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P8 RAe GCK49 DX 6 C UVfm XX

Uploaded by

premdhiman
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Amines

Amines:

(i) Derivatives of ammonia

(ii) Obtained by the replacement of one, two or all the three H-atoms of ammonia by
alkyl and/or aryl group

(iii) Structure of Amines

Nitrogen on amines is sp3 hybridised.

Geometry − Pyramidal

Example: Pyramidal shapes of trimethylamine

Classification: Primary (1 ), secondary (2 ) and tertiary (3 )

(i) If one H-atom of NH3 is replaced by R or Ar, RNH2 or ArNH2 is obtained (primary
amine, 1°).

(ii) If two H-atoms of NH3 or one H-atom of RNH2 are replaced by alkyl or aryl group
(R′), R2NH is obtained (secondary amine, 2°).
(iii) On the replacement of another hydrogen atom by alkyl or aryl group, R3N is
obtained (tertiary amine, 3°).

Nomenclature

Common System

Aliphatic amine: Named by prefixing alkyl group to amine, i.e., alkylamine. Example:
Methylamine (CH3NH2)

Secondary and tertiary amines: Prefix di- or tri- is appended before the name of alkyl
group when two or more groups are the same.

IUPAC System

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

Example: CH3NH2 − Methanamine

When more than one amino group is present −

(i) Suitable prefix such as di-, tri-, etc., is attached to amine.

(ii) ‘e’ of the suffix of hydrocarbon is retained.

(iii) Positions of −NH2 group are specified by giving numbers to the parent chain.

Example: Ethane-1, 2-diamine

(iv) or aryl amines −NH2 group is directly attached to the benzene ring

While naming arylbenzenes by IUPAC system, the suffix ‘e’ of arene is replaced by
‘amine’.

Preparation:

(i) By reduction of nitro compounds –


(ii) By ammonolysis of alkyl halides – Ammonolysis is the process of cleavage of the
C–X bond by ammonia molecule.

Primary amine obtained behaves as a nucleophile and further reacts as

Order of reactivity of halides with amines − RI > RBr > RCl

(iii) Reduction of Nitrites

(iv) Reduction of Amides

(v) Gabriel Pthalimide Synthesis: Used for the preparation of primary amine.
(vi) Hoffmann Bromamide Degradation Reaction:

Physical properties:

Solubility –
(i) Lower aliphatic amines are soluble in water, but higher amines are insoluble in
water. This is because lower amines can form H-bonds with water, but higher amines
cannot.

(ii) Solubility of amines in water decreases with increase in molar mass of amines as
the size of the hydrophobic alkyl part increases.

(iii) The order of increasing boiling points of isomeric amines is


3o amine < 2oamine < 1oamine. This because of intermolecular association of 1amines
due to H-bonding.

Chemical reactions:

(i) Basic character of amines –

The order of increasing basicity is

(a) Aromatic amines < Ammonia < Aliphatic amines

Aliphatic amines are stronger bases than ammonia due to +I effect of alkyl groups.
Aromatic amines are weaker bases than ammonia due to electron-withdrawing nature of
the aryl group.

Structure–basicity relationship of amines

The increasing order of basicity of amines in the gaseous phase is

NH3 < 1 amine < 2 amine < 3 amine

The increasing order of basic strength in the case of methyl-substituted amines and
ethyl-substituted amines in aqueous solution.

NH3 < (CH3)3 N < CH3NH2 < (CH3)2 NH

NH3 < C2H5NH2 < (C2H5)3N < (C2H5)2NH

The above order is due to the combined effect of steric hindrance of the alkyl group,
inductive effect and salvation effect.

In the case of substituted aniline, electron-withdrawing groups (– NO2, –SO3, – COOH,


– X) decrease the basicity while electron-donating groups (– OCH3, – CH3) increase
the basicity.

(ii) Alkylation

Amines undergo alkylation on reaction with alkyl halides.

Sandmeyer’s reaction
(iii) Acylation

For example:

(iv) Benzoylation − Reaction of amines with benzoyl chloride (C6H5COCl)

Carbylamines reaction (or isocyanide test) – Used as test to distinguish 1o , 2o , and


3o amines. As 2o and 3o amines do not react to this test.

Reaction with nitrous acid –Nitrous acid is prepared in situ from a mineral acid and
sodium nitrate.

Primary aliphatic amines:


Aromatic amines:

Reaction with arylsulphonyl chloride – Hinsberg’s reagent Benzenesulphonyl


chloride (C6H5SO2Cl). This reaction can be used for distinguishing and separating 1o ,
2o and 3o amines

(i) Primary amine: The amide formed is soluble in alkali because the hydrogen attached
to nitrogen is strongly acidic due to the presence of a strong electron-withdrawing
sulphonyl group.

(ii) Secondary amine: The amide formed is insoluble in alkali. As it does not contain
any hydrogen atom attached to nitrogen atom, it is not acidic.

(iii) Tertiary amines do not react with Hinsberg’s reagent.

Electrophilic substitution –

(i) Bromination: Electrophilic substitution reaction of aromatic amines is of very high


reactivity − tends to occur both at ortho and para positions.
To prepare monosubstituted aniline, −NH2 group is protected by acetylation with acetic
anhydride; then the desired substitution is carried out, followed by hydrolysis.

(ii) Nitration: In strong acidic medium, anilinium ion is formed, which is meta
directing. Hence, significant amount of meta derivative is also formed along with ortho
and para isomers.
By protecting −NH2 group by acetylation reaction, para isomer can be obtained as the
major product.

(iii) Sulphonation:

(iv) Aniline does not undergo Friedel–Crafts reaction (alkylation and acelytation).
Diazonium salts:

Preparation:

Diazotisation : The conversion of primary aromatic amines into diazonium salts.

Chemical reactions:

Reactions that involve displacement of nitrogen

(i) Replacement by halide or cyanide ion

Sandmeyer’s reaction

Gattermann reaction

Replacement by iodide ion


Replacement by fluoride ion

(ii) Replacement by NO2 group

(iii) Reactions that involve retention of diazo group:

Coupling reactions (Electrophilic substitution reaction)

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