Amines

 Amines are alkyl or aryl derivative of ammonia.

 They are basic in character.
 Amines are present in structure of many natural compounds
like proteins, vitamins, hormones and many plant products like
nicotine.
1Classification of amines : Classification of Amines:
 Amines are classified as primary (1°), secondary (2°) and tertiary
(3°) amines.
 Their structures are obtained by replacing one, two or all three
hydrogen atoms of NH3 molecule by alkyl / aryl groups .
 Secondary and tertiary amines are further classified as simple /
symmetrical amines and
mixed / unsymmetrical amines.

 When all the alkyl or aryl groups on nitrogen are same, it is a simple
amine.
 If these groups are different, then the amine is a mixed amine.
3
 Amines are also divided into two major classes, namely, aliphatic and aromatic
amines on the basis of nature of the groups attached to the nitrogen
atom

AMINES

Aliphatic amines Aromatic amines

CH3 – NH2 methyl amine aniline

 13.2 : Nomenclature of Amines
1. Common names of aliphatic amines are given by writing the name of alkyl
group followed
by suffix-amine, that is, ‘alkyl amine’.

2. In the case of mixed amines, the names of alkyl groups are written in
alphabetical order.

3. If two or three identical alkyl groups are attached to nitrogen atom, the
prefix ‘di-’ or ‘tri-’
is added before the name of alkyl group.

4. The parent aryl amine, C6H5-NH2, is named as aniline.

5. Other aromatic amines are named as derivatives of aniline.

13.2.2 IUPAC names

1. In IUPAC system, primary amines are named by replacing the ending ‘e’ of
the parent alkane by suffix -amine (alkanamine).
2. A locant indicating the position of amino group is added before the suffix
amine.
3. When two or more amino groups are present, the prefix ‘di-’, ‘tri-’ etc. are
used with proper locant. In this case the ending ‘e’ of parent alkane is retained.
4. Secondary or tertiary amines are named as N-substituted derivatives of
primary amines.
5. The largest alkyl group attached to nitrogen is taken as the parent alkane and
other alkyl groups as N-substituents.
6. While naming aryl amines ending ‘e’ of arenes is replaced by ‘amine’.
7. The common name of aniline is also accepted by IUPAC .
7
 Preparation of Amines
By ammonolysis of alkyl halides :
 When alkyl halide is heated with alcoholic solution of excess ammonia it
undergoes nucleophilic substitution reaction in which the halogen atom is replaced by
an amino
(-NH2) group to form primary amine. This process is known as ammonolysis.
 This reaction is also known as alkylation of ammonia.
 This reaction is carried out in a sealed tube at 373 K.
 It may be noted that the primary amine obtained in the 1st step is stronger
nucleophile than ammonia. Hence, it further reacts with alkyl halide to form secondary
∆
and tertiary amines and finally quaternary ammonium salt if NH3 is not used in large
excess. R-X + NH3(alc) R-NH2
(excess) 10 amine

 The order of reactivity of alkyl halides with ammonia is R-I > R-Br > R-
Cl.
13.3.2 : Reduction of nitro compounds

Aliphatic and aromatic nitro compounds can be reduced to primary amines by using
metal-acid mixture (Sn/HCl or Fe/HCl or Zn/HCl) or catalytic hydrogenation (H2/Ni or
Pt or Pd) or LiAlH4 in ether.

Sn/HCl
R-NO2 + 6[H] R-NH2 + 2H2O
Reduction of alkyl cyanide (alkanenitriles))
13.3.3 :
Primary amines can be obtained by the reduction of alkyl cyanide with sodium
and ethanol.
This is known as Mendius reduction.
Na +C 2 H 5 OH or
The reaction can also be brought about by lithium aluminium hydride.
R-C N + 4[H] LiAlH 4 R-CH2-NH2
Alkyl cyanide
 By Reduction of amides :
Primary amines having same number of carbon atoms can be
obtained by the reduction of amides by LiAlH4 in ether or by Na /C2H5OH.

