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Class-XII Amines  

Preparation
[1] Reduction Method The primary amines may be prepared by the reduction of
nitro compounds,nitriles,amides and oximes.

R NO 2 H2 / Pt or H2/Pd or H2 / Ni or LiAlH 4 R NH 2
Zn / HCl or Sn/ HCl or Fe / HCl
NO 2 NH 2
Sn/ HCl or Fe / HCl

[Fe/HCl is preferred ,because FeCl 2 formed gets

Nitro compounds hydrolysed to release hydrochloric acid,thus a small
amount of HCl is required to initiate the reaction.]

LiAlH 4 or H2 / Ni or Na(Hg) / C 2H5OH

R C N R CH 2 NH2
Nitrile O
LiAlH 4 / H2O
R C NH2 R CH 2 NH2
 Amines
 Amide

[2]Hoffmann Bromamide Degradation Reaction

O

R C NH2 + Br 2
+ 4 NaOH R NH2 + Na 2CO 3 + 2 NaBr  + 2 H 2O

In this reaction ,the amine formed contain one carbon less than those of amide.
[3] Gabriel phthalimide synthesis
O O
O
C KOH C R X C
- +
N H N K
N R NaOH
C C
C
Phthalimide O N-Alkylphthalimide
O O
- +
Aromatic primary amines can not be prepared by COO Na
this method because aryl halides do not undergo + R NH2
nucleophilic substitution with the anion formed by - +
COO Na
phthalimide.
[4] Ammonolysis of alkyl halides
The process of cleavage of the C-X bond by ammonia molecule is known as ammonolysis.

NH3 RX RX RX + -
RX R NH2 R2NH R3 N R 4N X

The primary amine thus obtained behaves as a nucleophile and can further react with
alkyl halide to form secondary and tertiary amines, and finally quaternary ammonium
salt.
xx
+ - NaOH
NH3 + R X R NH 3 X R NH2 + H2O + NaX
Primary amine is obtained as a major product by taking large excess of ammonia.
The order of reactivity of halides with amines is RI > RBr > RCl
 

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 1 

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Class-XII Amines  

Properties
[1] Salt formation
+ - NaOH
R NH2 + HX R NH 3 X R NH2 + H2O + NaX
Substituted ammonium salt

NH + - NaOH
HCl H O
2
+ NH 3 Cl NH2
+ 2
+ NaCl
 Anilinium chloride
[2] Alkylation
RX RX RX + -
R NH2 R 2NH R3 N R 4N X

[3] Acylation
The replacement of hydrogen atom of -NH 2 group by acyl group is known as acylation.
O H O H
Base
H3C C Cl + H N C2H5 H3C C N C2H5
N-Ethylethanamide

The base stronger than amine, like pyridine is used to removes HCl so formed.
O C2 H 5 O C2H5
Base
H3 C C Cl + H N C2H5 H3C C N C 2 H5
Ethanoyl chloride N,N-Diethylethanamide
O O H O H

H3C C O C CH3 + H N H3C C N

Ethanoic anhydride N-Phenylethanamide
Aniline
[ acetanilide ]
O
H O H
C Cl + H N CH 3
C N CH3
N- methylbenzamide
Methanamine
Benzoyl chloride

[4] Carbylamine reaction

Heat
NH2 + CHCl 3 + 3 KOH NC + 3 H 2O
+ 3 KCl

Heat
R NH2 + CHCl 3 + 3 KOH R NC + 3 H 2O + 3 KCl

Primary amine Isocyanide

/ Carbylamine
[ Foul smell ]
[5] Reaction with Nitrous acid
[ Nitrous acid is prepared in situ from mineral acid and sodium nitrite.]
NaNO 2 + HCl + - H2O
R NH2 + HNO 2 R N 2 Cl R OH + N2
+ HCl
Alcohol
Aliphatic diazonium salt

NaNO 2 + HCl + -
NH2
+ HNO 2 N 2 Cl + NaCl + H2O

Benzenediazonium chloride
Benzenediazonium chloride is stable due to resonance.
 

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 2 

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Class-XII Amines  
[6] Reaction with Hinsberg's reagent
Benzenesulphonyl chloride is known as Hinsberg's reagent.
O O + O
KOH K
R N H + Cl S R N S R N
-
S

H O O O
H
o Water soluble
1 amine
potassium salt
Acidic hydrogen
N-alkylbenzenesulphonamide of sulfonamide

O O
KOH Water insoluble
R N H + Cl S R N S
precipitate
O R O
R
N,N-Dialkylbenzenesulphonamide
2o amine
O

R N R + Cl S No reaction
R O
3o amine

O
+ O O
K H2 O
R N S
HCl
R N S
R N H + Cl S
- KOH O
O H
O H
1o amine
O O
H2O
R N S
KOH
R N H + Cl S

O R O
R o
2 amine

These days benzenesulphonyl chloride is replaced by p-toluenesulphonyl chloride.

