AMINES

Amines
Derivatives of NH3, obtained by replacement of one, two or all the three
hydrogen atoms by alkyl and/or aryl groups, e.g.
CH3 – NH2, C6H5NH2, CH3 – NH -CH3, CH3N(CH3)2

Structure:
Amines have pyramidal shape and the N atom is sp3 hybridised. The
three sp3 hybrid orbitals are bonded with carbon atom and the fourth
orbital contains an unshared pair of electrones.

Classification
Amines are classified as 1°, 2°, and 3° depending upon the number of
alkyl/aryl groups in NH3.

Nomenclature
Common system-Alkyl amines, IUPAC system-Alkanamines i.e., ‘e’ of the
alkane replaced by amine.

Preparation of Amines
(1) Reduction of nitro compounds:
They are reduced to amines by using H2/Pd, Sn + HCI, Fe + HCI.

(2) Ammonolysis of Alkylhalides:

Alkyl or benzyl halides on reaction with an ethanolic solution of NH 3 give
a mixture of 1°, 2°, 3° amines, and quaternary ammonium salt.
R – X + NH3 → R – NH2 + HX
R – NH2 + R – X → R2NH + HX
R2 – NH + R – X → R3N + HX
R3N + R – X → R4N+X–
(Quarternary ammonium salt)
1° amine is obtained as major product by taking large excess of NH 3.

(3) Reduction of Nitriles:

On reduction with LiAlH4 or catalytic hydrogenation they produce 1°
amines.

(4) Reduction of amides:

On reduction with LiAlH4 they yield amines.

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(5) Hoffmann Bromamide Degradation Reaction:

When an amide is treated with Br2 in presence of aqueous or ethanolic
solution of NaOH a 1° amine with one carbon less than that present in
the amide is formed. This reaction is used to step down the series.
(6) Gabriel Phthalimide Synthesis:
Phthalimide on treatment with ethanolic KOH forms its potassium salt
which on heating with alkyl halide followed by alkaline hydrolysis
produces the corresponding 1° amine.

Aromatic 1° amines cannot be prepared by this method because aryl

halides do not undergo nucleophilic substitution with the anion formed
by phthalimide.

Physical Properties
Lower aliphatic amines are soluble in water because they can form
hydrogen bonds with water molecules. The solubility decreases with
increase the molar mass of amines due to increase in size of the
hydrophobic alkyl part.

Amines are soluble in organic solvents like alcohol, ether and benzene.
The boiling points of isomeric amines increases in the order 1° > 2° > 3°
because association through intermolecular hydrogen bonding is more
in 1°amines.

Chemical Reactions
(1) Basic character of amines:
Amines react with acids to form salts.

Due to the unshared electrons on N atom, amines behave as Lewis

bases. Basicity is expressed in Kb values or pKb values. Largerthe value of
Kb, or smaller the value of pKb, stronger is the base.

Structure – Basicity Relationship of Amines:

The more stable the cation formed by protonation of the amine, more
stable is the amine.

(a) Alkyl Amines versus Ammonia:

In gas phase:
Due to the electron releasing nature of alkyl group (+l effect) it pushes
electron towards N and thus makes the unshared electron pair more
available for sharing. Also the substituted ammonium ion formed gets
stabilised due to dispersal of the positive charge.

Hence, alkyl amines are stronger bases than NH3. The order of basicity of
amines in the gaseous phase is 3° > 2°> 1°> NH3.

In aqueous phase:
The greater the size of the substituted ammonium cation, lesser will be
the solvation and the less stabilised is the ion. The extent of H-bonding
and stability of the protonated ions follows the order: 1° > 2° > 3°. When
the alkyl group is small there is no steric hindrance to H- bonding.

Thus, an interplay of +l effect, solvation effect and steric hindrance of

the alkyl group decides the basic strength of alkyl amines in the aqueous
state, e.g.
(CH3)2 NH > CH3NH2 > (CH3)3N > NH3
(C2H5)2 NH > (C2H5)3N > C2H5NH2 > NH3

(b) Aryl amines versus Ammonia: Aniline and other aryl amines are
weaker bases than NH3 because, the – NH2 group is attached directly to
the benzene ring. It results in the unshared electron pair on N atom to
be in conjugation with the benzene ring and thus making it less available
for protonation.

But anilinium ion obtained by accepting a proton has only two

reasonating structures.

Thus aniline is more stable than anilinium ion. In the case of substituted
aniline, the electron releasing groups like – OCH3, -CH3 increase basic
strength where as electron-withdrawing groups – NO2, -SO3H, -COOH, -X
decrease the basicity.

(2) Acylation:
Aliphatic and aromatic 10 and 2° amines react with acid chlorides,
anhydrides and esters to form corresponding amides. 3° amines do not
undergo acylation.

(3) Carbylamine Reaction:

Aliphatic and aromatic 1° amines on heating with chloroform and
alcoholic KOH form foul smelling substances known as isocyanide or
carbylamine.