LiAlH 4 /
ether
or Na /C H
CH3-C-NH2 + 4[H] CH3-CH2-NH2
2
OH 5
O
(Acetamide) (Ethylamine)

13.3.5
Gabriel phthalimide synthesis :

This method is used for the synthesis of primary amine. It involves the following
three stages.
i. Formation of potassium salt of phthalimide from phthalimide on reaction with
alcoholic
potassium hydroxide.
ii. Formation of N-alkyl phthalimide from the potassium salt by reaction with alkyl
halide.
 Aromatic amines cannot be prepared by this method because aryl halides do
not undergo nucleophilic substitution with the anion formed by phthalimide.
15
16
 By Hofmann degradation (Hofmann bromamide degradation / Hofmann rearrangement /
Hofmann hypobromite degradation) :
 This is a good laboratory method for the conversion of an amide into primary amine
containing one carbon less.
 The reaction is brought about by warming the amide with bromine and concentrated

∆
aqueous KOH solution.
R-C-NH2 + Br2 + 4KOH (aq) R-NH2 + 2KBr+ K2CO3 + 2H2O
O
(Amide) (1° amine)

∆
For example :
CH3-C-NH2 + Br2 + 4KOH (aq) CH3-NH2 + 2KBr + K2CO3 + 2H2O
O
(Acetamide) (methyl amine)
 The overall result is removal of the carbonyl ( C=O )group from the amide.
 It is a step down reaction , as the product contains one carbon atom less than the
original amide.
reactant
 Physical properties of Amines:
Intermolecular forces, boiling points and solubility:
Intermolecular forces:
1.
 The N-H bond in amines is polar because the electronegativities of Nitrogen (3.0)
and Hydrogen (2.1) are different.

 Due to the polar nature of N-H bond primary and secondary amines have
intermolecular hydrogen bonding.

 The intermolecular hydrogen bonding is to greater extent in primary amine than in

secondary amines, because primary amines have two hydrogen atoms bonded to nitrogen
for hydrogen bond formation.

 While tertiary amines do not have intermolecular hydrogen bonding as there is no hydrogen

atom on nitrogen of tertiary amines

  
H
H  R N-H
R-N-H    N -R
H H
Hydrogen bond

H-N-R
H

 But due to polar N-C bonds, tertiary amines are polar molecules, and have
intermolecular dipole-dipole attractive forces.

 Thus intermolecular forces of attraction are strongest in primary amines

and
weakest in tertiary amines.
2.BOILING POINT :
The observed order of boiling points of isomeric amines is :
primary amine > secondary amine > tertiary amine. It can be explained on the basis of the
intermolecular forces in them.
3. STATE :
The lower aliphatic amines are gases with fishy odour, middle members are liquids and higher members are
solids under ordinary temperature and pressure.
Aniline and other arylamines are usually colourless liquids but get coloured as they are
easily oxidised by air.
4.SOLUBILITY :
Due to their ability to form hydrogen bond with water molecule, lower aliphatic amines are soluble in water
Solubility of amines decreases with increase in molar mass of amines due to increase in size of hydrophobic
alkyl group.
Aromatic amines and higher aliphatic amines are insoluble in water
 Since N-H bonds in amines are less polar than O-H bond in alcohol, the
water solubilities of alcohols, amines and alkanes of comparable molar mass in water are
in decreasing order:
Alcohols > Amines > Alkanes.
The order of boiling points of alkanes, amines, alcohols and carboxylic acid
of comparable
molar mass is as follows :
Alkanes < Amines < Alcohols < Carboxylic acid.
Boiling points of alkane, alcohol and amines of similar molar masses

Sr. No COMPOUND MOLAR MASS B.P. (K)

1 n-C4H9NH2 73 350.8

2 (C2H5)2NH 73 329.3

3 C2H5N(CH3)2 73 310.5

4 C2H5COOH 74 414.4

5 n-C4H9OH 74 390.3

6 (CH3)3C-NH2 73 318.15
7 C2H5CH(CH3)2 72 300.8
 Basicity of Amines
 The basic nature of amines is due to presence of a lone pair of electrons on the
nitrogen atom.
 In terms of Lewis theory, amines are bases because they can share a lone pair of
electrons
on ‘N’ atom with an electron deficient species.
 For example: Trimethylamine shares its lone pair of electrons with the electron
deficient boron trifluoride.

 Basic strength of amines is expressed quantitatively as Kb or pKb value.

 In terms of Lowry-Bronsted theory, the basic nature of amines is explained by writing the
following equilibrium.

 In this equilibrium amine accepts H⊕, hence an amine is a Lowry-Bronsted base.