NH2
[7] Electrophilic substitution Br  Br 
Br 2 / H 2 O

Br 

NH2 NH2 NH2 NH2

NO 2
HNO 3 , H 2 SO 4 . 288 K
+ +
NO 2
(2%)
Aniline NO 2 ( 47 % )
( 51 % )

+ - +
NH 3 HSO 4 NH2 NH 3

H2 SO 4 453 - 473 K

 Aniliniumhydrogensulphate -
SO 3 H SO 3
Sulphanilic acid Zw itter ion  

Jayanta kumar sahu – PGT : Chemistry – Kendriya Vidyalaya Sangathan  Page  - 3 

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Class-XII Amines  
Controlled Bromination O O
xx
NH2 H N C CH3 H N C CH3 NH2

( CH 3CO ) 2O Br 2 - +
OH / H
Pyridine CH 3 COOH

N-Phenylethanamide Br  Br 

( Acetanilide )

Controlled Nitration O O
xx
H N C CH 3 NH2
NH2 H N C CH3

( CH 3CO ) 2O - +
HNO 3 , H 2SO 4 , 288 K OH / H
Pyridine

NO 2 NO 2
The lone pair of electrons on nitrogen is less available for donation to benzene ring by
resonance. Therefore, activating effect of -NHCOCH3 group is less than that of amino
group.
Explanations  
Aniline and other aryl amines are colourless but get coloured on storage due to
atmospheric oxidation.
Alcohols are more soluble than amine in water because, alcohols are more polar than
amines and form strong intermolecular hydrogen bonds than amine.
The intermolecular association is more in primary amine than in secondary amines as there
are two hydrogen atoms avilable for hydrogen bond formation in primary. Tertiary amines
do not have intermolecular association due to absence of hydrogen atom available for
hydrogen bond formation. Therefore, the order of boiling points of isomeric amines :
Primary > Secondary > Tertiary
The basicity of amines in gaseous phase : 3o amine > 2o amine >1o amine > NH3
H
xx +
+
N + H N

[ Base ] [ Conjugate acid ]

R
The stability of substituted ammonium ion:
+ + +
R NH 2 +
The positive charge get neutralised by R HN R NH 3 NH 4
the +I effect of alkyl groups. R R

In aqueous phase the stability of substituted ammonium cation depend upon both the +I
effect of alkyl group and solvation by water molecules. The greater the size of the ion
lesser will be the solvation and less stabilised is the ion.
CH3
So the basicity of methyl substituted H3C NH H3C NH2
H3C N NH3
amines in aqueous phase: CH3
CH3
When alkyl group is bigger methyl group, 2o 1o 3o
there will be steric hindrance to
H-bonding with water, so the stability C2H5
H5C2 NH2 NH3
of substituted ammonium ion decreases. H5C2 NH H5C2 N
So the basicity of ethyl substituted C2 H 5
2o 3o C2H5 1o
amines in aqueous phase:
 

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Class-XII Amines  
Aniline does not undergo Friedel-Crafts reaction (alkylation / acetylation) 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.
Besides the ortho and para derivatives, significant amount of meta derivative is also formed
during nitration of aniline.Because, in the presence of mineral acids,the aniline readily
forms anilinium ions. The anilinium ion is a strong electron withdrawing group, which

directs the electrophile towards meta+position.

-
NH2 NH 3 NO 3 NH2
Ring deactivator

HNO 3

NO 2

Aniline is less basic than ammonia, because the availability of electron on

xx
nitrogen atom of aniline decreases due to delocalisation of electron by NH2
resonance
In case of aliphatic amine due to +I effect of alkyl group, the xx  Aniline
electron density on nitrogen atom increases, as a result basic R > NH2

strength increases.  Aliphatic amine

Amines are less acidic than alcohols, because N-H bond is less polar than O-H bond. Therefore, amine
releases H+ ion with more difficulty.
Aromatic amines are insoluble in water because, the phenyl group is bulky in size and has
-I effect. As a result, its hydrogen bonding with water is negligible.

Methylamine forms a soluble hydroxide on reacting with water. The OH - ions released by
the hydroxide combine with Fe3+ ions of ferric chloride to give ferric hydroxide or
hydrated ferric oxide which is brown in colour.
xx
+ -
H3C NH2
+ H OH H3C NH 3
+ OH
3+ -
2 Fe + 6 OH 2 Fe(OH) 3 or Fe 2O 3. 3H 2O ( Brown ppt )

Basicity of
NH2 Incase of aromatic amines, the basicity
NH2 NH2
depends upon:
NO 2 [i] Inductive effect o- > m- > p-
[ii] Resonance effect, observed
at o- & p- positions.
NO 2
NO 2 o-Nitroaniline
m-Nitroaniline
p- Nitroaniline
The electron withdrawing substituents on aromatic ring reduce the basicity of substituted
anilines. The -R effect of nitro group is observed maximum at ortho and para positions.Thus,
m-nitroaniline is relatively more basic compared to ortho and para isomers as it withdraws
electrons through inductive effect(-I effect) only. Out of o-nitroaniline and p-nitroaniline, -I
effect is found to be stronger in ortho isomers as compared to para. Thus,o-nitroaniline
experiences a strong -R and -I effect and is least basic.

