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Amines

Amines are organic compounds derived from ammonia by replacing hydrogen atoms with alkyl or aryl groups, classified into primary, secondary, and tertiary amines based on the number of substitutions. They possess unique physical properties, such as higher boiling points due to hydrogen bonding, and exhibit basicity influenced by structural factors. Amines undergo various chemical reactions, including alkylation and electrophilic substitution, and can be separated using methods like fractional distillation and Hofmann's method.

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29 views10 pages

Amines

Amines are organic compounds derived from ammonia by replacing hydrogen atoms with alkyl or aryl groups, classified into primary, secondary, and tertiary amines based on the number of substitutions. They possess unique physical properties, such as higher boiling points due to hydrogen bonding, and exhibit basicity influenced by structural factors. Amines undergo various chemical reactions, including alkylation and electrophilic substitution, and can be separated using methods like fractional distillation and Hofmann's method.

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madhu bonam
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AMINES

Amines are the organic compounds derived from ammonia (NH 3) by


replacing its one or more hydrogen atoms by alkyl or aryl group.
For example:

CH3NH2 C2H5NH2 C6H5NH2


Methyl Amine Ethyl Amine Aniline

Structure of Amines
Nitrogen atom of amines carries an unshared pair of electrons and
is sp3 hybridised with pyramidal shape. Due to the presence of unshared
pair of electrons, the angle C–N–E, (where E is C or H) is less than 109.5°.

In aromatic amines, the C‒N bond is slightly stronger due to the partial
double bond character which arises as a result of delocalisation of lone pair
of N with the benzene ring.

Classification of Amines
On the basis of number of hydrogen atoms replaced in NH 3 molecule, amines
are categorized into three types:
• 1° amine: One hydrogen atom of NH3 is replaced by an alkyl or aryl
group.
For example: CH3NH2

Methyl Amine
• 2° amine: Two hydrogen atoms of NH3 are replaced by alkyl or aryl
groups.
For example: CH3NHCH3

Dimethyl Amine

• 3° amine: All three hydrogen atoms of NH3 are replaced by alkyl or aryl
groups.
For example:

Nomenclature of Amines
Common naming system:
• Aliphatic amines are named by prefixing an alkyl group to a mine, i.e.,
alkylamine.

For example:

• Secondary and tertiary amines, having two or more similar groups are
named by adding prefix ‘di’ or ‘tri’ before the name of alkyl group.

For example:

• Aromatic amines are named as derivatives of the parent member,


aniline (C6H5NH2).
For example:
IUPAC naming system:
• Aliphatic or aromatic amines are named by replacing ‘e’ in the end of
the parent hydrocarbon by ‘amine’.

For example:

CH3NH2 C6H5NH2
Methanamine Benzenamine

• Amines containing more than one amino groups at different positions in


the parent chain, are named by specifying numbers to the carbon atoms
bearing –NH2 groups along with attaching a suitable prefix such as di, tri, etc.
to the amine. The ending ‘e’ of the hydrocarbon is retained.
For example:

H2N ‒ CH2 ‒ CH2 ‒ NH2


Ethane-1, 2-diamine

Preparation of Amines
1. By reduction of nitro (RNO2) compounds:
Both aromatic and aliphatic amines can be prepared by reduction of
nitro compounds with LiAlH4 or catalytically.

2. By reduction of nitriles (RCN):


Alkyl cyanides on reduction with sodium amalgam in the presence of
ethanol produces the corresponding amines with one carbon more.

3. By reduction of amides (RCONH2):


Amides on reduction produces primary amines with one carbon more.

4. By ammonolysis of alkyl halides:


Ammonolysis of alkyl halides is the most versatile method for the
preparation of all the three classes of amines (1 0, 20 & 30)

Physical Properties of Amines


• The lower aliphatic amines are gases with fishy smell.

• Primary amines wit three or more carbon atoms are liquid and higher
members are all solids.

• Lower amines are soluble in water as they can form hydrogen bonds with
water, however the solubility decreases with increase in hydrophobic alkyl
group.

• Amines have a higher boiling point than the hydrocarbon of comparable


molecular mass. This is due to their ability to associate via intermolecular
hydrogen bonding.

• Boiling points order of various isomeric amines is:


1o > 2o > 3o

Basic strength of amines


Amines act as Lewis bases due to the presence of lone pair of electrons on
the nitrogen atom. Basic character of amines can be better expressed in
terms of their Kb and pKb values.

All aliphatic amines are strong bases than NH 3 while aromatic amines are
weaker bases than NH3 due to the electron withdrawing nature of the aryl
group.
o Factors affects the basicity of aliphatic amines are:
• Inductive effect
• Solvation effect
• Steric hinderance
Considering all the above factors the basic strength of methyl substituted
amines and ethyl substituted amines in aqueous medium follows the order:

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


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

Reactions of Amines:

Alkylation All the three types of amines react with alkyl halides to form
quaternary ammonium salt as the final product provided alkyl halide is
present in excess.

Aromatic amines also undergo alkylation as given below.


But secondary and _tertiary amines react with nitrous acid in different
manner.

Methyl amine give dimethyl ether with HNO . 2

(vi) Reaction with aryl sulphonyl chloride [Hinsberg reagent] The


reaction of benzenesulphonyl chloride with primary amine yield N-ethyl
benzenesulphonyl amide.

Tertiary amines does not react with benzenesulphonyl chloride.

(vii) Reaction with aldehydes Schiff base is obtained.

(viii) Electrophihc substitution reactions Aniline is ortho and para


directing towards electrophilic substitution reaction due to high electron
density at ortho and para-positions.
To prepare monosubstituted derivative, activating effect of -NH group must
2

be controlled. It can be done by protecting the -NH group by acetylation with


2

acetic anhydride.

(b) Nitration Direct nitration of aniline is not possible as it is susceptible to


oxidation, thus amino group is first protected by acetylation.

In strongly acidic medium, aniline is protonated as anilinium ion which is


meta directing so it gives meta product also.
(d) Aniline does not undergo Friedel-Crafts reaction 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. behave like a
strong deactivating group for further chemical reaction.

(ix) Oxidation Use of diffrent oxidising agents gives difTerent products.


e.g.,

Separation of Mixture of Amines (1°, 2° and 3°)


(a) Fractional distillation This method Is based on the boiling points of amines
and is used satIsfactorily in Industry.

(b) Hofmann’s method Diethyloxalate is called Hofmann’s reagent with which


mixture of amines is treated.
 1° amine forms solid dialkyl oxamide (CONHR)2

 2° amine forms liquid dialkyl oxamlc ester(CONR -COOC H )


2 2 5

 3° amlnes do not react

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