 For stronger base, this equilibrium shifts towards right, thereby the Kb value is larger and pKb
value is smaller and vice versa .
 Basic strength of aliphatic amines :
The trend in the observed pKb values and basic strength of 1°, 2°, 3° amines and NH3 can
be represented as shown below :
Order of pKb values:
NH3 > R-NH2 > R2NH < R3N
Order of basic strength :
NH3 < R-NH2 < R2NH > R3N Thus as per the observed pKb values of the
aliphatic amines, secondary amines are the strongest bases.
 Basic strength increases as we move from NH3 to R-NH2 and from R-NH2 to R2NH,
but basic strength decreases as we move from R2NH to R3N.
 The basic strength and the corresponding pKb value depends upon the position of the equilibrium

Greater the stabilization of the conjugate acid more on right side the equilibrium will lie
and stronger will be the base and smaller will be its pKb value.
 An alkyl group exerts electron releasing inductive effect (+I) which stabilizes positive
charge on atom bonded to it.



 As we move from conjugate acid of ammonia ( NH ) to that of tertiary amine (R NH ),
4 3
the number of alkyl groups (R) bonded to Nitrogen goes on increasing steadily.

 This results in increasing stabilization of the conjugate acids and thereby an

increasing order of basic strength is expected.
   
NH
Order
4 < of stabilization:
RNH3 < R2NH2 < R3NH
 Basicity of amines is related to the structural effects which influence stabilization of
various species.

 Greater is the stabilization of the protonated amine, that is, the conjugate acid, greater is
the basicity of the amine.

a. Influence of +I effect on stabilization of conjugate acids of aliphatic amines and NH3

can be represented as shown below :
Expected order of basic strength:
NH3 < R-NH2 < R2NH < R3N
 The expected order of basic strength on the basis of +I effect differs from the observed
order
 It is seen that the observed increasing basic strength from ammonia to amine and from
1° amine to 2° amine is explained on the basis of increased stabilization of conjugate acids

 by
However, decreased basic strength of 3° amine implies that the conjugate acid of 3° amine
is 
less stabilized
+I effect even though
of increased theof+Ialkyl
number effect(R)
ofgroups.
three alkyl groups R3NH is expected to be
in large.

 This is suggestive of existence of another influencing factor in stabilization of

conjugate
acids of amines.
 b. Influence of solvation by water on stabilization of conjugate acids of
aliphatic
amines and ammonia can be represented as shown below:

Solvation of Solvation of Solvation of Solvation of

Ammonium ion primary amine secondary amine tertiary amine
c. Combined influence of +I effect and solvation on stabilization if conjugate acids of
aliphatic amines decides the observed basic strength and pKb value.

 These two influencing factors operate in opposite directions.

 The net results is that as we move from NH3 to RNH2 to R2NH, the basic strength
increases due to better stabilization of the corresponding conjugate acids.

 But 3° amine is weaker base than 2° amine because the stabilization of conjugate acid
of 3° amine by solvation is very poor.
 Basicity of arylamines :

 From the pKb values we understand that aryl amines in general are weaker bases
than ammonia and aliphatic amines.

 Strength of arylamines is explained in accordance with Lowery Bronsted theory by

writing the following equilibrium

 Here, both the species base and conjugate acid, are resonance stabilized but to
different extent.
 In aryl amines, the -NH2 group is attached directly to an aromatic ring. The lone pair

of electrons on nitrogen is conjugated to the aromatic ring and is less available for
protonation.
 Aniline is resonance stabilized by the following five resonance structures.
 On the other hand anilinium ion obtained by accepting a proton does not have lone
pair of electrons on nitrogen.
 Hence it can be stabilized by only two resonance structures and therefore less
stabilized than aniline.

 As a result the equilibrium is shifted towards left side. This makes aniline
(and also other arylamines) weaker bases than aliphatic amines and ammonia.
Chemical properties of amines

Chemical
Properties of
Amines

34
 1. Laboratory test for amines :
13.6
a. Test for amines as the ‘base’ :
 All amines 1°, 2° and 3° are basic compounds. Aqueous solution of water
soluble amines turns red litmus blue.
 The ‘basic’ nature of amines is detected in laboratory by reaction with aqueous
solution of strong mineral acid HCl.

Water insoluble amine dissolves in aqueous HCl due to

formation of water soluble substituted ammonium chloride, which on reaction with
excess aqueous NaOH regenerates the original insoluble amine.
b. Diazotization reaction/ Orange dye
test:
 In a sample of aromatic primary amine, 1-2 mL of concentrated HCl is added.

 The aqueous solution of NaNO2 is added with cooling.

 This solution is transferred to a test tube containing solution of - naphthol in

NaOH. Formation of orange dye indicates presence of aromatic primary amino
group.

