AMINO COMPOUNDS JEE MAINS - VOL - IX

AMINO COMPOUNDS

amino alkanes or alkanamines

SYNOPSIS
AMINE COMMON NAME IUPAC NAME
CH3  CH 2  NH 2 Ethylamine Ethanamine
CH 3  CH2  CH2  NH2 n-Propylamine Propan-1-amine
Classification CH 3  C H  CH 3
| Isopropylamine Propan-2-amine

NH2

Amino compounds are derivatives of NH3 CH 3  N  CH2  CH 3

| Ethylmethylamine N-Methylethanamine
H

CH 3  N  CH 3
| Trimethylamine N,N-Dimethylmethanamine
CH3
1 2 3 4
C 2H 5  N  C H 2  C H 2  C H 2  C H 3 N,N-Diethylbutylamine N,N-Diethylbutan-1-amine
|
C2 H5

1 2 3 Prop – 2 – en – 1 – amine
NH2  C H 2  C H  CH 2 Allylamine
NH 2   CH 2  6  NH 2 Hexamethylenediamine Hexane - 1, 6 – diamine
NH 2

Anilline Aniline or Benzenamine

NH 2
CH 3
O – Toluidine 2 – Aminotoluene

NH 2

where R = alkyl ( or ) aryl group 4-Bromobenzenamine

p-Bromoaniline or
 The secondary (or) tertiary amines with same alkyl 4-Bromoaniline

groups are simple amines and with a different alkyl Br

N  CH 3 2
groups are mixed amines.
N,N-Dimethylaniline N,N-Dimethylbenzenamine
Simple amines : CH3 - NH - CH3;
C2H5 - NH - C2H5
(CH3)3 N;
Isomerism
Mixed amines : CH3-NH-C2H5;
 Amines shows the following types of isomerism
C2H5-NH-C3H7
a. Chain Isomerism
(CH3)2N(C2H5) ;
b. Position Isomerism
(C3H7)N(CH3)(C2H5)
c. Metamerism
 In the process of Nitrogen fixation atmospheric
nitrogen is reduced to ammonia and finally is d. Functional Isomerism
converted into organic Nitrogen compounds e. Optical Isomerism
Structure of amines
 Like ammonia, nitrogen atom of amines is Basic nature of Amines
trivalent and carries an unshared pair of electrons (i) Basicity of Aliphatic Amines :
Nitrogen orbitals in amines are in sp 3 Base strength is measured by the position of
hybridisation and the geometry of amines is equilibrium in reaction with water. The further the
pyramidal due to the presence of unshared pair reaction go to the right, the greater the basic
of electrons, the angle C-N-E , (where E is C or
H) is less than 109.50; for instance, it is 1080 in
case of trimethylamine
..
strength

N  HOH

N OH
Nomenclature
Ammonium ion
IUPAC Names of alkyl derivatives of NH3 are
 JEE MAINS - VOL - IX AMINO COMPOUNDS
thus basicity  stability of ammonium ion Stability
of amine cation depends on two factors : Basicity 
1
Number of resonanting structures
(1) magnitude of positive charge on nitrogen atom

Structure Number of resonanting structures
Less is the magnitude of positive charge , more
will be the stability
..
C6 H 5 NH 2 4

 ..
C6 H 5  NH  C6 H 5 7
Basicity   I power of group ..
C6 H 5  N  C6 H 5
1 10
Basicity  I power of group
C6 H 5
Basicity in decrea sin g order

According to this, basicity order will be as follows:

(iii) Basicity of other Nitrogen Containing Copounds:
ter. amine  sec. amine  p  amine  NH 3
Basicity depends on the following factors :
(1) Electronegativity of nitrogen
(2) Degree of Solvation : Solvation always
1
increases stability of cation Basicity 
Thus basicity  stability of cation  degree of Electronegativity of nitrogen
solvation. Example :
Degree of solvation of ammonia, 10  amine and
20  amine is almost the same but degree of
solvation of 30  amine is very-very less, i.e.,
(a)
almost zero. According to this, 30 -amine is least
basic. In solution basicity order of aliphatic amines
is as follows: (II) Is more basic than (I)


Sec.amine > P-amine > Ter.amine > NH3
Basicity of aliphatic amines in decreasing order
..
R  NH 2
..
R  CH  NH R   N
..
Note :
(i) In gas phase tertiary amines are more hasic sp3 sp 2 sp
than secondary amines which are more basic (b)
Electronegativityininincreasing
Electronegativity omcreasomg order
order
than primary amines.
(ii) In aq. medium basicity of methyl amine is : basicity
Basic ininderea
decreasing order
sin g order
.. .. .. ..
 CH 3 2 NH  CH 3 NH 2   CH 3 3 N  NH 3 sp 3 ..
CH 3  CH 2 CH 2  NH 2
(iii) In aq. medium basicity of ethyl amine is :
C2 H5 2 NH  C2 H5 3 N  C2 H5 NH2  NH3
sp 2
CH 3  CH  CH  NH 2
..
(ii) Basicity of Aromatic Amines : Basicity of
aromatic amines depends on electric density on
sp
CH 3  C  C  NH 2
..
nitrogen, more will be basicity. (c)
In aromatic amines, alone pair of electrons present Flectronegativity of carbons
on nitrogen is delocalised. Hence electron density Electronegativity
attached carbons
to a min o gp is in attached
increa sin g to
decreases due to resonance. amino group is a increasing order
order hencebasicity is in decrea sin g order and
hence basicity is in decreasing order
Thus
 AMINO COMPOUNDS JEE MAINS - VOL - IX
(d) ..
NH 2

NO2

Decrease in electron density

on nitrogen by  R and  I
effect and  I effect is max imum
hence I is more basic than II.
(min nimum) electron density
on nitrogen)
(2) Inductive effect:
Basicity   I power of the group on nitrogen ..
NH 2
1
Basicity 
 I power of the group on nitrogen
NO2
Decreasein electron density
Decreasing electron
on nitrogen by  I effectdensity
only on nitrogen by  I
effect
..
NH 2
Hence amines are more basic than hydroxyl amines

NO2
Decrease in electron density
hence (II) more than (I) in nitrogen by  R and  I effect
and  I effect and  I power is min imum
(3) Resonance : Delocalisation of lone pair of
electrons present on nitrogen decreases basicity, Thus order of basicity is as follow :
hence (II) is more basic than (I)
         
aniline > m-derivative > p-derivative > o-derivative
Basicity in decreasing order

Case II : When group is  R and  I group

NH 2

(iv) Basicity of Substitude Anilines :Para

substituted aniline is more basic than ortho
No group, hence electron
substituted aniline due to streic effect and the effect
is known as ortho  R and  I effect density does not change
due to group
 JEE MAINS - VOL - IX AMINO COMPOUNDS
.. Case : III When group is  R and -I group.
NH 2 Suppose group is  OCH 3  or  OH  group.
With a methoxy substituent, the inductive effect
CH 3
of the oxygen withdraws electron density form
the nitrogen of the amino group, but the
Increase in electron density resosnance effect involving the nonbonding
electrons on oxygen works in the opposite
on nitrogen by  R and  I group and  1 direction to donate eletron density to amino
power is max imum group. Knowing that methoxy (and hydroxy) are
strong activating groups in electrophilic aromatic
.. substitution, the resonance effect should
NH 2 predominate. A methoxy group has a net effect
of releasing electrons when present at ortho or
para position

CH 3 ..
NH 2
Increasein electron
density on nitrogen OCH 3
by  I group
Increase in electron density
.. on nitrogen by  R effect
NH 2 on nitrogen

