Chemistry 20

Chapter 8

Amines
 Amines

Amines:

• Are derivatives of ammonia NH3.

• Contain N attached to one or more alkyl (Aliphatic amine) or

aromatic groups (Aromatic amine).

-NH2 amino group

CH3-NH2 CH3-NH-CH3 NH2

 Amines

Amines are classified into three groups:

depending on the number of carbon groups bonded to nitrogen.

CH3 CH3
⏐ ⏐
CH3—NH2 CH3—NH CH3—N—CH3

Primary 1° Secondary 2° Tertiary 3°

 Naming Amines
IUPAC name – 1° amines

The same method as we did for alcohols.

- Drop the final “-e” of the parent alkane and replace it by “-amine”.

- Use a number to locate the amino group (-NH2) on the parent chain.

NH2 NH2
3 5 3 1
2
CH3-CH-CH3 CH3-CH-CH-CH3 6 4

3 2 1 1 2 4
Cl
2-propanamine 3-chloro-2-butanamine 1,6-hexanediamine
 Naming Amines
Common name

Names of alkyl groups (In alphabetical order) + “amine”

CH3—CH2—NH2 ethylamine

CH3—NH —CH3 dimethylamine

CH3
|
CH3—N—CH2—CH3 ethyldimethylamine
 Aniline (common name)

NH2

Aniline

NH2 NH2
NH2
2 1 2
1
1 2

3 3 CH3 4
3
4 CH3
Cl
NO2

4-Nitroaniline 3-Methylaniline 4-Chloro-3-methylaniline

 Naming Amines
IUPAC name – 2° and 3° amines

– Take the largest group bonded to nitrogen as the parent amine.

– Name the smaller group(s) bonded to nitrogen, and show their locations
on nitrogen by using the prefix “N”.

aniline

CH3
CH3-N-CH2-CH3 N,N-Dimethylethanamine
 Heterocyclic amines

When N is one of the atoms of a ring.

N CH3
H H

Pyrrolidine Pyridine Nicotine

 ISOMERISM IN AMINES
Four different types of isomerism are exhibited in amines –
(a) chain isomerism (b) positional isomerism
(c) metamerism (d) functional isomerism.
 ISOMERISM IN AMINES
Four different types of isomerism are exhibited in amines –
(c) metamerism (d) functional isomerism.
 METHODS OF PREPARATION
1o, 2o, 3o, 4o AMINES:
(a) Ammonolysis of Alkyl Halides
 METHODS OF PREPARATION
1o, 2o, 3o, 4o AMINES:
(a) Ammonolysis of Alkyl Halides
Ammonolysis of Alkyl Halides contd….
b. Reductive amination of Alkanals and Alkanones
 Synthesis of Amines
Preparation of Primary, Secondary, or Tertiary Amines
through Reduction of Nitriles, Oximes, and Amides
 Methods of Preparation of 1o Amines Only
(a) By the Reduction of Nitroalkanes

Boiling with tin and concentrated hydrochloric or with hydrogen

gas, under pressure, in presence of a catalyst, reduces
Nitroalkanes.
 Methods of Preparation of 1o Amines Only
(b) By Reduction of Alkyl Cyanides (Alkanenitriles)
The reaction of an alkanenitrile with reducing agents like sodium
in absolute ethanol or lithium aluminium hydride (lithium
tetrahydroaluminate (III)) in ether solution, converts the former
into a primary amine:
 Methods of Preparation of 1o Amines Only
(c) Hoffman Degradation Reaction between an Acid
Amide and Bromine / Caustic Potash
The Hoffman Degradation reactionof acid amides involves
warming of an acid amide, (RCONH2), with liquid bromine and
concentrated aqueous solution of an alkali; the product is a
primary amine:

For example:
 Physical properties of Amines

1. They have unpleasant odors (rotting fish like ammonia).

2. They are polar compounds.

Difference in electronegativity between N - H (3.0 – 2.1 = 0.9)

3. 1° and 2° amines have hydrogen bonds (N-H).

Weaker than alcohols (O-H).

3° amines do not form hydrogen bonds (no H atom).

4. Boiling points: Hydrocarbons< Amines < Alcohols

5. Almost soluble in water (hydrogen bonding).

Chemical properties of Amines
 Chemical properties of Amines

They are weak bases (like ammonia): react with acids.

(to form water-soluble salts)

H H
.. -...
N.. . ..O – H
+
CH3 + H – ..
O–H CH3 N H

H H
Ammonium salt

Some amines present in our blood and make it approximately basic (pH = 7.4).
 Chemical properties of Amines

Aliphatic amines are weak bases by comparison with inorganic bases

such as NaOH, they are strong bases among organic compounds.

Aliphatic amines are stronger bases than aromatic amines.

(slightly stronger than NH3)
relative base strength
RNH2 > NH3 > ArNH2
Kb ionization of the base in water
:Base + H2O H:Base+ + OH-
Kb = [ H:Base+ ] [ OH- ] / [ :Base ]

Kb
aliphatic amines 10-3 – 10-4
ammonia 1.8 x 10-5
anilines 10-9 or less
Why are aliphatic amines more basic than ammonia?

