Magical Chemistry @ FTA ,+2 HSS/VHSS - Amines

AMINES
XII ORGANIC CHEMISTRY CHAPTER 4

Amines can be considered as derivatives of ammonia,obtained by replacement of one, two or all

the three hydrogen atoms by alkyl and/or aryl groups.
For example:

Classification
Amines are classified as primary (1 o ), secondary (2 o ) and tertiary (3 o ) depending upon the
number of hydrogen atoms replaced by alkyl or aryl groups in ammonia molecule.

1. Primary amines (10) Ammonia derivatives in which 1 hydrogen atom is replaced. It is

characterized by the general formula RNH2.

Eg: CH3NH2, C2H5NH2, C6H5NH2 etc.

2. Secondary amines (20) Ammonia derivatives in which 2 hydrogen atoms are replaced. It is
characterized by the general formula R2NH.

Eg: (CH3)2NH, (C2H5)2NH, (C6H5)2NH etc.

3. Tertiary amines (30) Ammonia derivatives in which 3 hydrogen atoms are replaced.It is
characterized by the general formula R3N.

Eg: (CH3)3N, (C2H5)3N, (C6H5)3N etc.

Nomenclature

In IUPAC system, amines are named as alkanamines, derived by replacement of ‘e’ of alkane by
the word amine.
For example, CH 3 NH 2 is named as methanamine.

 Aliphatic 10 amines are named as alkanamines or amino alkanes.

 In the case of 20 and 30 amines, the word N-alkyl or N,N-dialkyl is prefixed to the word
aminoalkane.

 Aromatic amines are named as amino benzene or benzenamine.

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PREPARATION OF AMINES
1. Reduction of nitro compounds

 Nitro compounds are reduced to amine by passing hydrogen gas in the presence of finely
divided Ni, Pt, Pd or with Sn and HCl. also by reduction with metals in acidic medium
Example Sn in HCl

2. Ammonolysis of alkyl halides

The process of cleavage of the C–X bond of alkyl halide by ammonia molecule is known as
ammonolysis. The reaction is carried out in a sealed tube at 373 K. Here ethanolic solution of ammonia is

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used.The primary amine thus obtained behaves as a nucleophile and can further react with alkyl halide to
form secondary and tertiary amines, and finally quaternary ammonium salt.

NH3+ R-X RNH2 + HX

Mechanism

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. The order of reactivity of halides with amines is RI > RBr >Rcl.
3. Reduction of nitriles
Nitriles on reduction with lithium aluminium hydride (LiAlH 4 ) 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. 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. Aromatic primary amines
cannot be prepared by this method because aryl halides do not undergo nucleophilic substitution with
the anion formed by phthalimide.

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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. In this degradation reaction, migration
of an alkyl or aryl group takes place from carbonyl carbon of the amide to the nitrogen atom. The amine
so formed contains one carbon less than that present in the amide.

Physical Properties
• The lower aliphatic amines are gases with fishy odour.
• Primary amines with three or more carbon atoms are liquid and still higher ones are solid.
• Aniline and other aryl amines are usually colourless but get coloured on storage due to
atmospheric oxidation.
• Lower aliphatic amines are soluble in water because they can form hydrogen bonds with water
molecules.
• Primary and secondary amines are engaged in intermolecular association due to hydrogen
bonding between nitrogen of one and hydrogen of another molecule
• The order of boiling points of isomeric amines is as follows: Primary > Secondary > Tertiary
Chemical Reactions
Difference in electronegativity between nitrogen and hydrogen atoms and the presence of
unshared pair of electrons over the nitrogen atom makes amines reactive.

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.

The reaction of amines with mineral acids to form ammonium salts shows that these are basic in
nature. Amines have an unshared pair of electrons on nitrogen atom due to which they behave as Lewis
base.

Comparison of basic character of aliphatic and aromatic amines

Aliphatic amines are stronger bases than ammonia. Or alkylamines are stronger bases than
ammonia. Or methyl amine is more basic than ammonia.
This is due to the +I effect of alkyl group.This increases the electron density on nitrogen atom and
facilitates protonation. Due to the electron releasing nature of alkyl group, it (R) pushes electrons

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towards nitrogen and thus makes the unshared electron pair more available for sharing with the proton
of the acid.That is + I effect of the mehyl group reduces the electron density on nitrogen.

Aromatic amines are weaker bases than ammonia. Or Aniline is less basic than ammonia
Because, the lone pair of electrons on the nitrogen atom enters into resonance with the  electron
of the benzene ring. As a result, the availability of the lone pair of electrons on the ‘N’ atom is decreased
and thus makes the unshared electron pair less available for sharing with the proton of the acid. That is
- I effect of the phenyl group reduces the electron density on nitrogen.

Comparison of basic strength of aliphatic methyl amines

The +I effect of methyl group will increase the electron density on nitrogen.With increase in the
number of alkyl groups , the basic nature of aliphatic amines should increase.Therefore, its basic
character should increase in the order
10 amines < 20 amines < 30 amines
stable
 30 amines are unexpectedly less basic due to two factors.
Steric factors:- Addition of proton increases crowding around nitrogen and causes strain. This strain is
maximum in 30 amines.As a result, it will not readily undergo protonation.
Solvation effect:- The +vely charged ion formed by protonation must be stabilized by solvation.Due
to the large size of the protonated 30 amines, they are less solvated.Therefore, 30 amines are less stable.
2. Alkylation
Amines react with alkyl halides to form
quarternary ammonium salt.

3. Acylation Aliphatic and aromatic primary and secondary amines react with acid chlorides,
anhydrides and esters by nucleophilic substitution reaction. This reaction is known as acylation and
benzoylation respectively.