..
NH 2

CH 3
Increase in electron ensity on
OCH 3
nitrogen by  R and  I group and  I
power is min imum Decrease in electron density
on nitrogen by  1effect
Thus among o, m and p derivatives, meta
derivative is least basic. Among o- and p-
..
derivatives, p is more basic than o-derivatives NH 2
due to ortho effect. Thus basicity order is as
follows :

p  de rivatives  o  derivative  m  derivative  aniline

 Decrea sin g order of basicity
OCH 3
Increase in electron density
Note : p- derivative is more basic than ortho derivative
due to ortho effect. on nitrogen by  R effect on nitrogen
But experimentally it has been found that order
Thus m- derivative is least basic. Among ortho and
of basicity is as follows:
para is more basic due to ortho effect.
p  derivative  aniline  o  derivative
 AMINO COMPOUNDS JEE MAINS - VOL - IX
p- derivative > o -derivative > m-derivative
Thus CH 3  N  CH 3
Basicity in decreasing order CH 3
CH 3
Experimentally it has been found that aniline is
less basic than p-derivative but more basic than
o- and m- derivatives. Basicity in increasing order
Why o-derivative is weaker base than
aniline? Basicity of different nitrogen compound in
Sol. Ortho derivative is weaker base than alliline due decreasing order
to steric hindrance. Steric effect and solvation Guanidine > Aliphatic amines > NH 3 >
effect in ortho derivative is less than in 
Aromatic amines > Imine > Amide > Cyanide
Basicity in decrea sin g order

aniline.Thus order is as follows :
p-derivative > aniline > o-derivative > m-derivative
Problem:
Arrange basicity of given compounds in
(v) Effect of cross conjugation on basicity :
decreasing order.
a) CH 3  CH 2  NH 2
O O
 b) CH 2  CH  NH 2
..
CH3 C NH3 CH3 C NH2 c) CH  C  NH 2
Due to delocalisation and -I effect of CO group, amides d) C6 H 5  NH 2
are less basic than amines.
1) a  b  c  d
O
2) d  c  b  a
..
C6 H 5 C NH 2 3) c  b  a  d
4) a  c  b  d
In this amide there is cross conjugation which Sol. (1)
increases basicity; thus C6 H 5CONH 2 is more
Preparations
basic than CH 3CONH 2 .  bond of C  O  Aniline was first prepared by Unverborden in
group is in conjugation to benzene rong as well 1826 by the destructive distillation of indigo.
as lp of NH 2 group. ii) The name word aniline is derived from the
spanish word anil, meaning: indigo
(vi) Steric Effect on Basicity : Bulky groups present Reduction of nitro compounds
at ortho position inhibit delocalisation of lone pair  
C6 H 5 NO2  C6 H 5 NH 2  2 H 2O
6 H
of electrons present on nitrogen, hence increase Sn / HCl

basicity, Industrial Method

.. .. C6 H5 NO2 
Fe / H 2O / HCl
 C6 H5 NH 2  2H 2O
CH 3  N  CH 3 CH 3  N  CH 3
From phenol
CH 3 C6 H 5OH 
NH 3 / An hyd . ZnCl2
3000 reduced pressure

 C6 H 5 NH 2  H 2O
JEE MAINS - VOL - IX AMINO COMPOUNDS
From chlorobenzene Li AlH4 or 
R  C  N 
H2 /Ni or NaHg/C2H5OHR  CH2  NH2
C6 H 5Cl 2 NH 3
Cu O ,2000 C
 C6 H 5 NH 2  NH 4Cl
2
Reduction of amides
Reduction of nitro compounds

R  CONH 2 
 ii  H2O  R  CH 2  NH 2
i LiAlH
4
Nitroalkanes are reduced to the corresponding
alkanamines
Gabriel phthalimide synthesis
H 2 / Ni  or Pt or Pd 
RNO 2  
Sn  HCl  or Fe+HCl 
 RNH 2 It is used for the synthesis of only aliphatic primary
amine. Aromatic primary amines cannot be
Reduction with iron scrap and HCl is
prepared by this method because aryl halides do
preferred because FeCl2 formed gets hydrolysed
not undergo nucleophilic substitution with the
to release HCl during the reaction thus, only a
anion formed by phthalimide.
small amount of HCl is required to initiate the
reaction O
Ammonolysis of alkyl halides C alc.KOH
NH
 Alkyl (or) benzyl halide on reaction with an C
ethanolic solution of ammonia undergoes O
nucleophilic substitution reaction, in which the Phtha limide
halogen atom is replaced by an amino (-NH2 )
group this process of cleavage of the C - X bond O
by ammonia molecule is known as ammonolysis.
N K 
C R-X
C
 The primary amine thus obtained behaves as a O
nucleophile and can further react with alkylhalide potassium phtha lim ide
to form 20 and 30 amines, and finally quaternary
ammonium salt.
O
  ||
RX  NH  RNH X
3 3 C  
N  R  
NaOH aq

RNH2  RX RX R N

RX
R4NX C
HX

R2NH
HX 3 ||

1  2  3 
O
0 0 0
Quaternary ammoniumsalt
N  Alkylphthalimide
 The free amine can be obtained from the
O
ammonium salt by treatment with a strong base ||


C ONa   R  NH 2

R N H3X  NaOH  RNH2  NaX  H2O ONa 
10 amine 
C
||
O
 Ammonolysis has the disadvantage of yielding a
mixutre of 10 , 20 , and 30 amines and also a Hofmann bromamide degradation
reaction
quarternary ammonium salt. However 10 amine
is obtained as a major product by taking large R C O N H 2  B r2  4 N aO H  aq  
R N H 2  N a 2 C O 3  2 N aB r  2 H 2 O
excess of NH3 .
 The order of reactivity of halides with amines is In this reaction amine so formed contains one
RI > RBr > RCl carbon less than that present in the amide
Reduction of nitriles-Mendius reaction
AMINO COMPOUNDS JEE MAINS - VOL - IX
From Grignard reagent:
MECHANISM :
x
O|| O||   

R  C  NH 2 
 OH

 H 2O

 
R
 C  N 
H 
Br  Br

Br from NaOBr
R Mgx +ClNH 2  RNH 2  Mg


O|| O|| 
Cl
OH  
R  C  NHBr 
 
H O

 
R
 C  N Br 
rearrangement
 Physical properties
2 

   Fresh aniline is odourless, Colourless oily toxic

OH 
O  C  N R  Br    R  N   C||  OH 
 
 liquid, on long standing colour becomes dark

O brown, due to action of air and light.
O||  It is slightly soluble in water and readily soluble
R  NH  C  O  
H 2O
 R  NH 2  CO2  OH  in organic solvents like ether.
 It is steam volatile and it is purified by steam
distillation.
From carbonyl compounds.  It is a weaker base than NH3
1 2 Amines can be obtained by the reductive  It is Neutral to Litmus
amination of carbonyl compounds.  It is slightly heavier than water
 Lower aliphatic amines are gases with fishy
O
odour. Primary amines with three or more
||
 H 2O
H 3C  C  H  NH 3    CH 3  CH  NH 
carbon atoms are liquid and still higher ones are
solid.
H 2 Ni
 Lower aliphatic amines are water soluble through
CH 3  CH 2  NH 2 hydrogen bonds. Solubility decreases with
increase in the size of alkyl (or) aryl group
 Higher amines are insoluble in water.
 Among isomeric amines the boiling points are of
the order 1o  2o  3o
It is due to the decreasing ability to form hydrogen
bonds with decrease in hydrogen atoms on
nitrogen.
Eg : Order of boiling points is
O
|  
H 3 C  C  O  N H 3   
H 2O
  H 3C  C  N H  CH3  CH2  CH2  CH2  NH2  (CH3.CH2 )2 NH 
 | 
 CH 3 
C2 H5 N(CH3 )2  (C2 H5 )NHCH(CH3 )2
H 2 Ni

H 3 C  C H  NH 2
 Comparision of bp’s of amines, alcohol and
|
CH 3 alkanes of similar molecular masses.
Using amination 1 amine con be converted in to n  C4 H9OH  n  C4 H9 NH2  C2 H5 2 NH
2 amine  C2 H 5 N  CH 3  2
H
|
 H 2O  Alcohols are more polar than amines and form
H 3  C  O  CH 3 NH 2   H 3C  CH  N  CH 3
H2 H2
stronger intermolecular hydrogen bonding than
amines
H 3C  CH 2  N H
|
CH 3
Chemical properties
JEE MAINS - VOL - IX AMINO COMPOUNDS
Basic character of amines. Amines, being basic C 2H 5  N  C CH 3
| ||
in nature, react with acids to form C2H5 O

..  
salts. R  N H 2  HX € R  NH3 X  salt  ..
C6 H5  N  H  CH3  C  O  C  CH3 
| || ||
 H
O O
C6 H 5 NH 2  HCl € C6 H 5 N H 3Cl  Benzena min e
Ethanoic anhydride

