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Amines ppt

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cloudy.heather03
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Amines

Chapter 13
What is the use of this medicine?
Amine

• Derivatives of ammonia, obtained by replacement of one, two or all


the three hydrogen atoms by alkyl and/or aryl groups.
Structure of Amines
• Nitrogen atom is trivalent with a lone pair
of electrons.

• Nitrogen is sp³ hybridized.

• Geometry: Trigonal pyramidal

• Due to lone pair of electrons, the bond


angle decreases from the tetrahedral
angle.
Classification of amines
Nomenclature

• Primary amines are named as alkanamines.

Example: Methanamine; ethanamine

• is named as: ethane-1,2-diamine

Note that the ‘e’ of alkane is retained when two or more amine group is
present.

• For secondary & tertiary amine, the locant ‘N’ is used.


LET’S PRACTICE
LET’S PRACTICE
S.No 2.5 (H.W)
IUPAC Nomenclature
• Exercise 13.1
Preparation of Amines
Reduction of nitro compounds

Reduction with Fe and HCl is preferred because FeCl2 formed gets


hydrolysed to release HCl. So, only small amount of HCl is needed initially.
Ammonolysis of alkyl halide
• Alkyl or benzyl halide on reaction with an ethanolic solution of ammonia
undergoes nucleophilic substitution reaction.
• Here, the halogen atom is replaced by an amino (–NH₂) group.
• This reaction is called ammonolysis.
Ammonolysis of alkyl halide
(contd.)
• Free amine can be obtained from the ammonium salt by treatment with a strong

base.

• DISADVANTAGE: a mixture of primary, secondary, tertiary amines and quaternary

ammonium salt is obtained.

• Primary amine is the major product if excess ammonia is used.

• Order of reactivity of halides with amines: RI > RBr > RCl


Reduction of nitriles
• Reagents: LiAlH₄ or catalytic hydrogenation
Reduction of amides
Gabriel phthalimide synthesis
• Product: Primary amine
Q) Aniline cannot be prepared
by Gabriel Phthalimide
synthesis. Why?

• Aromatic primary amines cannot be prepared by this method because


aryl halides do not undergo nucleophilic substitution with the anion
formed by phthalimide.
Hoffmann bromamide degradation
reaction
• Product: Amine with one less carbon atom
• Migration of an alkyl or aryl group takes place from carbonyl carbon
of the amide to the nitrogen atom.
Physical properties
• Lower aliphatic amines are gases with fishy odour.

• Primary amines with three or more carbon atoms are liquid.

• Aniline and other arylamines 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.

• Amines are soluble in organic solvents like alcohol, ether and benzene.
Boiling point of amine
• Order of boiling points of isomeric amines is as follows:

• This is due to the extent of intermolecular hydrogen bonding which is maximum


for primary amine due to two H-atoms available.
Chemical
Reactions
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.
Why aliphatic amines are stronger
bases than ammonia?

• Aliphatic amines are stronger bases than ammonia due to +I effect of


alkyl groups leading to high electron density on the nitrogen atom.
Why aromatic amines are weaker
bases than ammonia?

• Aromatic amines are weaker bases than ammonia due to the electron
withdrawing nature of the aryl group.
Basicity in gaseous phase

• Substituted ammonium ion formed from


the amine gets stabilised due to dispersal
of the positive charge by the +I effect of
the alkyl group.

• Thus, order of basicity:


Basicity in aqueous phase
• Substituted ammonium ion gets
stabilized by +I effect.
• Substituted ammonium ion gets
stabilized by solvation.
• Bulky groups will create steric
hinderance to H-bonding.

• Thus, order of basicity:


Acylation

• 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.
Carbylamine reaction
(isocyanide test)
• Only for aliphatic and aromatic primary amines.
• Isocyanides or carbylamines are foul smelling substances.
• Used to distinguish primary amines from secondary and tertiary amines.
Reaction with arylsulphonyl
chloride
(Hinsberg’s test)
• Hinsberg’s reagent: benzenesulphonyl chloride
• Distinguishes between primary, secondary and tertiary amines.

 Tertiary amines do
not react with
benzenesulphonyl
chloride.
 p-toluenesulphonyl
chloride can also be
used.
Reaction with nitrous acid
• Primary aliphatic amine: (unstable diazonium salt)

• Aromatic amine: (stable diazonium salt at low temperature)


Electrophilic substitution
• The –NH₂ group is ortho and para directing and a powerful activating group.

Monosubstitution by
protecting amine
group:
Nitration
• In the strongly acidic medium, aniline is protonated to form the
anilinium ion which is meta directing.
Sulphonation
Aniline does not undergo Friedel-
Crafts reaction. Why?
• Aniline does not undergo Friedel-Crafts reaction (alkylation and
acylation) 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.
DIAZONIUM SALTS
Stability

• Primary aliphatic amines form highly unstable alkyldiazonium salts.

• Primary aromatic amines form arenediazonium salts which are stable


for a short time in solution at low temperatures due to resonance.
Preparation of Diazonium Salts

Diazotisation:
Physical properties
Benzenediazonium chloride:
Colourless crystalline solid
Soluble in water
Stable in cold
Reacts with water when warmed
Decomposes easily in the dry state
Benzenediazonium fluoroborate is water insoluble and stable at room
temperature
Chemical Reactions
Sandmeyer reaction:
Gatterman reaction
• Reaction with KI:

• Reaction with HBF₄:


Formation of benzene:

Formation of phenol:

Formation of nitrobenzene:
Coupling reaction
(azo products)
• Azo compounds are coloured and used as dyes.
• Extended conjugate system
• Electrophilic substitution reaction
S.No 2.6 (H.W)
Conversions
• Exercise 13.5; 13.8; 13.9; 13.11

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