So PKb of o-nitroaniline > p-nitroaniline > m-nitroaniline

 

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Class-XII Amines  

Benzenediazonium Chloride
NaNO 2 + HCl + -
NH2
+ HNO 2
Diazotisation N 2 Cl + NaCl + H2O

Benzenediazonium chloride
Benzenediazonium chloride is stable due to resonance.

   l
  e Coupling do not H 3PO 2
+
  p
  u occur in strong H2O
H + N2 + H 3PO 3 HCl
  o
  c acidic medium
  n
  a  .
  c
 , +
  e   m NH2 NH 3 CH 3CH 2OH
   l   e
   i   t
   h  s +
H + N2 + CH 3CHO
+ HCl
  p  y
  s
H
  o
  r   c
   t   i -
  c   t OH
  e   a
   l
  e   m
   k  o CuCl / HCl
  a   r
  e   a
Less Cl + N2
  w   d activated
  e
  a   t aromatic
  g  a
   i
  n   t
   i
  v
  e   c
system CuBr / HBr  N2
   b  a
  y
- Br  +
  n   l OH O
  o  g
   i
    n -
  m  o
  r OH
   i   t
  u
  n  s +
  o  a H CuCN / KCN CN + N2
  z   h
  a   t
   i   i
   D  w

+
-
N N Cl Cu / HCl
Cl + N2 + CuCl

-+
   f O Na
  o N
  n  s KI
  o  e
   i I + N2 + KCl
   t   s
  a
N
  a
  r   e
   t   r
  n  c
  e  e
  c   d  r     .

  n   )
  o  e  u
HBF 4 + -
  c   l   c

  e   i
  c
  o
NaOH N 2 BF 4 F + N2 + BF 3

   h   h   t
   t   p   o
 ,   o
  r  n OH
  m   t   s
  u  c
   i   e  e N H2O
   l   o N2
   d  e    d OH HCl
N
  e
  m   s
  a  n + +
  o
  e   t   i
  c   t
  n
   i   a  c
   l   (   a
  a   e
   k  n  r
   l
HBF 4 + - NaNO 2
  o  g
  a   i
  y
    i
  n NaOH
N 2 BF 4
Cu 
NO 2 + N2 + NaBF 4
   l   m   l
  g  u  p
  n   i   u
  o   n  o N
  r
   t   o   c H OH
  s  z
  a   d
+
N N N OH ( Orange dye )
  n   i   n HO
-
Coupling reaction
   I   d  a
H NH 2 N N NH 2 ( Yellow dye )
-
HO Coupling reaction p-Aminoazobenzene  

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Class-XII Amines  

Predict the products

NC + 3 KCl + 3 H 2O
NH2 + CHCl 3 + alc. KOH
?
N H 3PO 3 HCl
N 2+ Cl
- + H 3PO 2
+ H2O
? + 2
+ +

HO 3S NH2
NH2
+ Conc. H 2SO 4
?
+ -
N2 Cl + C2H5OH
? + N2 + CH 3CHO + HCl

Br 

3 HBr 
NH2
+ aq. Br 2
? Br  NH2
+
Br 

O
NH2 + ( CH 3CO) 2O ? NH C CH3 + CH 3COOH

+ - (i) HBF 4 NO 2 + NaBF 4 + N2

N2 Cl
(ii) NaNO 2 / Cu 
?

+ -
H3C CH 2 CH 2 NH 3
H3C CH 2 CH 2 NH2 + HCl
? Cl

CH3 CH3
+
H3C N CH3 + HCl ? H3C NH
Cl
-
CH3

PKb value PhNH 2 > PhNHCH 3 > Et NH 2 > Et 2 NH

Basic strength Et 2 NH > CH 3NH 2 > Ph N Me 2 > PhNH 2

Basic strength p-Toluidine > Aniline > p-Nitroaniline

Basic strength in gaseous phase Et 3N > Et 2 NH > Et NH 2 > NH3

Boiling point Et OH > Et NH 2 > Et 2 NH

Solubility Et NH 2 > Et 2 NH > PhNH 2

Basic strength Et 2 NH > Et NH 2 > NH3 > PhNH 2

+
+ + - + N
+ -
N
+ -
N N N N N N

+
Resonating structures of diazonium ion.  

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Class-XII Amines  

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