH3-CH2-NH2 + 2H,0

Sn/HCI (conc.) Ethanamine
b) Ammonolysis of alkyl halides:
R-X+ 2NH
(excess) RNH2+
1 amine
NH4X
(Major product)
If alkyl halide is in excess, the amine
formed further reacts with
finally quaternary ammonium salts. alkyl halide to form 20, 3° amines a

R-NH2
1 amine
R, NH
2 amine
+R-X RaN
+R-X
RN X
3° amine
Quaternary
ammonium salt

c) Reduction of nitriles:
Ni
R-C= N+ 2H2 - R-CH2-NH2

1° amine

Na(Hg)/C2Hs OH
R-C=N+ 4[H] or LiAlH4 R-CH2-NH2
1° amine
 CEN
CH-NH2
(O +4[H] LiAIH4
Benzyl amine
(d)Reduction of amides:
R-CONH, + 4|H| LiNIH,/elther
Acid amile R-CH2-NH
1 amine
+ H,0
) Hoffmann's bromamide degradation
reaction:
R-CONH, +Br2 + 4NaOH
Acid amide
R-NH I amine
+
Na,CO+2NaBr +2H,0
Gabriel phthalimide synthesis:
KOOH
O NK
+R-X
-ONa + NaOH (aq)
C-ONa +R-NH
(1° amine) N-R
Aromatic amines cannot be
prepared
substitution with the anion formed by this method because aryl halides do
by phthalimide.
not undergo nucleophilic
Preparation of Aniline
) From nitrobenzene
NO2 NH2
Sn/HCI (conc.)
+6[H] or O +2H,0
Fe/HCI (conc.)
Nitrobenzene Aniline
i) By Hoffmann bromamide degradation reaction
çONH2 NH
+Bry + 4KOH +K,CO + 2KBr + 2H,0
Benzamide Aniline
5, Physical Properties
Ower members are combustible gases, members from C to C are volatile liquids and from Ca
ards are solids. Lower aromatic amines are liquids while the higher ones are low melting solids.
amines are almost colourless but develop colour on keeping in air for long time, especially, the
amines. The colouration is due to oxidation of amines by air.
ii) atic
The boiling
DOling point increases with the increase in molecular weight. However, primary and secondary
e s have higher boiling points than the tertiary amines of the same molecular weight. This is again
due to the possibility of intermolecular hydrogen bonding between molecules of primary as well as
Secondary amines.
Amines 527
 CH3
HC-N-H..N-H
*****.H H
is weaker than that
between alcohols or carhn
between amine molecules
The hydrogen bonding of comnae
carboxylic acids of
acids therefore amines have lower boiling points than the alcohols or
comparable
molecular masses.
solubility
the in water decreases and in or.
(v) The lower members are readily
soluble in water, organic
the increase in molecular weight.
solvents(alcohol and ether) increases with
Solubility of all the three classes of aliphatic amines in water is due to the formation of hydrogen hDond
in higher amines, the alkyl group predominates over
between amine and water molecules. However,
less tendency for forming hydrogen bond with watae
water.
the amino group with the result that they have
This explains why the higher amines are insoluble in
water.
Aromatic amines are insoluble in water. This is because of the larger hydrocarbon part. Thus, anjline
is almost insoluble in water. However, all amines are quite soluble in organic solvents like benizene
ether, alcohol, etc.
6. Basic Character of Amines: Amines have a lone pair of electrons on nitrogen atom due to which they
behave as Lewis base. Basic character of amines can be better understood in terms of K, and pK, values as
explained below.
R-NH2 + H0 =RNH, + OH
IRNH,1IOH]
R-NH]
pk, =- log K»
Larger the value of K, or smaller the value of pK, stronger is the base.
(a) Amines versus alcohols, ethers and esters: Since nitrogen is less
a better position to accommodate the
electronegative than oxygen, it IS
positive charge of the proton. Therefore, amines are more basie
than alcohols, ethers, esters, etc.
b) Alkylamines versus ammonia: In
aliphatic amines, the electron-releasing alkyl groups stabiIS
their ammonium cations
by dispersing the positive charge, and in parent amines make the nitrog
unshared electrons more available for
amines should increase with the
sharing
with a proton. Thus, the basic character of alipha
increase of alkyl substitution. But it ar
manner as a does not occur in a re
econdary aliphatic amine is unexpectedly more basic than a
Basicity Order: (Et),NH > Et,N> tertiary amine in soluno
In
EtNH,> NHs; (Me),NH> MeNH,> (Me),N > NH3
gas phase, where the solvent effect is
i.e., tertiary amine > missing, the basic trend in nature is as exp ected,
secondary amine > primary amine > ammonia.
Anomalous basic strength of
cations are stabilised not tert-alkylamines: In aqueous solution, the onium
with water molecules. It is
only by electron-releasing effect of the alkyl groupssubstituted amu
but also by
determine the stability of
a combination of
electron-releasing, H-bonding and sterie fact Sh
order of aliphatic amines as
the ammonium cations in solution and thereby
resulting in the bast
S t r e n g t h
secondary >
tertiary > primary amines.
(c) Aromatic amines versus ammonia
and aliphatic
ammonia and aliphatic amines. Since amines: Aromatic amines are weakerbases than
ammonium cation, the resonance stabilises an aromatic amine
Das is
proton acceptability more than it
stad b
less. It may also be
argued that due to
and thereby basic strength of aromatic amines
are less available for resonance, unshared electrons
sharing with a on
nitrogen in
am.
proton--a feature opposite to that in alkyl amines.aromau