1

13 AMINES
Amines: Amines are regarded as derivatives of ammonia in which alkyl or aryl group
replaces one,two or all three hydrogen atoms.
Classification

Classified as primary (1), secondary (2), and tertiary (3)

NH2----------------------PRIMARY AMINES [R-NH2]

NH------------------------SECONDARY AMINE [R2NH]
N------------------------- TERTIARY AMINE [R3NH]

Structure of Amines
Nitrogen is trivalent with one lone pair.
Nitrogen on amines is sp3 hybridised. Geometry is Pyramidal. Each of the three sp3
hybridised orbitals of nitrogen overlap with orbitals of hydrogen or carbon. The fourth orbital
contains a lone pair. Due to the presence of lone pair, the bond angle is less than 109.5;
Example: Pyramidal shapes of trimethylamine

Nomenclature - Common System

Aliphatic amine: Alkylamine.

Example: Methylamine (CH3NH2)
IUPAC System

Named as alkanamines; derived by replacing the e of alkane with the word amine.

CH3NH2 Methanamine
CH3CH2NH2 Ethanamine

When more than one amino group is present Suitable prefix such as di-, tri-, etc., is
attached to amine. e of the suffix of hydrocarbon is retained.

Positions of NH2 group are specified by giving numbers to the parent chain.

Ethane-1, 2-diamine
For aryl amines NH2 group is directly attached to the benzene ring
C6H5NH2 (Common name aniline, IUPAC name aniline / benzenamine)
Common and IUPAC names of some alkylamine and arylamines are given in the
table.

Preparations of amines
Reduction of Nitro Compounds
By passing H2 gas in presence of finely divided Ni, Pd, or Pt or Sn/HCl or Fe/HCl

Q. Reduction with iron scrap and hydrochloric acid is preferred.

Because FeCl2 formed gets hydrolysed to release HCl during the reaction. Thus, only a small
amount of HCl is required to initiate the reaction.
Ammonolysis of Alkyl Halides
An alkyl or benzyl halide reacts with an ethanolic ammonia undergoes nucleophilic
substitution reaction in which the halogen atom is replaced by an amino (NH2) group.This
process of cleavage of the CX bond by ammonia molecule is known as ammonolysis. The
reaction is carried out in a sealed tube at 373 K.

Disadvantage: Ammonolysis is not a best method to prepare primary amine.

Ammonolysis yields a mixture of primary, secondary and tertiary amines and also a
quaternary ammonium salt.

Reduction of Nitriles [R-CN]-

Q. Convert Methanol to ethanamide

Q. Convert Methanol to Ethanoic acid.

Q. Convert Methanol to ethanamine

Q. Convert Ethanenitrile to Ethanamine

Reduction of Amides

Gabriel Phthalimide Synthesis

Gabriel synthesis is used for the preparation of primary amines.
Phthalimide on treatment with ethanolic potassium hydroxide forms potassium salt of
phthalimide which on heating with alkyl halide followed by alkaline hydrolysis produces the
corresponding primary amine

Q.Gabriel phthalimide synthesis is preferred for synthesising primary amines:

Gabriel phthalimide synthesis gives pure 1 amine without the contamination of 2 or 3
amines.

Q.Why Aromatic primary amines cannot be prepared by Gabriel phthalimide synthesis

It is because aryl halides do not undergo nucleophilic substitution with the anion formed by
phthalimide, due to partial double bonds character in C-X bond.

Hoffmann Bromamide Degradation Reaction

Preparation of primary amines by treating an amide with Br2 in an aqueous or ethanolic
NaOH solution, amine so formed contains one carbon less than that present in the amide.

T
Q. Write structures and IUPAC names of
(i) the amide which gives propanamine by Hoffmann bromamide reaction.

(ii) the amine produced by the Hoffmann degradation of benzamide Physical Properties of

Amines &

Q. Convert Ethanamide to methanamine.

Q. Convert Benzamide to aniline.

Q.Write chemical equations for the following reactions:

i.Reaction of ethanolic NH3 with C2H5Cl.
ii.Ammonolysis of benzyl chloride & reactn of amine so formed with 2 moles of CH3Cl.

Q. Write chemical equations for the following conversions:

(i) CH3CH2Cl into CH3CH2CH2NH2
(ii) C6H5CH2Cl into C6H5CH2CH2NH2

Q. How will you convert

(i) Benzene into aniline

(ii) Benzene into N, N-dimethylaniline

(iii) Cl(CH ) Cl into hexan-1,6-diamine?

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ic: Physical Properties of Amines & Chemical Reaction of Amines - I
Topic: Physical Properties of Amines & Chemical Reaction of Amines - I
Physical properties of aminesTake a Chapter TestView NCERT Solutions
Lower aliphatic amines are gases with fishy odour.
Primary amines with three or more carbon atoms are liquid. Higher ones are solid.
Aniline and other arylamines are colourless, but get coloured on storage due to
atmospheric oxidation.
Lower aliphatic amines are soluble in
These form H-bonds with water molecules
water.

2. Ethylamine is soluble in water whereas

aniline is not.