 (It may be noted that temperature of all the solutions and reaction mixtures is
maintained near 0°C throughout the reaction).

 The reaction involved in this test will be discussed in section 13.6.5. ( on

slide number
42 )
 Chemical properties of amines
Alkylation of amines:
Hofmann’s exhaustive alkylation:

 When a primary amine is heated with excess of primary alkyl halide it gives a mixture
of
secondary amine, tertiary amine along with tetra alkyl ammonium

R−X R−X
halide .

R-NH2 R−X
−HX −HX
R2NH R3 N R4NX
(1° Amine)−HX (2° Amine) (3° (Tetraalky
Amine) l
 ammoniu
If excess of alkyl halide is used tetra alkyl ammonium halide is obtained as
m halide)
major product. The reaction is known as exhaustive alkylation of amines.
Quaternary ammonium

salts :The tetraalkylammonium halides are called quaternary ammonium salts which are
crystalline solids.
 They are the derivatives of ammonium salts in which all the four hydrogen
atoms attached to nitrogen in NH4 are replaced by four alkyl groups (same or
different).
 Primary, secondary and tertiary amines consume three, two and one moles of
alkyl
halide respectively to get converted into quaternary ammonium salt.
 This reaction is carried out in presence of mild base NaHCO3, to neutralize the
large quantity of HX formed.
 If the alkyl halide is methyl iodide, the reaction is called exhaustive methylation of
amines.
∆
 For example:
 WhenCH methylamine
-NH + CHis heated
-I with(CH
excess methyl iodide, it gives
3)2NH + HI
∆
3 2 3
tetramethyl ammonium iodide.
(CH3)2NH + CH3-I (CH3)3N + HI
(CH3)3N + CH3-I (CH3)4N +I
 Hofmann Elimination :

 When tetraalkylammonium halide is heated with moist silver oxide, it gives quaternary
ammonium hydroxide which is a deliquescent crystalline solid, and strongly basic like
NaOH or KOH.

 Quaternary ammonium hydroxides on strong heating undergo -elimination to

give an alkene; the reaction is called Hofmann elimination.

 The least substituted alkene is obtained as major product (in contrast to Saytzeff
elimination)

 For example:
Acylation of amines :

 Aliphatic and aromatic primary and secondary amines undergo acylation reaction.
 These amines contain replaceable hydrogen atoms (positively polarised H) on
the nitrogen atom.
 These hydrogen atoms are replaced by acyl groups such as acetyl group.

 On reaction of amines with acetyl chloride or acetic anhydride, acetyl

derivative of amine is obtained. It is also called amide.

 Amide is less basic than the amine.

 Acylation is a nucleophilic substitution reaction.

 The reaction is carried out in presence of strong base like pyridine, which
neutralizes
the acid produced during the reaction. For example---
iii) Benzoyl chloride also gives similar reaction with amines.
Carbylamine reaction:

 Aliphatic or aromatic primary amines on heating with chloroform give

foul (offensive) smelling products called alkyl/aryl isocyanides or
carbylamines.
 This reaction is a test for primary amines.
 Secondary and tertiary amines do not∆ give this test.
R-NH + CHCl + 3KOH
2 3 R-NC + 3KCl + 3H O 2
(Primary amine) (Alkyl isocyanide)

Reaction with nitrous acid:

 Primary, secondary and tertiary amines react differently with nitrous acid.
 Reactions of only primary amines will be considered here.
 Nitrous acid is an unstable compound.
 Hence it is prepared in situ by adding aqueous sodium nitrite to hydrochloric
acid .
a. Aliphatic primary amines on reaction with nitrous acid form aliphatic diazonium salt
which is very unstable intermediates so decompose immediately by the reaction with
solvent water and corresponding alcohol is formed as the product and nitrogen gas is
liberated.

273−278 K -
H2 O
+

(NaNO +
R-NH2 + HNO2  R-N2 Cl  R-OH + N2 + HCl
2
HCl) (alkyl diazonium chloride) (alcohol)

b. Aromatic primary amines react with nitrous acid to form diazonium salts which

273−278
have reasonable stability at 273 K.
K
+ -
(NaNO +
C6H 5-NH 2 + HNO2 C6H5-N NCl
2
 HCl) (benzene diazonium chloride)
Aryl diazonium salts under go resonance stabilized and is useful intermediates to obtain
a variety of products.