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Amines react with acetyl chloride in the presence of pyridine to form acetyl derivatives is called
as acylation. ( 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.)

Amines react with benzoyl chloride in the presence of NaOH to form benzoyl derivatives called as
benzoylation

4. Carbylamine reaction
Aliphatic and aromatic primary amines on heating with chloroform and ethanolic potassium
hydroxide form isocyanides or carbylamines which are foul smelling substances. This reaction is
known as carbylamine reaction or isocyanide test and is used as a test for primary amines.
Secondary and tertiary amines do not show this reaction.

5. Reaction with nitrous acid

Primary aliphatic amines react with nitrous acid to form aliphatic diazonium salts which being
unstable, liberate nitrogen gas quantitatively and alcohols are formed. Quantitative evolution of
nitrogen is used in estimation of amino acids and proteins.

Aromatic amines react with nitrous acid at low temperatures (273-278 K) to form diazonium salts,
This reaction is called as diazotisation

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6. Hinsberg’s Test - Reaction with Benzene sulphonyl chloride (C6H5SO2Cl)

Benzenesulphonyl chloride (C6H5SO2Cl), which is also known as Hinsberg’s reagent, reacts with primary
and secondary amines to form sulphonamides.
(a) The reaction of benzene sulphonyl chloride with primary amine yields N-ethyl benzene sulphonyl
amide.

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) In the reaction with secondary amine, N,N-diethyl-benzene sulphonamide is formed.

Since N, N-diethyl benzene sulphonamide does not contain any hydrogen atom attached to
nitrogen atom, it is not acidic and hence insoluble in alkali.
(c) Tertiary amines do not react with benzene sulphonyl chloride. This property of amines reacting with
benzene sulphonyl chloride in a different manner is used for the distinction of primary, secondary and
tertiary amines and also for the separation of a mixture of amines. However, these days benzene
sulphonyl chloride is replaced by p-toluene sulphonyl chloride
7. Electrophilic substitution
Ortho- and para-positions to the –NH 2 group become centres of high electron density.
Thus –NH 2 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-tribromo aniline.

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If we have to prepare mono substituted aniline derivative, how can the activating effect of –NH 2
group be controlled ?
This can be done by protecting the -NH 2 group by acetylation with acetic anhydride, then
carrying out the desired substitution followed by hydrolysis of the substituted amide to the substituted
amine.

(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.

However, by protecting the –NH 2 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 hydrogen sulphate
which on heating with sulphuric acid at 453-473K produces p-amino benzene sulphonic acid,
commonly known as sulphanilic acid, as the major product.

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Aniline does not undergo Friedel-Crafts reaction (alkylation andacetylation) 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

II. DIAZONIUM SALTS

+
The diazonium salts have the general formula R N 2 X- where R stands for an aryl group and X
ion may be Cl- Br-, HSO4 − 4 , BF 4 − , etc. The N 2 group is called diazonium group.
For example,
C 6 H 5 N 2+ Cl- is named as benzene diazonium chloride and
C 6 H 5 N 2+ HSO 4- is known as benzene diazonium hydrogen sulphate.
Method of Preparation of diazonium Salts
Benzene diazonium chloride is prepared by the reaction of aniline with nitrous acid at
273-278K. Nitrous acid is produced in the reaction mixture by the reaction of sodium nitrite with
hydrochloric acid. The conversion of primary aromatic amines into diazonium salts is known as
diazotisation.

Physical Properties Benzenediazonium chloride is a colourless crystalline solid.

Chemical Reactions
The reactions of diazonium salts can be broadly divided into two categories, namely (A) reactions
involving displacement of nitrogen and (B) reactions involving retention of diazo group.
A. Reactions involving displacement of nitrogen
Diazonium group being a very good leaving group, is substituted by other 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.
1.Sandmeyer reaction. (Replacement by halide or cyanide ion):
The Cl- , Br- and CN- nucleophiles can easily be introduced in the benzene ring in the presence of
Cu(I) ion. This reaction is called Sandmeyer reaction.

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2.Gatterman reaction.
The chlorine or bromine can also be introduced in the benzene ring by treating the
diazonium salt solution with corresponding halogen acid in the presence of copper powder.

2. Replacement by iodide ion: Iodine is not easily introduced into the benzene ring directly, but, when
the diazonium salt solution is treated with potassium iodide, iodo benzene is formed.

3. Replacement by fluoride ion: When arene diazonium chloride is treated with fluoro boric acid, arene
diazonium fluoro borate is precipitated which on heating decomposes to yield aryl fluoride.

4. Replacement by H:
Certain mild reducing agents like hypo phosphorous acid (phosphinic acid) or ethanol reduce
diazonium salts to arenes and themselves get oxidised to phosphorous acid and ethanal, respectively.

5. Replacement by hydroxyl group: If the temperature of the diazonium salt solution is allowed to rise
upto 283 K, the salt gets hydrolysed to phenol.

6. Replacement by –NO2 group: When diazonium fluoroborate is heated 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
The azo products obtained have an extended conjugate system having both the aromatic
rings joined through the –N=N– bond. These compounds are often coloured and are used as dyes.

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Benzene diazonium chloride reacts with phenol in which the phenol molecule at its para position
is coupled with the diazonium salt to form p-hydroxy azo benzene. This type of reaction is known as
coupling reaction.
Similarly the reaction of diazonium salt with aniline yields p-amino azobenzene. This is an
example of electrophilic substitution reaction.

How will you convert 4-nitrotoluene to 2-bromobenzoic acid ?

THE END

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