SOME COMMON AMINES

Structure of Amines

Nitrogen orbitals in
amines are therefore, sp3
hybridised and the
geometry of amines is
pyramidal.
Due to the presence of
unshared pair of
electrons, the angle C–N–
E, (where E is C or H) is
less than 109.5°; for
instance, it is 108o in case
trimethylamine
Nomenclature
A
R
O
M
A
T
I
C

A
M
I
N
E
S
DO IT YOURSELF
Preparation of Amines
1. Reduction of nitro compounds

Iron scrap and

hydrochloric acid
reduction is preferred
because FeCl2 formed
gets hydrolysed to release
hydrochloric acid during
the reaction. Thus, only a
small amount of
hydrochloric acid is
required to initiate the
reaction.
2. Ammonolysis of alkyl halides
The primary amine thus obtained can further react with R-X to
form secondary and tertiary amines

Ammonolysis has the

disadvantage of
yielding a mixture of
primary, secondary
and tertiary amines
and also a
quaternary
ammonium salt.
However, primary
amine is obtained as
a major product by
taking large excess of
ammonia.
3. Reduction of nitriles
Nitriles on reduction with lithium aluminium hydride (LiAlH4 ) or catalytic hydrogenation
produce primary amines. This reaction is used for ascent of amine series, i.e., for preparation
of amines containing one carbon atom more than the starting amine.

4. Reduction of amides
The amides on reduction with lithium aluminium hydride yield amines.
5. Gabriel phthalimide synthesis
Gabriel synthesis is used for the preparation of primary amines. Aromatic primary amines
cannot be prepared by this method because aryl halides do not undergo nucleophilic
substitution with the anion formed by phthalimide.
6. Hoffmann bromamide degradation reaction
Hoffmann developed a method for preparation of primary amines by treating an amide with bromine in an aqueous or
ethanolic solution of sodium hydroxide
 5 Physical Properties
1. SOLUBILITY
Out of butan-1-ol and butan-1-amine, which will be more soluble in water and why? Amines are soluble
in organic solvents like alcohol, ether and benzene. You may remember that alcohols are more polar
than amines and form stronger intermolecular hydrogen bonds than amines.
2. BOILING POINT

the order of boiling points of isomeric amines is as follows:

Primary > Secondary > Tertiary

Intermolecular hydrogen bonding in primary amines is shown:
Chemical Reactions :
1. Basic character of amines
Amines, being basic in nature, react with acids to form salts.

Amine salts on treatment with a base like NaOH, regenerate the parent amine.
Kb and pKb
Basic character of amines can be better understood in terms of their Kb and pKb values as explained
below:
Larger the value of Kb or smaller the value of pKb , stronger is the base.

Aliphatic amines are stronger bases than ammonia due to +I effect

of alkyl groups leading to high electron density on the nitrogen
Atom.
On the other hand, aromatic amines are weaker bases than
ammonia due to the electron withdrawing nature of the aryl group.
Order of basicity (gas phase):

FACTORS :
+I effect of the alkyl groups
(CH3)3N>(CH3)2NH>CH3NH2>NH3

This is reasonable because the conjugate acids, R3N⊕H , are likely to be stabilized by
electron-donating and polarizable alkyl groups, thereby making R3N
a stronger base.
ORDER OF BASICITY IN AQUEOUS PHASE
Arylamines versus ammonia
Arylamines are less basic than ammonia.It is because in aniline or other arylamines, the -NH2 group is
attached directly to the benzene ring. It results in the unshared electron pair on nitrogen atom to be in
conjugation with the benzene ring and thus making it less available for protonation.

electron releasing groups like –OCH3 , –CH3 increase basic strength whereas electron withdrawing groups like –
NO2 , –SO3H, –COOH, –X decrease it.

DO IT YOURSELF
Arrange the following in decreasing order of their basic strength:
C6H5NH2 , C2H5NH2 , (C2H5 ) 2NH, NH3
2. Alkylation

3. Acylation
Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and esters by nucleophilic
substitution reaction. You can consider this reaction as the replacement of hydrogen atom of –NH2
or >N–H group by the acyl group. The products obtained by acylation reaction are known as amides. The reaction is
carried out in the presence of a base stronger than the amine, like pyridine, which removes HCl so
formed and shifts the equilibrium to the right hand side.
BENZOYLATION:
DISTINGUISHING TESTS B/W AMINES
4. Carbylamine reaction/ isocyanide test : test for primary amines
A . Aliphatic and aromatic primary amines on heating with chloroform and ethanolic potassium hydroxide
form isocyanides or carbylamines which are foul smelling substances.
B. Secondary and tertiary amines do not show this reaction.