(Resonating structures of aryl diazonium

salt )
Reactions of arene diazonium salts:
* Aryl diazonium salt show two type of reactions
1) Reactions involving displacement of diazo group
2) Reactions involving retention of diazo group: (Coupling reactions) :

13.7 Reactions of arene diazonium salts:

o The diazonium group (-N2 ) is a very good leaving group due to the positive
charge on nitrogen atom bonded to aromatic ring.

o As a result, the arene diazonium salts undergo nucleophilic substitution

reaction with a variety of nucleophiles.

o Next Table shows reactions of diazonium salts involving displacement of diazo

group.
Reaction with fluoroboric acid :

 Arene diazonium salt on reaction with fluoroboric acid gives precipitate of diazonium
fluoroborate which on heating decomposes to yield fluoroarene.
 On the other hand when heated with aqueous sodium nitrite in presence of copper it
gives nitroarene.

Fluoroarene Nitroarene
Reactions involving retention of diazo group:
(Coupling reactions) :
 Azo compounds are brightly coloured and are used as dyes.
 Arenediazonium salts when treated with certain reactive aromatic compounds
such as phenols or aromatic amines, give azo compounds.

 This is an example of electrophilic aromatic substitution reaction.

 Here the electrophiles are positively charged diazonium ions.

 These have extended conjugated system of double bonds in which two aromatic rings
are joined through azo group (-N=N-) . This reaction is called azo coupling.

 Substitution usually occurs para to the ring activating group.

 Azo coupling with -naphthol in NaOH is used as a confirmatory test for primary
amines.
aromatic
 For example:
1) Reaction with phenol :
Benzenediazonium chloride reacts with phenol in mild alkaline medium
to
give p-Hydroxy-azobenzene (orange dye).
Reaction with arenesulfonyl chloride: (Hinsberg’s test) :

 Benzenesulfonyl chloride (C6H5SO2Cl) is known as Hinsberg’s reagent.

a. Alkyl amine (primary amine) reacts with benzenesulfonyl chloride to

form N-alkyl benzenesulfonyl amide. The hydrogen attached to nitrogen in
sulfonamide of alkanamine (a primary amine) is strongly acidic. Hence it is
soluble in alkali. Example:
Ethyl amine (primary amine) reacts with benzenesulfonyl chloride to
form N-ethylbenzenesulfonyl amide (N-ethylbenzenesulfonamide ) .

Ethyl amine N-Ethylbenzenesulfonamide ,

Soluble in alkali
The hydrogen attached to nitrogen in sulphonamide of ethanamine is strongly
Hence it is soluble in alkali
acidic.
 b. Dialkyl amine reacts with benzenesulfonyl chloride to give N, N- dilkylbenzene
sulfonamide.
The obtained N, N-dialkylbenzenesulfonamide does not contain any H-atom
attached to nitrogen atom. Hence it is not acidic and does not dissolve in alkali.
Example :
Diethyl amine reacts with benzenesulfonyl chloride to give N, N-
diethylbenzenesulfonamide.

Benzene sulphonyl Diethyl amine N, N-diethylbenzenesulfonamide ,

chloride Insoluble in alkali

N, N-diethylbenzenesulfonamide does not contain any H-atom attached to nitrogen atom.

Hence it is not acidic and does not dissolve in alkali.
c. Trialkyl amine does not contain any hydrogen atom attached to nitrogen , hence
does not react with benzenesulfonyl chloride
Electrophilic aromatic substitution in aromatic amines :

 Amino group is ortho and para directing and powerful ring activating group.
 As a result aromatic amines readily undergo electrophilic substitution
reactions.
a. Bromination:
Aniline reacts with bromine water at room temperature to give a white precipitate
of 2, 4, 6 - tribromoaniline.
b. Nitration :
 Direct nitration of aniline yields a mixture of ortho, meta and para nitroanilines.
 In acidic medium -NH2 group is protonated to -NH3 group which is meta-directing
and deactivating.
 Hence considerable amount of m-nitroaniline is obtained.
 However, to get p-nitroaniline as
major product, -NH2 group is first
protected by
acetylation, nitration is carried out
then amide is hydrolysed.
 c. Sulphonation :
Aniline reacts with concentrated sulphuric acid to form anilinium hydrogen sulphate
which on heating with sulphuric acid at 453-473K produces p-aminobenzene sulfonic
acid (sulphanilic acid) as major product.

 Sulfanilic acid exists as a salt; called dipolar ion or zwitter ion.

 It is produced by the reaction between an acidic group and a basic group present in the
same molecule.