 Amine salts on treatment with a base like NaOH,

regenerate the parent amine
   .. 
..
R N H3 X  O H  R N H 2  H 2O  X C6 H5  N  C  CH3  CH3COOH
| ||
 Amine salts are soluble in water but insoluble in H
O
organic solvents like ether. The reaction is the N  Phenylethanamideor Ace tan ilide

basis for the separation of amines from the non

basic organic compounds insoluble in water. Note : Base such as pyridine which removes the
Alkylation acidic hydrogen and shifts the equlibrium towards
Aromatic amines react with alkylhalides to form products.
secondary amines, tertiary amines and finally Reactivity order of acylation is
forms quaternary salts. In this reaction acid
formed is neutralised by basic carbonates like  CH 3COCl  (CH 3CO ) 2 O  CH 3COOC2 H 5
K 2CO3 . Benzoylation
CH 3 NH 2  C6 H 5COCl  CH 3 NHCOC6 H 5  HCl
C6 H 5 NH 2 
CH3 I
 C6 H 5 NHCH 3 Benzoylchloride N-Methyl benzamide
 N-methyl aniline  C6 H 5 NH 2  C6 H 5COCl  C6 H 5 NHCOC6 H 5  HCl

CH I3
 C6 H 5 N  CH 3 2 Benzoylchloride N-Phenyl benzamide

N,N- dimethylaniline This reaction is known as Schotten-Baumann

reaction

CH3I
 C6H5 N  CH3 3 I Carbylamine reaction (Isocyanide test)
Only primary amine (Both aliphatic and aromatic)
Phenyl Trimethyl Ammonium Iodide reacts with chloroform and alcoholic KOH to
Quaternary salt  form foul smelling compound isocyanide.
This reaction is used to identify the both primary
Acylation amine and chloroform.
Aliphatic and aromatic primary and secondary
amines react with acid chlorides, anhydrides and R  NH 2  CHCl 3  3KOH   R  NC  3KCl  3H 2 O
Heat

esters by nucleophillic substitution reaction. This Mechanism

reaction is known as acylation.
Step 1:

H
CHCl3  OH   H 2O  CCl3 : CCl2  Cl 
Cl Cl
.. | | |
C 2 H 5  N  H  C  C H 3    C 2 H 5  N   C  C H 3 
B ase Step 2:
| || | |
O
H
O H
E th a n a m in e

C 2H 5  N  C  C H 3  H C l
| P
H O

Cl
.. | B ase
C2H5  N  H  C  CH3   

| || HCl
C2H 5
O
N  E th yle th a n a m in e
AMINO COMPOUNDS JEE MAINS - VOL - IX
H Reaction with arylsulphonyl chloride
() (Hinsberg’s reagent)
.. .. ..

R  N H 2  C Cl2  R  N  C C l2 C6 H5 SO2Cl H N  C2 H5 C6 H5SO2 N  C2 H5HCl
| |
H H
H N-Ethylbenzene sulphonamide
(Soluble in alkali)
H
..  C H SO Cl  H  N ( C H ) 2 
 R  N H  C C l2  R  N H  CHCl 6 5 2 2 5

C H SO  N ( C H ) 2  HCl
6 5 2 2 5
.. 
 R  N  CHCl  R  N  CH
N,N-Diethylbenzenesulphonamide  insoluble in alkali 

 R  N  C ()
Reaction with benzaldehyde
Reaction with nitrous acid
Aniline reacts with benzaldehyde in the presence
Three classes of amines react differently with of concentrated H2SO4 to give imine also known
nitrous acid which is prepared ‘in situ’ from a as schiff’s base.
mineral acid and sodium nitrite .
. Primary aliphatic amines react with nitrous acid C6H5NH2  C6H5CHO 
Conc.H2SO4
C6H5  N  CC6H5  H2O
|
to form aliphatic diazonium salts which being H

unstable, liberate nitrogen gas quantitatively and Benzyledeneaniline

alcohols.Quantitative evolution of nitrogen is used
in estimation of amino acids and proteins
Electrophilic substituion
  R  N C l    Bromination : Aniline reacts with bromine water
 2  ROH  N2  HCl
NaNO2 H2O
R  NH2  HNO2
HCl at room temperature to give a white precipitate
of 2,4,6 - tribromoaniline

 20 amine:Yellow coloured oily layered NH2 NH2

nitrosoamines are produced. This test is called
+3Br2 
Br2 / H2O
 Br Br +3HBr
Liberman’s reaction
 30 amine:Nitrite salts are produced, which are
soluble in water Aniline Br

Diazotisation 2, 4, 6  Tribromoaniline

Aromatic amines react with nitrous acid at low (water soluble)

temperatures (273-278 K) to form diazonium
salts, a very important class of compounds used
for synthesis of a variety of aromatic compounds
.
 
NaNO  2HCl
C 6 H 5  NH 2  2
273 278 K
 C6 H5  N 2 Cl  NaCl  2H 2 O
Aniline Benzenediazonium chloride

Secondary and tertiary amines react with nitrous

acid in a different manner.
JEE MAINS - VOL - IX AMINO COMPOUNDS
nitro derivative can be obtained as the major
product

NH 2 NHCOCH 3

 3    
HNO3


i CH COCl or
 CH 3CO  O
2

NHCOCH 3 NH 2


H 2O


NO2 NO2
90% Paranitroaniline

Sulphonation
 Aniline reacts with concentrated sulphuric acid
to form anilinium hydrogensulphate which on
Nitration heating with sulphuric acid at 453- 473 K
 Direct nitration of aniline yields oxidation produces p - aminobenzene sulphonic acid,
products in addition to the nitro derivatives. commonly known as sulphanilic acid, as the major
Moreover, in the strongly acidic medium, aniline product
is protonated to form the anilinium ion which is
meta directing. That is why besides the ortho
and para derivatives, significant amount of meta
derivative is also formed

NH 2 NH 2 NH 2
Aniline does not undergo Friedel - Crafts

HNO3 ,H 2SO4 ,288K
 + + reaction (alkylation and acetylation) due to salt
formation with aluminium chloride, the Lewis acid,
NO2 which is used as a catalyst. Due to this, nitrogen
NO2
of aniline acquires positive charge and hence acts
 51%  47%
as a strong deactivating group for further reaction
NH 2 Uses
NO2  In nature, amines occur among proteins,
vitamins, alkaloids and hormones
 Two biologically active compounds, namely
 2%  adrenaline and epherdine, both containing
secondary amino group, are used to increase
blood pressure.
However, by protecting the -NH2 group by
 Novocain, a synthetic amino compound, is used
acetylation reaction with acetic anhydride, the
as an anaesthetic in dentistry
nitration reaction can be controlled and the p -
 Benadryl, a well known antihistaminic drug also
 AMINO COMPOUNDS JEE MAINS - VOL - IX
contains tertiary amino group   
  
O RCH=NH
R.CH 2 .NH 2 H / H2O
 Quaternary ammonium salts are used as
surfactants R  CHO  NH 3
 Aniline is used to prepare schiff’s base which acts R 2CHNH 2 

(O)
as an antioxidant in rubber industry.

R 2 C  NH H /  R 2CO  NH3
H 2O
 Aniline is used in the manufacture of benzene
diazonium chloride which is the starting material  20 amine:Tetraalkyl hydrazine is formed
for many Organic compounds especially azodyes. (O)
 The compounds like Acetanilide, Suphanilic R 2 NH 
 R 2 N  NR 2
acid,sulpha drugs are prepared from Aniline.  30 amine:No reaction
Identification of 1o ,2o and 3o amines  Action of caro’s acid (H 2SO 5 )
Hinsberg’s test  10 amine:Aldoxime and hydroxamic acid are
 (Action of benzene sulphonyl chloride) produced
10 amine: N-alkylbenzene sulphonamide is (O) RCH=NOH aldoxime
RCH 2 NH 2 

formed, which is soluble in alkali
RNH 2  ClSO2 . C6 H 5 
RNH.SO 2C6 H 5 + HCl
20 amine: N,N-dialkyl benzene sulphonamide 
is formed,which is insoluble in alkali 20 amine:Dialkyl hydroxyl amine is produced
(O)
R 2 NH  Cl.SO 2 .C 6 H 5  R 2 N.SO 2 .C6 H 5 R 2 NH 
 R 2 NOH
 30 amine:Tertiary amine oxide is formed
30 amine: No characteristic change
 R 3 N  R 3 N  O
Hofmann mustard oil reaction (Reaction with O