Solubility decreases with increase in molar

mass.
Alcohols are more soluble (high B.pt) in
water than amines.

Order of boiling points of isomeric amines

is Primary > Secondary > Tertiary (or)
Primary amines have higher boiling point
than tertiary amines.

Ethylamine forms intermolecular Hbonds

with water. Hence, it is soluble in water.
But aniline does not undergo Hbonding
with water due to the presence of a large
hydrophobic C6H5 group. Hence, aniline is
insoluble in water.
Large alkyl gp is hydrophobic, resist Hbond formation.
O is more electronegative than N, hence
alcohols are more polar than amines and
form stronger intermolecular H-bonds
than amines.
In tertiary amine, there is no Hatom, hence
there is no intermolecular H-bonding
whereas in primary amines, two hydrogen
atoms are present and hence undergo
extensive intermolecular Hbonding.

Basic strength
Order of basic strength Aliphatic amine > NH3 >Aromatic amine
pKb of aniline is more (less basic) than that In aniline, lone pair of electrons on
of methylamine.(or) Aliphatic amines are
nitrogen is in conjugation with the benzene
stronger bases than aromatic amines.
ring [involved in resonance] (+R effect),
less protonated, less basic.
In methylamine due to the +I effect of
methyl group (CH3 gp is EDG), the electron
density on the N-atom is increased, hence
more basic.
Amines behave as nucleophiles
Amines behave as Lewis base.

Due to the presence of lone pair of electrons.

Amines can donate lone pair of electrons on
nitrogen atom .

In gas phase, 30 >20 >10 amine > NH3

As the no. of EDG increases, +I effect of alkyl group increases, basic strength increases.
Basic strength in aqueous solution.

In aqueous solution basic strength depends on inductive effect, solvation effect and steric
hindrance to H- bonding. These three factors are favarouble for 20 amine, hence it is most
basic in aq. solution..
The order of basic strength in aqueous solution,

For small CH3 group, 20 >10 >30 >NH3 [S > P > T]

Reason: For CH3 group, there is no steric hindrance to H- bonding. The stability of cation
due to solvation effect > inductive effect, hence 10 amine is more basic than 30 amine.
For big C2H5 group, 20 >30 >10 >NH3 [S > T > P]
Reason: For C2H5 group, there is steric hindrance to H- bonding. The stability of cation due
to inductive effect > solvation effect, hence 30 amine is more basic than 10 amine.

EDG (CH3, -OCH3), increases the basic strength [increases the e- density on N].
EWG (NO2, halogen), decreases the basic strength [decreases the e- density on N]

Order of basic strength

Aliphatic amine > Benzyl amine >NH3 >Aromatic amine
In gas phase, 30 >20 >10 amine > NH3
For small CH3 group, 20 >10 >30 >NH3 [S > P > T]
For big C2H5 group, 20 >30 >10 >NH3 [S > T > P]
EDG (CH3, -OCH3), increases the basic strength
EWG (NO2, halogen), decreases the basic strength
1. Arrange the following in decreasing order of their basic strength:
C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
(C2H5)2NH > C2H5NH2 > NH3 > C6H5NH2
2. Arrange the following in increasing order of their basic strength:
(i) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH
C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH
(ii) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
C6H5NH2 < C2H5NH2 < (C2H5)3N < (C2H5)2NH
(iii) CH3NH2, (CH3)2NH, (CH3)3N, C6H5NH2, C6H5CH2NH2.
C6H5NH2 < C6H5CH2NH2 < (CH3)3N < CH3NH2 < (CH3)2NH
3. Arrange the following:
(i) In decreasing order of the pKb values[ basic strength]:
C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
C6H5NH2 ,C6H5NHCH3 ,C2H5NH2 , (C2H5)2NH
(ii) In increasing order of basic strength: C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and
CH3NH2
C6H5NH2 < C6H5N(CH3)2 < CH3NH2 < (C2H5)2NH

(iii) In increasing order of basic strength:

(a) Aniline, p-nitroaniline and p-toluidine [CH3, B.S ; NO2 B.S]
p-nitroaniline < Aniline < p-toluidine
(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2.
C6H5NH2 < C6H5NHCH3 < C6H5CH2NH2
(iv) Decreasing order of basic strength in gas phase: C2H5NH2, (C2H5)2NH, (C2H5)3N,
NH3
(C2H5)3N > (C2H5)2NH > C2H5NH2 > NH3
(v) In increasing order of boiling point: C2H5OH, (CH3)2NH, C2H5NH2
(CH3)2NH < C2H5NH2 < C2H5OH
(vi) In increasing order of solubility in water: C6H5NH2, (C2H5)2NH, C2H5NH2.
C6H5NH2 < (C2H5)2NH < C2H5NH2

3.Acylation
Aliphatic and aromatic primary and secondary amines react with acid chlorides,
anhydrides and esters to give amides by nucleophilic substitution reaction. This reaction
is known as acylation. Here, H atom of amino group is replaced by the acyl group.