5. Reaction with nitrous acid

A. PRIMARY AMINES:
B. SECONDAARY AMINES:

A YELLOW
OILY LIQUID
IS FORMED

C. TERTIARY AMINES

A SOLUBLE SALT IS
FORMED
Aromatic amines
react with nitrous acid at low temperatures (273-278 K) to form diazoniu salts,

HINSBERG’S TEST
Hinsberg’s reagent : Benzenesulphonyl chloride (C6H5 SO2Cl),
reacts with primary and secondary amines to form sulphonamides.
1. PRIMARY AMINES

The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of strong electron
withdrawing sulphonyl group. Hence, it is soluble in alkali.
2. SECONDARY AMINES:

In the reaction with secondary amine, N,N-diethylbenzenesulphonamide is formed. Since N, N-diethylbenzene

sulphonamide does not contain any hydrogen atom attached to nitrogen atom, it is not acidic and hence
insoluble in alkali.

3.Tertiary amines do not react with benzenesulphonyl chloride.

This property of amines reacting with benzenesulphonyl chloride in a different manner is used for the separation of a
mixture of amines. However, these days benzenesulphonyl chloride is replaced by p-toluenesulphonyl chloride.
7. Electrophilic substitution
–NH2 group is ortho and para directing and a powerful activating group.

(a)Bromination:
Aniline reacts with bromine water at room temperature to give a white precipitate of 2,4,6-
tribromoaniline.

To prepare monosubstituted aniline derivative, the

activating effect of –NH2 group be controlled by
protecting the -NH2 group by acetylation with acetic
anhydride, then carrying out the desired substitution
followed by hydrolysis of the substituted amide to
the substituted amine.
The lone pair of electrons on nitrogen of acetanilide interacts with oxygen atom due to
resonance as shown below:

Hence, the lone pair of electrons on nitrogen is less available for donation to benzene ring by
resonance. Therefore, activating effect of –NHCOCH3 group is less than that of amino group.

(b) Nitration:
Direct nitration of aniline yields tarry oxidation products in addition to the nitro derivatives. Moreover, in the
strongly acidic medium, aniline is protonated to form the anilinium ion which is meta directing. That is why besides
the ortho and para derivatives, significant amount of meta derivative is also formed.
 by protecting the –NH2 group by acetylation reaction with acetic anhydride, the nitration
reaction can be controlled and the p-nitro derivative can be obtained as the major product.

(c) Sulphonation:
Aniline reacts with concentrated sulphuric acid to form anilinium hydrogensulphate which on heating with
sulphuric acid at 453-473K produces p-aminobenzene sulphonic acid, commonly known as sulphanilic acid, as the
major product.
 Friedel-Crafts reaction (alkylation and acetylation
Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) due to salt formation with
aluminium chloride, the Lewis acid, which is used as a catalyst. Due to this, nitrogen of aniline acquires
positive charge and hence acts as a strong deactivating group for further reaction.
Method of Method of preparation of Diazoniun Salts
1. Benzenediazonium chloride is prepared by the reaction of aniline with nitrous acid at 273-
278K.
2. Nitrous acid is produced in the reaction mixture by the reaction of sodium nitrite with
hydrochloric acid.
3. The conversion of primary aromatic amines into diazonium salts is known as diazotisation.
4. Due to its instability, the diazonium salt is not generally stored and is used immediately after
its preparation.
Chemical Reactions
(A) reactions involving displacement of nitrogen and
(B) reactions involving retention of diazo group.
(A) groups such as Cl– , Br– , I – , CN– and OH– which displace nitrogen from the aromatic ring. The
nitrogen formed escapes from the reaction mixture as a gas.
REPLACEMENT BY NITRO GROUP:

REPLACEMENT BY HYDROGEN: Certain mild reducing agents like hypophosphorous acid (phosphinic acid) or
ethanol reduce diazonium salts to arenes and themselves get oxidised to phosphorous acid and ethanal,
B. Reactions involving retention of diazo group
coupling reactions

This is an example of electrophilic substitution reaction.