CS2 followed by HgCl2 ) Carbylamine test

1 amine:Black precipitate is formed due to the
0
(Amine + CHCl3 + alc.KOH)
formation of HgS
 10 amine:Foul smell is observed due to the
formation of RNC (isocyanide)
RNH 2  CS2  RNH

C =S 
HgCl2
 HgS  RNCS  2HCl RNH 2  CHCl3  3KOH   RNC  3KCl  3H 2 O
HS  20 amine:No reaction
 30 amine:No reaction
 2 amine:No precipitate is observed
0
 Reaction with nitrous acid ( NaNO2  HCl )
 10 amine:Alcohols are formed with the liberation
of N 2 gas . With CH 3 NH 2 , it produces methyl
nitrite with the liberation of N 2 gas
no precipitate
  20 amine:Yellow coloured oily layered
30 amine:No reaction
nitrosoamines are produced. This test is called
 Oxidation by KMnO4 Liberman’s reaction
 10 amine:Aldehydes and ketones are formed
JEE MAINS - VOL - IX AMINO COMPOUNDS
 30 amine:Nitrite salts are produced, which are insoluble and stable at room temperature.
soluble in water Chemical properties
Diazonium Salts  Reactions involving displacement of N2 .
 As diazonium group is a good leaving group, it
General formula of diazonium salts is R N 2 X  . may be substituted by
Here R is alkyl or aryl group and X  may be
Cl  , Br  , I  , CN  , OH  etc.
  
Cl  , Br , HSO4 , BF4 etc. Sandmeyer’s reaction
Primary aliphatic amines form highly unstable
alkyl diazonium salts.
Primary aromatic amines form arene diazonium
salts which are stable for a short time in solution
at low temperature.
The stability of arene diazonium ion is because
of resonance. Gatterman’s reaction

N 2 group ( N  N) is called diazonium group.
The process of conversion of a primary Aromatic
amine in to its diagonium salt is called diazotisation
all benzen diazonium salte contain benzene
More yield is observed in Sandmeyer’s reaction
diazanium ion which has the following structure.
than in Gatterman’s reaction. In these reactions,

NN nucleophile has been introduced into benzene
ring.
the ion is stabilised by resonance. Replacement by iodide ion
(Balz-Schiemann reaction)



NN 
NN 
NN

NN Ar N 2 Cl   KI  ArI  KCl  N2
Replacement by fluoride ion


Ar N 2 Cl   HBF4   ArN2 BF4  ArF  BF3  N2
fluoroboric acid
Preparation of diazonium salts
Replacement by ‘H’
0 50 C
C6 H 5 NH 2  NaNO 2  2HCl  

Ar N 2 Cl   H3 PO2  H 2O   ArH  N2  H3 PO3  HCl
C6 H 5 N 2 Cl  NaCl  2H 2 O
hypophosphorous acid
Properties of benzene diazonium 

chloride Ar N 2 Cl   C2 H 5OH   ArH  N 2  CH 3CHO  HCl
 It is colourless crystalline solid Replacement by OH  group
 It is highly soluble in water.
 It is stable at 0oC, but on warming it reacts with
water
 In dry state it easily decomposes, but in the form
of benzene diazonium fluoroborate, it is water
 AMINO COMPOUNDS JEE MAINS - VOL - IX
 (yellow dye)
Ar N 2 Cl   H 2O  ArOH  N 2  HCl
283 K
The azo products have extended conjugate
Replacement by NO 2 system with aromatic ring and -N=N-.
Therefore, these compounds are coloured and
ArN2 Cl   HBF4  ArN 2 BF4 used as dyes.
NaNO / Cu , 
 2   Ar  NO 2  N 2  NaBF4
Cyanides and Isocyanides
Importance of diazonium salts in Introduction
synthesis of aromatic compounds The general formula for cyanide and Isocymide
 Diazonium salts are intermediates in the are R  C  N or Ar  C  N
 
preparation of variety of aromatic compounds R  N  C or Ar  N  C
including dyes. Cyanides and iso cyanides are functional
 Substituted arenes are easily prepared through isomeric compounds. Both which exists in two
diazonium salts. dyad type of Tauto meric forms
 
Fluorides and iodides can not be prepared by H C  N  H  N  C
direct reaction of halogen. A group having two different sites avaailable
 Cyano group cannot be introduced by for linkage is konwn as ambident group.
nucleophilic substitution of chlorine in
chlorobenzene but cyanobenzene can be easily
obtained from diazonium salt. IUPAC NOMENCLATURE
 Reactions involving retention of diazogroup
Formula Common IUPAC
name name
(Azodyes) coupling reactions CH3 C  N Methyl Ethanenitrile
Coupling is an example for electrophilic cyanide
substitution reaction in which diazonium cation CH3CH2CN Ethylcyanide Propanenitrile

with Ve charge on the terminal nitrogen acts as C6H5 C  N Phenyl Benzene
cyanide coarbo nitrile
a electrophile while the electron rich compounds
(phenol and aniline) act a nucleophiles. CH  N  C
3
Methyl Methyl
Isocyanide carbylamines

C6H5  N  C Phenyl Phyenyl
 Benzene diazonium chloride reacts with phenol, Isocyanide carbylamine
aniline etc in which these compounds attach to
the diazonium ion through their para positions
giving azo products. These reactions are  METHODS OF PREPARATION
electrophilic substitution reaction. 1. From Grignard Reagent
N 2 Cl OH
Cl

+   N=N OH  Cl   H 2 O R  Mg  X  ClCN  R  C  N  Mg
OH

Cyanogen chloride

P-hydroxy azobenzene X
(orange dye)

P-amino azobenzene
 JEE MAINS - VOL - IX AMINO COMPOUNDS
X Physical properties
R  Mg  X  NC  CN  R  C  N  Mg
c ya n o g e n
Alkyl Isocyanides have lower dipole
Cl
moments than alkyl cyanides have
2. From aldoximes generally pleasant odour but alkyl
isocyanides have very unpleasant adour.
CH CO
H3C  CH  NOH  CH3  C  N  H2O
O
3

2
Lower alkyl cyanides are soluble in water
where as isocyanides are insoluble in water
P2 O 5 , POC l3 and SOCl2 are also used as
because they do not from hydrogen bonds.
dehydrating agents
Isocyanides generally have low Boiling
points than the corresponding cyanides.
C6 H 5CH  NOH 
P2O5

 C6 H 5  C  N  H 2 O

Chemical properties
1. Cyanides
3. From N  Alkyl formamides a. complete hydrolysis
O 

POCl3  H3 O
H  C N  R R  N  C  H2O R  C  N  2 H 2O RCOOH  NH 3
|  Pyridine  or  OH
H

4. Carbyl amine reaction b. Reduction (stephens)

 SnCl4  2  H 
SnCl2  HCl 

R / Ar  NH 2  CHCl3  3 alc . KOH 
 R / Ar  N  C
CH3  C  N  2 H   HCl 
CH3  CH  NH.HCl
 3 KCl  3 H 2 O
This reaction is used for the CH 3  CH  NHHCl 
H 2O

 CH 3CHO  NH 4Cl
identification of 1 amine (both aliphatic
and aromatic) and chloroform. c. Complete Reduction
5. From Alkyl halides. Ni
R  C  N  2H RCH NH
or 
2 2 2
C 2 H 5O H  Pt
R  X  A gC N R  N  C  A gX
 H 2O
d. Catalytic Rediction.
C 2 H 5 OH
R  C  N  KX
Mendius reaction
R  X  KCN
alcoholic  H 2 O LiAlHCl
R  C  N  4 H  CH 3CH 2 N 2 H
C2 H 5OH Na
2 alkyl halides gives both substitution and
elimination products.
3 Alkyl halides give elimination product. RC  N  R 1 MgX 
 R  C  NMgX  
H 2O / H
|



R1
6. from Ammonium salts of carboxylic acids |
R  C  O  Mg  OH  X
and amides.
CH 3COONH 4 
P2O5

 CH 3  C  N  2 H 2O Isocyanides


CH 3CONH 2 
P2 O5

 CH 3  C  N  H 2O RNC  H 2O 
H 3O
 RNH 2  HCOOH

RNC  4  H  
LiAlH 4
 R  NH  CH 3
 AMINO COMPOUNDS JEE MAINS - VOL - IX
CH 3 NC  Cl2 
 CH 3 N  CCl2 3. Iso-Propylamine 4. 20  Pr opyla min e
5. IUPAC name of C6H5-CH2-CH2-NH2
CH 3 NC  2 HgO 
 CH 3 N  C  O  Hg 2O 1) 2-phenyl ethanamide
2) 2-phenyl ethanamine
CH 3 NC  O3 
 CH 3 N  C  O  O2 3) 2-phenyl ethylamine
CH 3  N  C  O 4) 3-phenyl ethanamine

is called Methyl iso cyanate (MIC)