Benzoylation Reaction of amines with benzoyl chloride (C6H5COCl)

Q. Acetylation is carried out in the presence of base pyridine.

Base pyridine removes HCl formed and shifts the equilibrium to the right hand side.

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2. Alkylation
Amines undergo alkylation on reaction with alkyl halides

3.Carbylamine Reaction or isocyanide test ---- Test for primary amines

4.Reaction with Nitrous Acid ---Test to distinguish aliphatic and aromatic 10 amines.
HNO2is prepared in situ from a mineral acid (HCl) and sodium nitrite (NaNO2).
Aliphatic 10 amines reacts with nitrous acid gives unstable aliphatic diazonium salt, liberate
N2 gas and alcohols. [Quantitative evolution of nitrogen is used in estimation of amino acids
and proteins.]

Aromatic 10 amines react with nitrous acid at 273-278 K to form diazonium salts which
undergo coupling reaction with phenol to form orange dye - azobenzene

5.Hinsberg test with Hinsbergs reagent [Benzenesulphonyl chloride (C6H5SO2Cl)]

Test to distinguish 1, 2 and 3 amines.
(a) Hinsbergs reagent reacts with 1 amine yields a product N-ethylbenzenesulphonamide,
which has acidic H, hence, soluble in alkali.
[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.]

(b) Hinsbergs reagent reacts with 2 amine yields a product N,N-Diethyl benzene
sulphonamide, which does not contain any acidic H [H atom attached to N atom], hence,
insoluble in alkali.

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(c) Hinsbergs reagent does not react with tertiary (3) amine as it does not have replaceable
H atom.
Electrophilic Substitution Reactions
NH2 group is ortho and para directing and a powerful activating group. Due to resonance
( +R effect} electron density is more at ortho and para positions.
Bromination
Test for aniline
Aniline reacts with bromine water to give a white ppt of 2,4,6-Tribromoaniline.

To prepare monosubstituted aniline, NH2 group is protected by acetylation with

acetic anhydride; then the desired substitution is carried out, followed by hydrolysis.
Convert aniline to p-Bromoaniline.

Q. How can be the activating effect of NH2 group in amines be controlled? (or) Why
does the reactivity of NH2 get reduced in acetanilide? (or)Activating effect of
NHCOCH3 is less than that of the amino group.
This can be done by protecting the NH2 group by acetylation. In acetanilide, the lone pair
of es- on nitrogen is less available for donation to benzene ring by resonance. Thus, N
acquires positive charge which reduces the activating effect of NH2 group.

Nitration
Direct nitration of aniline yields tarry oxidation products in addition to the nitro
derivatives.

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Q. Although amino group is o, p directing in aromatic electrophilic substitution

reactions, aniline on nitration gives a substantial amount of m-nitroaniline.
In strongly acidic medium, aniline is protonated to give anilinium ion which is metadirecting.
Q. Convert aniline to p- Bromoaniline.

Sulphonation
Q. Convert aniline to sulphanilic acid.

Q. Aniline does not undergo Friedel-Crafts reaction.

Aniline reacts with AlCl3 to form a salt in which nitrogen acquires a positive charge,
hence acts as a strong deactivating group.
C6H5NH2 + AlCl3 C6H5NH2+AlCl3Diazonium salts
R An aryl group, X ion

group Diazonium group

Benzenediazonium chloride
Q. Aromatic diazonium salts are more stable than aliphatic diazonium salts.
Aromatic diazonium salts are more stable because of resonance, there is dispersal of positive
charge.

Preparation of diazonium salts.

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Diazotisation- Benzenediazonium chloride is prepared by the reaction of aniline with nitrous

acid at 273-278K

Chemical properties
1.Sandmeyer reaction
Diazonium salt reacts with CuCl/HCl or CuBr/HBr or CuCN/KCN to form Chlorobenzene or
Bromobenzene or Benzonitrile.

2.Gatterman reaction
Diazonium salt reacts with Cu/HCl or Cu/HBr to form Chlorobenzene or Bromobenzene

3. Convert diazonium salt to iodobenzene.

4. Convert diazonium salt to fluorobenzene.
5. Convert diazonium salt to benzene.[ Reduction using Ethanol]
6.Convert diazonium salt to benzene.[ Reduction using Hypophosphorous acid
H3PO2/H2O]
7. Convert diazonium salt to phenol.
8. Convert diazonium salt to Nitrobenzene.

9. Coupling reaction.
Benzene diazonium chloride is coupled with phenol to form p-hydroxyazobenzeneorange
dye.
Diazonium salt is coupled with aniline to form p-aminoazobenzene yellow dye.

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Exercises

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Q. Methylamine in water reacts with ferric

chloride to precipitate hydrated ferric oxide.

Methylamine, being basic, reacts with

water to produce OH ions by accepting
H+ ions from water. Then, OH ion reacts
with Fe3+ ion to form a precipitate of
hydrated ferric oxide.

Q. Amines are less acidic than alcohols of

comparable molecular masses.

Since O is more electronegative than N,

the R-O-is more stable than R-NH- ion.
Hence, alcohols are more acidic than
amines.