NH3 + H2O ⇄ NH4+ + OH-

R-NH2 + H2O ⇄ R-NH3+ + OH-

The alkyl group, -R, is an electron donating group. The

donation of electrons helps to stabilize the ammonium ion
by decreasing the positive charge, lowering the ΔH, shifting
the ionization farther to the right and increasing the basicity.
Why are aromatic amines less basic than aliphatic amines?
R-NH2 + H2O ⇄ R-NH3+ + OH-

resonance stabilization of the

free base, increases the ΔH,
shifts the ionization to the left,
decreasing base strength.
Effect of substituent groups on base strength:

Electron donating groups will stabilize the anilinium ion,

decreasing the ΔH, shifting the ionization farther to the right and
making the compound a stronger base.
Electron withdrawing groups destabilize the anilinium ion,
increasing the ΔH, shifting the ionization towards the reactants,
making the compound a weaker base.
Common substituent groups:

-NH2, -NHR, -NR2

-OH
-OR
-NHCOCH3 electron donating
-C6H5 groups
-R
-H
-X
-CHO, -COR
-SO3H electron withdrawing
-COOH, -COOR groups
-CN
-NR3+
-NO2
Number the following in decreasing order of base strength (let
#1 = most basic, etc.

4 1 5 3 2
Reaction with acids
 Examples

Complete each acid-base reaction and name the salt formed.

 Examples

Complete each acid-base reaction and name the salt formed.

Solutions:
2. Alkylation (ammonolysis of alkyl halides)
Exhaustive Methylation of Amines - Formation of
Quarternary Ammounium Salts
Acylation of Amines:
Reaction of ammonia, 1° and 2° amines with acid chloride,
anhydrides and esters to afford amides.

Primary and secondary amines (aliphatic and aromatic)

contain two and one replaceable hydrogen atom respectively
and are therefore readily acylated to yield the corresponding
(substituted) amide.

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Isocyanide (Carbylamine) Test for Primary Amine

Primary amine (aliphatic or aromatic) when warmed with

chloroform and a few drops of alcoholic KOH give
isocyanide with foul odour).

This test is used to detect the presence of a primary

amine

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Ring Substitution in Aromatic Amines
When the amino group, NH2, or the alkylamino group, -
NHR and - NR2 are present on the benzene ring, it has been found that:
(a) The ring is activated towards further substitution - that is, the amino
group is an activating group.
(b) Product orientation is ortho and para.

A product in which all the

available ortho and para
positions are taken up by the
incoming electrophile

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Reaction of Amines with Nitrous Acid

All classes of amines react with nitrous acid, HNO2, yielding

different kinds of products.
The nitrous acid is unstable and so is usually prepared in situ
(that is, as needed in the reaction medium) by the action of
dilute mineral acid (H2SO4 or HCI) on sodium or potassium
nitrite.

Reaction of Aliphatic Primary Amine with HNO2

The primary product of the reaction of an aliphatic primary
amine with HNO2 is a diazonium salt, precisely an
alkyldiazonium salt

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Reaction of Amines with Nitrous Acid (contd.)

The alkyldiazonium ion, RN2+, is unstable and immediately

decomposes into a carbonium ion R+ with the evolution of
nitrogen gas.

Subsequent reactions of the carbonium ion produce a

complicated mixture of organic products including alcohols
alkenes, ethers, and nitro alkanes

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Reaction of Aliphatic and Aromatic Secondary Amines

Secondary amines react with nitrous acid to yield

N-nitrosoamines which are yellow oils

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Reaction with Aliphatic and Aromatic Tertiary Amine
Aliphatic tertiary remain in solution in form of their salts.
Aromatic counterparts behave differently from them. The
activating effect of the - NR2 group on the benzene ring
makes an aromatic amine very reactive and is susceptible to
electrophilic attack of the nitrosonium ion(NO).
Aromatic tertiary amine thus undergo nitrosation with Nitrous
acid in the para - position

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Reaction with Primary Aromatic Amines

A primary aromatic amine, like aniline (phenylamine) reacts

with nitrous acid in the cold (0 – 5oC) to yield a diazonium (in
particular, a benzendiazonium) salt, ArN2X

Reaction of primary arylamines with nitrous acid results in the formation

of relatively stable arenediazonium salts
– This reaction occurs through the intermediacy of an N-nitrosoamine
– The N-nitrosoamine is converted to a diazonium ion

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Mechanism of the reaction 1o Aromatic Amines with HONO

44
Reaction with Primary Aromatic Amines

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Reaction with Primary Aromatic Amines

Conversion to Benzene
Diazotisation is effected using sulphuric acid and the product
run into boiling ethanol

Coupling Reactions of Diazonium Salts

Coupling reactions are those in which diazonium salts react with
certain aromatic compounds to form products of general formula
Ar - N = N - Ar, called azo compounds. The nitrogen of the
diazonium group is retained in the product;

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Coupling Reactions of Diazonium Salts (Contd.)
Azo compounds
A class, are highly coloured - they could be intensely
yellow, red, blue, orange or green depending on the structure
of the molecule.
They are very important in the dyestuff industry

(4-hydoxphenyl) azobenzene

bright yellow or red solid

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Coupling Reactions of Diazonium Salts (Contd.)
Azo compounds
The azo coupling results in compounds which are highly
conjugated
– The -SO3 -Na+ group is added to the molecule for solubility
and to link the dye to the polar fibers of wool, cotton etc.
– Orange II is made from 2-naphthol

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