PROPERTIES
Was respeonsible for bhopal gas tragedy in
december 1984.
6. Carbylamine reaction is given by
1.aliphatic 10 amines only
CONCEPTUAL
2. aromatic 10 amines only
3.Both aliphatic and aromatic primary amines
NOMENCLATURE 4. all secondary amines and diazonium salt
7. How many primary amines are possible for
1. Which of the following systematic name & the formula C4H11N
names are correct for 1) 1 2) 2 3) 3 4) 4
NH 2 8. Which of the following should be most
C2 H5
volatile ?
I) CH 3CH 2CH 2 NH 2 II)  CH 3 3 N
Br
CH 3CH 2
A) 4-Bromo-2-Ethyl aniline NH IV) CH CH CH
B) 4-Bromo-2 Ethyl Benzenamine III) 3 2 3
CH 3
C) 4-Bromo-2-Ethyl Amino benzene
1) II 2) IV 3) I 4) III
D) 3-Bromo-1-Ethyl benzanamine
9. The structure given below represents
1) only D 2) A and B only
CH 3
3) A,B,C, only 4) A,B,C, & D |
CH 3  C  NH 2
|
CH 3

1. Quarternary ammonium Salt

2. IUPAC name of
2. Primary amine
3. Secondary amine
1) 1,2-Propane diamine 4. Tertiary amine
2) Propanamine 1,2 10. Aniline is more basic than
3) Dipropane 1,2 - amine 1. NH3 2. CH3NH2
4) Diamino 1,2 Propane 3. N-methyl aniline 4. P - nitroaniline
3. The structural formula of N-methyl 11. Which of the following is the strongest base?
Aminomethane is 1. Aniline 2. N - methyl aniline
1.(CH3)2 CHNH2 2. (CH3)3N 3. O-methyl aniline 4. Benzylamine
3.(CH3)2 NH 4. CH3 NH2 12. In the reaction of
4 IUPAC name of CH3  CH2 2 NH2 is C6 H 5OH 
NH3
 X; 'X'may be
ZnCl2
1. 1 - Propanamine 2.2-Methyl ethanamine
 JEE MAINS - VOL - IX AMINO COMPOUNDS
1. C6 H 5 NH 2 2. C 6 H 5 C l CH 3  CH  CH 2  NH 2
3. C6 H 5CHO 4. C6 H 5COOH CH 3
13. During the nitration of aniline, the amino
group is protected by CH 3  CH 2  CH  CH 3
1) converting it to NO2 group NH 2
2) converting it to Carboxylic group
3) Acylation 4) Benzoylation CH 3
14. Aniline when treated with benzoyl chloride, CH3  C  NH 2
gives benzanilide the reaction is known as
1. Perkin 2. Hofmann CH 3
3. Schotten baumann 4. Benzoin
9. R  NH 2 is 10 - amine
15. In phenyl isocyanide the carbons are ____
hybridised. 10. Nitro group is electron with drawing group
1. sp3, sp2 2. sp3, sp 11. C6 H 5  CH 2  NH 2 is an aliphatic amine
3. sp2, sp 4. sp3 12. Preparation method
16. Schiffs base is used as a
13. NHCOCH 3 is less active than NH 2
1. oxidant 2. Hydrolysing agent
14. Schotten baumann reaction.
3. antichlor 4. antioxidant
r
N  C

KEY 15.
CONCEPTUAL
1) 3 2) 1 3) 3 4) 1 5) 2 16. In rubber industry it is used as anti oxidant
6) 3 7) 4 8) 2 9) 2 10) 4
11) 4 11) 2 13) 3 14) 3 15) 3 LEVEL - I
16) 4 CLASS WORK
HINTS NOMENCLATURE
CONCEPTUAL
1. Least sum rule 1. Systematic name of H2 N CHO

2. Two ' NH 2 ' groups 1) 4-amino benzene carbaldehyde

2) P-amino benzaldehyde
3. 20 amine
3) 3- amino benzaldehyde
4. CH 3  CH 2  CH 2  NH 2 4) 4- formylamine
2 The IUPAC name of CH3NH2 is
5. C6 H 5 is aryl group 1. methylamine 2. amino ethane
3. methanamine 4. Ethylamine
6. Characteristic property of both aliphatic and
aromatic 10 amine
PREPARATION
CH 3  CH 2  CH 2  CH 2  NH 2 ,
7. 3. Aniline can be industrially prepared from
nitro benzene by using
1. LiAlH4
AMINO COMPOUNDS JEE MAINS - VOL - IX
2. Na / C2H5OH
3. Sn/HCl NH 2
4. Fe steam and HCl NH 2
4. In Gabriel synthesis, halide may be
Br
1) Benzyl halide 2) Allyl halide
3. +
3) both 4) 30 alkyl halide
5. Which of the following reagents would not
be a good choice for reducing an aryl nitro Br
compound to an amine ?
1) H2(excess)/Pt 2) LiAlH4 in ether NH 2
3) Fe and HCl 4) Sn and HCl Br Br

PROPERTIES 4.
6. Arrange the following in the correct order
of their basic character in gaseous phase Br
I) NH3 II) RNH2 III) R2NH IV) R3N 10. For the conversion of Aniline to
1) IV>III>II>I 2) III>IV>II>I N-Methyl aniline, the reagent used is
3) III>II>IV>I 4) I>II>III>IV 1. CH3I 2. C6H5Cl
7. Out of the following compounds, which is the 3. CH4 4. CH3 NH2
most basic ? 11. Activation of benzene by - NH2 group can
1. CH 3 NH 2 2.  CH 3 2 NH be reduced by treating the compound with
1. acetic acid 2. acetyl chloride
3.  CH 3 3 N 4. C6 H 5 NH 2 3. dilute HCl 4. Methyl alcohol
8. Benzene diazonium chloride is the product 12. Aniline when treated with chloroform in
when aniline is treated with presence of basic medium, gives following
1. NaNO2 and HCl at 0-50 C compound
2. HNO3 and HCl at 40 C
3. C6H5NO2 at 40 C 4. NaNO2 at 40 C
9. Aniline is treated with Br2 water at room 1 2.
temperature to give the following product

NH 2
Cl
NH 2
3. 4.
Br
1. 2. 13. 2,4,6-tribromo aniline is a product of
1. electrophilic addition on C6H5NH2
Br 2. electrophilic substitution C6H5NH2
3. nucleophilic addition on C6H5NH2
4. nucleophilic substitution on C6H5NH2
14. Aniline undergoes condensation to form
Schiff’s base on reacting with
1. acetyl chloride 2. Ammonia
 JEE MAINS - VOL - IX AMINO COMPOUNDS
3. Acetone 4. Benzaldehyde LEVEL - I
15. Primary amines can be distinguished from
1) 1 2) 3 3) 4 4) 3 5) 2
other amines by the following test.
6) 1 7) 2 8) 1 9) 4 10) 1
1. Tollen’s 2. Schifff’s
11) 2 12) 1 13) 2 14) 4 15) 3
3. Carbyl amine 4. Fehling
16) 2 17) 4 18) 1 19) 1 20) 2
21) 3
ASSERTION & REASON
1 A and R are true and R is the correct
explanation of A HINTS
2. A and R are true and R is not the correct LEVEL - I
explanation of A 1. Order of Priority CHO  NH 2
3. A is true R is false 4. A is false R is true
16 Assertion : Benzylamine is more basic than 2. 10 amine
aniline 3. Conceptual
Reason : NH2group is electron releasing 4.
group 5.
17 Assertion : Acetanilide is more reactive than 6. 30  20  10  NH 3
aniline towards electrophilic substitution
reactions 7. 20  30  10  NH 3  C 6 H 5 NH 2 .
Reason : The activating effect of 05 C
C6 H5 NH2  NaNO2  2HCl  C6 H5 N2Cl  NaCl  2H2O
0
8.
NHCOCH 3 is less than that of amino group
05 C
C H NH  NaNO  2HCl  C6 H5 N2Cl  NaCl  2H2O
0