This reaction is used as a test for 1° amines.

(4) Reaction with Nitrous Acid:

Three classes of amines react differently with nitrous acid.

(a) Primary Alphatic Amines:

They react with nitrous acid (HNO2) to form aliphatic diazonium salts,
which being unstable, liberate N2 gas quantitatively and form alcohols.
(b) Aromatic Amines:
They react with HNO2 at low temperature (273 – 278 K) to form
diazonium salts

(5) Reaction with Arylsulphonyl Chloride (Hinsberg’s Test):

Hinsberg’s reagent – Benzene sulphonyl chloride (C6H5SO2Cl).

(a) Reaction with 1° amine -N-alkylbenzene-sulphonyl chloride is formed

which is soluble in alkali due to the presence of acidic hydrogen.

(b) Reaction with 2°amine – N,N-dialkyl benzene sulphonyl chloride is

formed which is insoluble in alkali due to the absence of acidic
hydrogen.

(c) Tertiary amine do not react with Hinsberg’s reagent. This test is used
for the distinction of 1°, 2° & 3° amines and also for the separation of a
mixture of amines.

(6) Electrophilic Substitution:

The -NH2 group an activating group which directs the incoming
electrophile to ortho and para postions.

(a) Bromination:
Aniline reacts with Br2 water at room temperature to give a white ppt. of
2, 4, 6- tribromoaniline.
To get para and ortho product, the activating effect of -NH2 group should
be controlled by acetylation.

(b) Nitration:
Direct nitration of aniline yields tarry oxidation products in addition to
the nitro derivatives. Significant amount of m- derivative is also formed.
This is due to protonation of aniline to anilinium ion which is m-
directing.

However, by protecting -NH2 group by acetylation, nitration gives para

and ortho derivatives. Para derivative is obtained as the major product.

(c) Sulphonation:
Aniline reacts with cone. H2SO4 to form anilinium hydrogen sulphate
which on heating with H2SO4 at 453 – 473 K produces p-aminobenzene
sulphonic acid (sulphanilic acid), as the major product.

Aniline does not undergo Friedel – Crafts alkylation and acylation due to
salt formation with the catalyst, AlCl3 Due to this, N of aniline acquires
positive charge and hence acts as a strong deactivating group for further
reaction.

(II) Diazonium salts:

Diazonium salts have the general formula RN2+X– where R stands for an
aryl group and X– ion may be Cl–, Br–, HSO4, BF4– etc. e.g. C6H5N2+Cl– –
Bezene diazonium chloride. Its stability is explained on the basis of
resonance.

Methods of Preparation
Benzenediazonium chloride is prepared by the reaction of aniline with
nitrous acid (HNO2) at 273 – 278 K. Nitrous acid is produced in the
reaction mixture by the reaction of NaNO2 with HCI. The conversion of 1°
aromatic amines into diazonium salts is known as diazotisation.

Physical Properties
Colourless crystalline solid, readily soluble in water, stable in cold but
decomposes in the dry state.

Chemical Reactions
A. Reactions Involving Displacement of Nitrogen:
(1) Replacement by halide or cyanide ion:
Sandmayerreaction – The Cl–, Br– and CN– ions can easily be introduced
in the benzene ring by treating benzene diazonium salt with HCI,
HBrorHCN in the presence of CuCl, CuBr and CuCN respectively.

Gatterman reaction – Cl or Br can be introduced in the benzene ring by

treating the diazonium salt solution with corresponding halogen acid in
the presence of Cu powder.

(2) Replacement by Iodide Ion:

When diazonium salt solution is treated with Kl, iodobenzene is formed.
ArN2+Cl– + Kl → Arl + KCl + N2

(3) Replacement by Fluoride Ion:

When arene diazonium chloride is treated with fluoroboric acid, arene
diazonium fluoroborate is precipitated which on heating decomposes to
yield aryl fuloride.

(4) Replacement by H:
When benzene diazonium salt is treated with mild reducing agents like
hypophosphorous acid (phosphenic acid) or ethanol, the diazonium salts
are reduced to arenes. ArN2+CI’ + H3P02 + H20

(5) Replacement by -OH:

When the diazonium salt solution is warmed upto 283 K, the salt gets
hydrolysed to phenol.

(6) Replacement by – NO2 group:

When diazonium chloride is treated with fluoroboric acid benzene
diazonium fluoroborate is formed which on heating with aqueous
sodium nitrite solution in the presence of copper, the diazonium group is
replaced by – NO2 group.

B. Reactions Involving Retention of Diazo Group-Coupling Reactions:

Benzene diazonium chloride reacts with phenol to form p-
hydroxyazobenzene.

Reaction of diazonium salt with aniline yields p-aminoazobenzene.

Importance of Diazonium Salts

In the manufacture of azo dyes, in the preparation of a number of useful
organic compounds, cyanobenzene can easily be obtained from
diazonium salt.