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Notes For Chemistry Class 12 Chapter 13 Amines

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2K views22 pages

Notes For Chemistry Class 12 Chapter 13 Amines

this file contains notes for cbse and icse board students and also for the jee aspirants to help the students excel in their examinations with flying colours.

Uploaded by

Vanshika Jain
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
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Methods of prepration:

Amines

Ammonolysis has the disadvantage of yielding a mixture of primary, secondary and tertiary amines and
quaternary ammonium salt.
However, primary amine is obtained as a major product by taking large excess of NH 3.
Order of reactivity of halides with amines is RI > RBr > RCI.
Aromatic amines could not be prepared since aryl halides are much less reactive towards
nucleophilic substitution reactions.
(iii) Reduction of nitriles or cyanides

2|Page

(v) Reduction of amides

It only produces 1 0 amines. This method is not suitable for 1 arylamine because aryl halide
does not give nucleophilic substitution reaction.
(viii) Hofmann bromamide degradation reaction

In Hofmann degradation reaction, the amine formed has one carbon less than the parent amide. To
obtain primary amine with same number of carbon atoms from primary amide, reduction is done
with LiAlH4/ether.
Physical Properties of Amines
1 The lower aliphatic amines are gases with fishy smell.
2 Primary amines witb three or more carbon atoms are liquid and higher members are all
solids.
3 Lower aliphatic amines are water suluble because they can form hydrogen bonds with
water molecules, however the solubility decreases with increase in hydrophobic alkyl
group.
4 Boiling points order primary > secondary > tertiary
3| P a g e

5 Tertiary amines does not have intermolecular association due to the absence of hydrogen

atom available for hydrogen bond formation.


Basic Strength of Amines
Amines act as Lewis bases due to the presence of lone pair of electrons on the nitrogen atom.
More the Kb (dissociation constant of base), higher is the basicity of amines.
Lesser the pKb higher is the basicity of amines.
Aliphatic amines (CH3NH2) are stronger bases than NH3 due to the electron releasing +/ effect
of the alkyl group.
Among aliphatic methyl amines, the order of basic strength in aqueous solution is as follows
(C2H5)NH > (C2H5)3N > C2H5NH2 > NH3
(CH3)2NH > CH3NH2 > (CH3)3N > NH3
Aromatic amines are weaker basesthan aliphatic amlnes and NH 3,due to the fact that the electron
pair on the nitrogen atom is involved in resonance with the -electron pairs of the ring.
Electron releasing groups (e.g.,-CH3,-OCH3,-NH2 etc.) increase the basic strength of aromatic
amines while electron withdrawing groups (like NO2, -X,-CN etc.) tend to decrease the same.

o-substituted aromaticamines are usually weaker basesthan aniline irrespective of the nature of
substituent whether electron releasing or electron withdrawing. This is called ortho effect and is
probably due to sterk and electronic factors.
chemical Properties of Amines
(i) 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.

4| P a g e

5| P a g e

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.

6| P a g e

To prepare monosubstituted derivative, activating effect of -NH 2 group must be controlled. It


can be done by protecting the -NH2 group by acetylation with 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.

7| P a g e

(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) Hofmanns methoOd Diethyloxalate is called Hofmanns reagent with which mixture of amines
is treated.

8| P a g
e

a
m
in
e
fo
r
m
s
s
ol
id
di
al
k
yl
o
x
a
m
id
e
(
C
O
N
H
R
)2
2

a
m
in
e
fo
r
m
s
li
q
ui
d
di
al
k
yl
o
x
a
m
lc
es
te
r(
C
O
N

R
2C
O
O
C
2

H
5)
3

a
m
ln
es
d
o
n
ot
re
a
ct

(c) Hlns
berg
s
meth
od
see.c
hem
kal
react
ions.
Benzen
e
Diazoni
um
Chlorid
e
(C6H5N
+
2 ;Cl )

Prepara
tion
(Diazoti
sation
reaction
)

The
excess
acid in
diazotisa
tion
reaction
is
necessar
y to
maintain
proper
acidic
medium
for the
reaction
and to
prevent
combina
tion of
diazoniu
m salt
formed
with the
undiazot
ised
amine.

D
i
a
z
o
n
i
u
m
s
a
l
t
s
a
r
e
p
r
e
p
a
r
e
d
a
n
d
u
s

e
d
i
n
a
q
u
e
o
u
s
s
o
l
u
t
i
o
n
s
b
e
c
a
u
s
e
i
n
s
o
l
i
d
s
t
a
t
e
,
t
h
e
y
e
x
p
l
o
d
e
.
Propert
ies
It is a

colourle
ss
crystalli
ne solid,
soluble
in water.
It has
tendenc
y to
explode
when
dry.
Stabilit
y of
Arenedi
azoniu
m salts
It is
relativ
ely
more
stable
than
the
alkyldi
azoniu
m salt.
The
arenedi
azoniu
m ion
is
resona
nce
stabilis
ed as is
indicat
ed by
the
followi
ng
resonat
ing
structu
res:

9| P a g
e

Alkyl
Cyanide
s
These
compoun
d have
formula
RCN.
These are
the
derivativ
es of

RCN.
Accordin
g to
IUPAC
system,
cyanides
are
named as
alkane
nitrile,
e.g.,

10 | P a g e

Methods of Preparation

Physical properties
1.
2.
3.

These are neutral compound with pleasent odour, similar to bitter almonds.
These are soluble in water as well as organic solvents.
These are poisonous but less than HCN.
Chemical Properties

Alkyl iscoyanides (RNC)


Accordinlg to IUPAC system, these are named as alkane isonitrile
e.g., CH3NC methyl isonitrile

11 | P a
ge

C6H5NC
benzene
isonitrile
Methods
of
Preparat
ion
(a) From
alkyl
halides

Physical
Properti
es
1.

Th
ese are
colourles
s
unplease
nt
smelling
liquids.
2.
Th
ese are
soluble
in
organic
solvents
but
insoluble
in water.

Chemica
l
Properti
es
(i)
Hydroly
sis

12| P a g e

Nitro Compounds
These are obtained by replacing one H of hydrocarbon by -NO 2 group.
These are named according to IUPAC system as nitro alkane.
Methods of Preparation
(i) From alkyl halides

Physical Properties
1.
2.
3.

These are colourless pleasent smelling liquids.


Their boiling point are much higher than isomeric alkyl nitriles.
These are less soluble in water but readily soluble in organic solvents.
Chemical Properties
(i) Reduction With Sn/HCl or catalytic hydrogenation, nitroalkanes are reduced to amines.

13| P a g e

Nitrobenzene gives different prociucts with different reagents and in different mediums.

3 nitroalkanes does not react with HNO 2


iii Nef carbonyl synthesis Na or K salt of 1 or 2 nitroalkanes give carbonyl compounds on
acidification with 50% H2SO4 at room temperature. This reaction is called Nef carbonyl
synthesis.

14 | P a
ge

(iii)
Elect
rophifie
substituti
on
On
nitration,
nitrobenz
ene gives
mdinitrobe
nzene (as
-NO2 is a
mdirecting
group
and
strongly
deactivat
ing).

It does
not give
FriedelCrafts
alkylatio
n.
(v)
Nu
cle
op
hili
c
sub
stit
utio
n
rea
ctio
n
-N
O2
gro
up

acti
vat
es
the
rin
g
tow
ard
s
nuc
leo
phil
ic
sub
stit
utio
n.

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