6 5 2 2
18. A : Aniline does not undergo Friedel-Crafts
reactions. NH 2 NH 2
Br
R :  NH 2 group of aniline reacts with AlCl3 Br
 H
B r2

to give acid-base reaction. 9. 2O

0  50 C
19. A: Carbylamine reaction involves the
chemical reaction between primary amine Br
and chloroform in basic medium 10. Alkylation
R : In carbylamine reaction, NH 2 group 11. Acetyl chloride converts - NH2 to - NHCOCH3
changes to -NC group which reduces the activation of benzene ring
12. C6 H 5 NH 2  3KOH  CHCl3  C6 H 5 NC  3KCl  3H 2O
C6 H 5 NH 2  3KOH  CHCl3  C6 H 5 NC  3KCl  3H 2O
20. Which one of the following functional groups
NH 2 NH 2
undergoes hydrolysis with alkali to yield an Br Br
acid group
 H
B r2
2O

(1) CHO (2) CN (3) COCH 3 (4)  Br 13. 0  50 C
21. N-Ethyl formamide on dehydration with Br

POCl3 in presence of pyridine gives

(1) Ethyl amine (2) Ethyl cyanide
(3) Ethy isocyanide (4) Methyl isocyanide

KEY
 AMINO COMPOUNDS JEE MAINS - VOL - IX
C 6 H 5 N H 2  C 6 H 5 C H O  C  
onc H 2S O 4

caustic potash solution, we get
14. C 6H 5 N  C  C 6H 5  H 2O 1. Phenyl iso cyanide 2. o-Chloro aniline
|
H 3. Benzoic acid 4. Phenol
7. Aniline dissolves in HCl due to the formation
15. 20 ,30 amines donot give carbylamine test.
of
16. Benzylamine is aliphatic primary amine 1. Anilinium chloride 2. o-chloroAniline
17. Acetanilide less reactive than aniline 3. Azodye 4. diazonium chloride
18.  NH 2 group reacts with Lewis acid AlCl3 8. Acetanilide can be obtained by the following
19. In carbyl amine reaction, Isocyanides are formed. 1. Benzoylation of aniline
2. Alkylaion of nitro benezene
LEVEL - I 3. Acetylation of aniline
4. reaction between acetaldehyde and aniline
HOME WORK
9. Aniline reacts with excess alkyl halide to
NOMENCLATURE give
1. IUPAC name of aniline 1.amino compound
1. Phenyl amine 2. Amino benzene 2.tertiary compound
3. Benzyl amine 4. Benzenamine 3. azomethane
PREPARATION 4. quaternary ammonium compound
2. The reducing agent used for preparing 10. Which of the following compounds will
aniline from nitro benzene in the laboratory dissolve in an alkali solution after it has
is undergone reaction with Hinsberg
1. LiAlH4 2. Na / C2H5OH reagent?
3. Sn/HCl 4. Fe - steam and HCl 1.  C2 H5 2 NH 2.  CH 3 3 N
3. Gabriel phthalimide reaction is used for the
preparation of 3. CH 3 NH 2 4. C 6 H 5 NHC 6 H 5
1. primary aromatic amines 11. Aniline on heating with fuming sulphuric acid
2. secondary amines gives.
3. primary aliphatic amines 1. Aniline disulphate 2.Sulphanilic acid
4. tertiary amines 3. Aniline sulphate
4. Which of the following pair is correctly 4. Aniline-2, 4-disulphonic acid
matched. 12. Bromine water reacts with aniline to give
1) Curtius reaction, carboxylic acid 1. o-bromoaniline
2) Hoffmann rearrangement-acid azide 2. p-bromoaniline
3) Schmidt reaction-carboxylic acid 3. m-bromoaniline
4) Lossen rearrangement-acid chloride 4. symmetric tribromoaniline
13. N-alkyl aniline is the product of following
PROPERTIES 1. Nitration of benzene
5. Arrange the following in the correct order 2. Alkylation of aniline
of their basic character 3. Acylation of aniline
I) NH3 II) CH3NH2 III) C6H5NH2 4. Benzoylation of aniline
1)III>II>I 2) II>III>I 14. A : Nitration of aniline can only be done by
3) II>I>III 4).I=II=III protecting  NH 2 group through acetylation.
6. When aniline is heated with chloroform and
 JEE MAINS - VOL - IX AMINO COMPOUNDS
R : Acetylation of aniline results in the C. Oilof wintergreen 3. yellow
increase of electron density on the benzene D. 2,4,6-tribromo 4. pale yellow to
ring. aniline reddishbrown
1 A and R are true and R is the correct The correct matching is
explanation of A 1. A-2 B-3 C-4 D-1 2. A-4 B-3 C-2 D-1
2. A and R are true and R is not the correct 3. A-1 B-2 C-3 D-4 4. A-3 B-1 C-2 D-4
explanation of A
3. A is true R is false 4. A is false R is true 18. Ethyl isocyanide on reduction with sodium
15 Match the following and alcohol gives.
List - I List - II (1) Ethyl amine (2) Propyl amine
 (3) Dimethylamine (4) Ethyl methyl amine
A. Ar N 2 X  
CuBr
 1. ArF
HBr 19. Cyanide is an
 (1) Zwitter ion (2) Cation
B Ar N 2 X  
HBF4
 2. ArH
 (3) Ambident nucleophile (4) Electrophile

C. Ar N 2 X  
C2 H5 OH
 3 .
KEY
ArOH
LEVEL - I

D. Ar N 2 X  
H2O
 4. ArBr 1) 4 2) 3 3) 3 4) 3 5) 3
1. A - 4 B -1 C-2 D-3 6) 1 7) 1 8) 3 9) 4 10) 3
2 A-1 B -2 C-3 D-4 11) 2 12) 4 13) 2 14) 3 15) 1
3. A - 2 B -3 C-4 D-1 16) 2 17) 1 18) 4 19) 3
4. A - 3 B -4 C-1 D-2

16. List-I List-II 1. Aromatic compound.

A. HVZ reaction 1. NaNO2  HCl 2. Sn + HCl gives nascent hydrogens
B. Clemmensen 2. hydrazine + 3. Primary aliphatic amines
reduction
4.
KOH (alc)
C. Diazotisation 3. Sn / HCl 5. Aliphatic amine > NH 3 > aromatic amine
D. Wolf-Kishner 4. Zn-Hg/ Conc. 6. C6 H 5 NH 2  3KOH  CHCl3  C6 H 5 NC  3KCl  3H 2O
HCl  
7. C6H NH  H C l  C6H N H Cl
reduction 5 2 5 3

5. Cl2 / red P 8.R.W CH 3COCl + C6H5NH2  C6H5NHCOCH3 +

The correct matching is HCl
 C6 H 5 NR3  X 

1. A-3 B-1 C-4 D-3 2. A-5 B-4 C-1 D- 9. C6 H 5 NH 2 
3 RX

2
10. 10 amine
3. A-2 B-5 C-1 D-3 4. A-1 B-2 C-4 D-
5 11. Electrophilic substitution
12. Electrophilic substitution reaction
17. List-I List-II 13. Alkylation
A. Indigotin 1. White 14. COCH 3 decrease the electron density of
B. Iodoform 2. blue benzene ring.
15. A- Sandmeyer’s reactor
 4.AMINES

symmetrical tribromoanline. The amount of

bromine required is
LEVEL - II 1) 3.0 moles 2. 1.5 moles
CLASS WORK 3) 4.5 moles 4. 6.0 moles

PREPARATION 7. C6 H 5Cl NH 3

Cu O ,2000 C
 X;
2

X 
HNO2
0 50 C
 Z ; X  Z  A; the no.of
1. Aniline is not the major product in one of
the following reactions. Identify that reaction.  and  bonds in 'A' are

1) C6H5OH+NH3 
ZnCl2
 1. 25 , 6 2. 25 , 7
3000 C
3. 27 , 7 4. 27 , 6
2) C6H5NO2+Zn Powder 
alcoholicKOH

Hydrolysis Re d hot
3) C6H5Cl+NH3 
200 C

0
8. CaC2   A  B
Cu2O Cu tube
4) C6H5NO2+Fe+H2O  
HCl
 HNO  H SO
3 2 4 C

50600 c
2. Which of the following amines cannot be
NaNO  HCl , O0c
prepared by Gabriel phthalimide reaction? Fe
  HCl  D  2 E
1. Benzylamine 2. Aniline
Then E is
3. Ethylamine 4. Methalylamine
1. Aniline black
3. In the Hoffmann Bromamide
2. Benzene diazonium Chloride
rearrangement, intermediate species are
3. Phenyl osazone
1) R  CO  NHBr
4. Benzoyl chloride
 
  9. Aniline reacts with HCl and forms 'X' the
2)  R  CO N  Br  Na
  type of bonds in X are
1) ionic, covalent
3) R  N  C  O 4) All
2) ionic, covalent, dative
3). only covalent 4). only ionic
PROPERTIES 10. Which of the following is the strongest base?
4. Acetamide is treated separately with the
following reagents. Which one of these
1. NH 2 2. NHCH3
would give methylamine?
1. PCl5 2. Sodalime
NH 2
3. 4. CH 2NH 2
3. NaOH  Br2 4. Hot concentrated H 2SO 4
CH 3
5. Among the following, the strongest base is
1. C6 H 5 NH 2
DIAZONIUM SALTS
2. p  NO 2  C6 H 4 NH 2 11. Among the following incorrect resonance
structure of Benzene diazonium ion is
3. m  NO 2  C6 H 4 NH 2
4. C6 H 5CH 2 NH 2
6. Aniline (1 mole) react with bromine to give
 
(1) CH 3 N  CCl2 (2) CH 3 NCl  CCl2
 
N N: N N: 
(3) ClCH 2 NC (4) Cl2CHNC

1) 2) 
KEY
LEVEL - II

 
1) 2 2) 2 3) 4 4) 3 5) 3
N  N :


N N: 6) 1 7) 3 8) 2 9) 2 10) 4
11) 4 12) 3 13) 2 14) 1 15) 1
3) 4) 16) 1


HINTS
12. Which of the following statement is
incorrect? LEVEL - II
1. C6 H 5 N 2 Cl is soluble in water
Zn  KOH
1. C6 H 5 NO 2   C 6 H 5 NH  NHC 6 H 5
2. C6 H 5 N 2 BF4 is water insoluble
2.
3. C6 H 5 N 2 Cl is stable at room temperature 3.
4NaOH  Br2
4. C6 H 5 N 2 Cl is stable at 00 C 4. CH3  CO  NH 2 
13. A positive carbylamine test is given by CH3 NH 2  Na 2 CO3  2NaBr  2H 2O
1. N,N-dimethyl aniline 2. isopropyl amine
SO3 H SO3
3. diethyl amine 4. trimethyl amine
14. Acid hydrolysis of methyl isocyanide gives
5.
(1) CH 3 NH 2  HCOOH
NH 2 NH 3
(2) CH 3 NH 2  CH 3COOH
NH 2 NH 2
(3) C2 H 5 NH 2  HCOOH Br Br
 3Br2   3HBr
(4) CH 3 NH 2  CH 3CH 2COOH 6.
15. Acetaldoxime reacts with phosphorous Br
pentoxide to give
(1) Methyl cyanide (2) Methyl cyanate 7. X  C6 H 5 NH 2 , Z  C6 H 5 N 2Cl ,
(3) Ethyl cyanide (4) Ethyl isocyanide A  C6 H5  N  N  C6 H4 NH2
16. Which of the following product is obtained 8.
when methyl isocyanide reacts which
chlorine 9. C6 H 5 NH 3 Cl 
10. Aliphatic 10 amine
11.
12. At room temperature and it decomposes
13. 10 - amine
 LEVEL - II CH 3 CH 3
HOME WORK COCH 3
PREPARATION
1. Which of the following amides will not
undergo Hoffmann bromamide reaction? 3) 4)
COCH 3
1. CH 3CONH 2 2. CH 3CH 2CONH 2
NH 2 NH 2
3. C6 H 5CONH 2 4. CH 3CONHCH 3
2. Amongst the given set of reactants, the most 6. The compound C5 H13 N is optically active
appropriate for preparing 20 amine is ___
and reacts with HONO to give C5 H11OH .
1) 20 R-Br + NH3
The compound is
2) 20 R-Br + NaCN followed by H2/Pt
1. N - methylbutanamine
3) 10 R-NH2 + RCHO followed by H2/Pt
2. 2 - Aminopentane
4) 10 R-Br (2 mol) + Potassium phthalimide
followed by H3O+/heat 3. 1 - Aminopentane
4. N, N - Dimethylpropanamine
7. Which one of the following is the
PROPERTIES
strongest base in aqueous solution?
3. Zwitter ion can be formed by
1. Trimethylamine 2. Aniline
1) Acetanilide 2) Benzanilide
3. Dimethylamine 4. Methylamine
3) Sulphanilic acid 4) Benzene sulphonamide
8. What is the end product in the following
4. Aniline doesn’t react with sequence of operations ?
1. dil.HCl 2. dil NaOH
C2 H5 NH2   A   B  C
HNO2 5 PCl3 alc. NH
3. CH3COCl 4. Br2 water
5. 1. ethyl cyanide 2. Methyl amine
3. ethyl amine 4. Acetamide
CH 3 9. Which of the following shows optical
activity?
1. butanamine-1 2. butanamine-2
 CH CO  O 
3. isopropylamine 4. etyl methyl amine

3 2
A  Br2
CH 3COOH
 B 
H
H 2O
C

DIAZONIUM SALTS
NH 2 10. In the reaction ,
NaNO HCl
C6 H 5 NH 2  2  (A)
C is 05o C

CH 3 CH 3 Cu2  CN 
2
 (B) H / H O (C) the
KCN  
2

Br
product (C) is
1. C6 H 5CH 2 NH 2 2. C 6 H 5COOH
1) 2)
Br 3. C6 H 5OH 4. all the above
NH 2 NH 2
11. Which of the following converts Benzene
diazonium chloride to Benzene? 5 4 3 2 1

6. H3C CH2  CH2  CH  CH3

|
1. H 3 PO3 2. C2 H5OH NH2

3. H 2 O 4. HBF4
12. Which of the following can distinguish the 7. 20 > 30 > 10 > NH3
three amines, viz.., primary, secondary and 8. A  C2 H 5OH , B  C2 H 5Cl ,
tertiary?
C  C2 H 5 NH 2
1. Azo - dye test 2. Hinsberg reagent
3. Carbylamine test 4. Acetyl chloride 9. It contain chiralcarbon
13. Aniline and diphenylamine may be 10. A = C6 H 5 N 2Cl
distinguished by
B = C6 H 5CN
1. Lassaigne’s test 2. Schiff’s test
3. Carbyl amine reaction 4. Solubility test C = C6 H 5COOH
14. The only stable organic functional group in 11. Reduction
which carbon is divalent is 12. 10 amine reacts with Hinsberg reagent and the
1) : CCl2 2) : CH 2 3) : CBr2 4) R  NC product is soluble in alkali, 20 amine reacts with
15. Electrophilic and Nucleophilic reagents give Hinsberg reagent and the product is insoluble in
addition on the same atom of the molecule alkali where as 30 amine does not react with
in Hinsberg reagent
1) Cyanide 2) Isocyanide 13. Diphenyl amine is 20 amine
3) Aldehyde 4) Ketone
PREVIOUS YEARS QUESTIONS
1. In the chemical reactions,
KEY
LEVEL - II

1) 4 2) 3 3) 3 4) 2 5) 2 the compounds ‘A’ and ‘B’ respectively are

6) 2 7) 3 8) 3 9) 2 10) 2 1) nitrobenzene and fluorobenzene
11) 2 12) 2 13) 3 14) 4 15) 2 2) phenol and benzene
3) benzene diazonium chloride and fluorobenzene
HINTS 4) nitrobenzene and chlorobenzene
2. An organic compound A upon reacting with
NH3 gives B. On heating, B gives C. C in
LEVEL - II - HOME WORK
presence of KOH reacts with Br2 to give
CH3CH2NH2. A is
SO3 H SO3
1) CH 3COOH
2) CH 3CH 2 CH 2 COOH
3.
NH 2 NH 3 CH 3  CH  COOH
4. Weak base |
3)
CH 3

4) CH 3CH 2 COOH
3. On heating an aliphatic primary amine with
3.  NH 
chloroform and ethanolic potassium
hydroxide, the organic compound formed is:
1) an alkyl cyanide 2) an alkyl isocyanide
3) an alkanol 4) an alkanediol
4. Considering the basic strength of amines in 4.  NHCH3
aqueous solution, which one has the smallest
pKb value?
2. Which of the following orders is true
1)  CH 3 3 N 2) C6 H 5 NH 2
regarding the basic nature of NH 2 group?
3)  CH 3 2 NH 4) CH3 NH 2 1. o - Toluidine > Aniline > o - Nitroaniline
2. o - Toluidine < Aniline > o - Nitroaniline
KEY 3. o - Toluidine < Aniline < o - Nitroaniline
1) 3 2) 4 3) 2 4) 3 4. o - Toluidine > Aniline < o - Nitroaniline

HINTS PREPARATION AND PROPERTIES

3. Hofmann degradation of
m - bromobenzamide gives
1. 1. aniline
2. m - bromoaniline
3. bromobenzene
4. m - bromoethyl benzene
4. An aromatic amine(A) was treated with
2. alcoholic potash and another compound ‘Y’
then a foul smelling gas was formed with
formula C6H5NC, ‘Y’ was formed by reacting
a compound ‘Z’ with Cl 2 in presence of
3. RNH 2  CHCl3  3KOH  RNC  3KCl  3H 2 O slaked lime. The compound ‘Z’ is
4. Aliphatic amines are more basic than aromatic 1. C6H5NH2 2. CH3OH
amines. 3. CH3COCH3 4. CHCl3
(CH3)2NH > CH 3NH2 > (CH 3)3N (among 5. Which of the following would not react with
aliphatic amines in water). benzene sulphonyl chloride in aq. NaOH?
1. aniline 2. methylamine
3. N,N-dimethyl aniline 4. N-methyl aniline
LEVEL - III
6. Fluorobenzene (C6 H 5F) can be synthesized
BASICITY OF AMINES
in the laboratory
1. by heating phenol with HF and KF
1. Maximum pK b value is of 2. from aniline by diazotisation followed by
1.  CH3 2 NH heating the diazonium salt with HBF4

2.  CH 3CH 2 2 NH
3. by direct fluorination of benzene with F2 gas
4. by reacting bromobenzene with NaF solution
7. CH3CH2Cl 
NaCN
X 
Ni/ H2
Y 
Acetic
anhydride
Z NH 2
Z in the above sequence is
1. CH 3CH 2 CH 2 NHCOCH 3 10.  Br2 
CH 3COOH
 ?
2. CH 3CH 2 CH 2 NH 2
3. CH 3CH 2 CH 2 CONHCH 3 NH 2
NH 2
4. CH 3CH 2 CH 2CONHCOCH 3 Br
 NH 
C6 H 6   X  Y
Conc. HNO3 4 2 x S
8. Conc. H 2 SO4 ,363 K 1) 2)
In the above reaction requence, X and Y are
Br
1. Nitrobenzene, aniline
2. m - Dinitrobenzene, m - Phenylenediamine
NH 2
3. m - Dinitrobenzene, m - Nitroaniline NH 2
Br
4. p- Dinitrobenzene, p- nitroaniline
9. In the given reaction
3) 4)
CH 3
| Br Br
CH 3  CH 2  C  NH 2 
NaNO2
conc . HCl

|
BENZENE DIAZONIUM CHLORIDE
CH 3
product(s). Product(s) will be
11. In the diazotization of arylamines with
OH sodium nitrite and hydrochloric acid, an
| excess of hydrochloric acid is used
CH 3  CH 2  C  CH 3 primarily to
1) | 1. Supress the concentration of free aniline
CH 3 available for coupling
2. Supress hydrolysis of phenol
CH3  CH  C  CH3 3. Ensure a stoichiometric amount of nitrous acid
|
4. Neutralise the base liberated
2) 12. The compound which on reaction with
CH3
aqueous nitrous acid at low temperature
produces an oily nitrosoamine is
Cl
1. methylamine 2. ethylamine
|
3. diethylamine 4. triethylamine
CH 3  CH 2  C  CH 3
3) 13. Which of the following orders is correct
|
regarding basicity of indicated
CH 3
molecules?
4) All 1. N, N - Dimethyltoluidine > p - toluidine >
aniline > p - nitroaniline
2. Aniline > N, N - dimethyl - p - toluidine > p -
toluidine > aniline
 3. p - Toluidine > N, N - dimethyl - p - toluidine 1) Aniline 2) N-Methylaniline
> aniline > p - nitroaniline 3) N,N-Dimethylaniline
4. N, N-Dimethyltoluidine > aniline > p - 4) O-, m- or P-Toluidine
toluidine > p - nitroaniline 19. Amine which will not respond to
14. Towards electrophilic substitution, the most Benzoylation reaction is
reactive is
1. anilinium chloride 2. aniline 1) C6 H 5 NH 2 2)
3. N - acetylaniline 4. nitrobenzene
15. 'Z' in the following sequence of reaction is 3) 4) C6 H 5 NHCH 3
C6 H 6 
 W 
HNO3 / H 2SO4

Zn / HCl

X 
NaNO2
HCl, 0 50 C
Y  
H 2 O / H3PO2
Z
KEY
COOH
LEVEL - III
1. 2. 1) 3 2) 2 3) 2 4) 3 5) 3
6) 2 7) 1 8) 3 9) 4 10) 3

OH Cl 11) 1 12)3 13) 1 14) 2 15) 2

16) 3 17) 2 18) 2 19) 3
3. 4.
HINTS
16. The reaction of chloroform with alcoholic LEVEL - III
KOH and p - toluidine forms
1. H3C N2Cl 1. Lone pair of electrons on nitrogen involved in
the resonance
2. H3C NHCHCl2 2. Electron releasing increases the availability of lone
pair of electrons on nitrogen. While electron
3. H3C NC attracting group decreases this availability

4. H3C CN
CONH2 NH2
| |
NaOH  Br2
3.  
TESTS | Br |
Br

17. In the Hofmann’s method for separation of 4. Y  CHCl3

10 , 20 and 30 amines, the reagent used is 5. 30 - amine
1) Acetyl chloride 6. C6 H5 NH 2 
NaNO2
 C6 H5 N 2Cl 
HBF4
 C6 H 5 F
HCl
2) Benzenesulphonyl chloride
3) Diethyl oxalate 4) Nitrous acid 7. x  CH 3CH 2 CN Y=CH 3CH 2CH 2 NH 2
18. Libermann’s nitroso reaction is used for 11. Exess of HCl is used to convert free aniline to
testing aniline hydrochloride. Other wise free aniline
 would undergo coupling reaction with benzene 3. Which of the following has maximum pK b
diazonium chloride value ?
12. 20 a min e
13. CH3 group is electron releasing group were as 1) CH 3CH 2 NH 2 2)

NO 2 group is electron withdrawing group

 NH 2 is electron releasing group
3)  CH 3CH 2 2 NH
14.
4)
15. w  C6H5 NO2 x=C6H5 NH2 y  C6H5 N2Cl
16. Similar to carbylamine reaction
COMPREHENSION-II
An aromatic compound ‘A’ on treatment with
LEVEL-IV aqueous ammonia and heating forms compounds
COMPREHENSIVE TYPE QUESTION
‘B’ which on heating with Br2 and KOH forms
COMPREHENSION-I a compound ‘C’ of molecular formula C6 H 7 N .
Electron releasing group pushes electrons to ward 4. The conversion of B to C is
nitrogen and hence increases the availability of 1) Hoffmann bromamide degradation reaction
lone pair of electrons and thus increases its 2) Bromoform reaction
basicity on the other hand, electron with drawing 3) Wurtz fitting reaction
group decreases the availability hence makes the
4) Hoffmann mustard oil reaction
amine less basic
5. The compound ‘B’ is
1. Among the following which is more basic
1. CH3O -- -- NH2

2. O 2N - --N H 2 1) 2)

3. --NH2

4. HOOC -- --NH2
2. Which of the following is the strongest base? 3) 4)

NH2 NH2
| | 6. The compound ‘A’ may be
1. 2.

NO2
NH | 1) 2)
NH

3. 4.

3) 4)
 KEY

LEVEL - IV
1) 1 2) 2 3) 4 4) 1
5) 1 6) 4

HINTS
LEVEL - IV
1. CH3O group is electron releasing group
2. Aliphatic amines are stronger bases than aromatic
amines
3. C6 H 5 NH 2 is a weak base.
4. The conversion of benzamide to aniline is
Hoffmann degradation reaction.
5. B is amide
6. A is benzoylchloride.