AMINES

Introduction and Nomenclature

Amines are alkyl or aryl derivatives of NH3. The amines are classified as primary
(1o ),secondary(2o) and tertiary (3o) amines according to the number of hydrogen atoms
attached with nitrogen

NH3 RNH2 R2NH R3N

O o o
Ammonia 1 Amine 2 Amine 3 Amine

Amines are named by combining in one word the name of each group on the N with the
suffix -amine : (C6H5)2NCH3 is methyldiphenylamine. Amines are also named by placing
the prefix amino-, N-alkylamino - or N, N-dialkylamino - before the name of the parent
chain.

Aromatic and cyclic amines often have common names such as aniline, C6H5NH2,
p-toluidine, p-CH3C6H4NH2, and piperidine etc.

Like the oxa method for naming ethers the aza method is used for amines.

Di-n-propylamine,CH3CH2CH2NHCH2CH2CH3 is 4-azaheptane and piperidine is


azacyclohexane. The 4 H’s of NH4 can be replaced to give a quaternary (4°) tetra alkyl
(tetra aryl) ammonium ion.

CH3
|
C6H5CH2N+  CH3 OH-
|
CH3

is benzyltrimethylammonium hydroxide.

Basicity

Aliphatic bases

As increasing strength in nitrogenous bases is related to the readiness with which they are
prepared to take up protons, and therefore, to the availability of the unshared electron pair
on nitrogen, we might expect to see an increase in basic strength on going : NH3  RNH2
 R2NH R3N, due to the increasing inductive effect of successive alkyl groups making the
nitrogen atom more negative. An actual series of amines was found to have related pKa
values as follows, however :

Rankers-JEE by Saurabh Maurya

 Me Me

Me NH2 NH Me N
Me Me

10.64 10.77 9.80

NH3
9.25 Et Et

Et NH2 NH Et N
Et Et

10.67 10.93 10.88

It will be seen that the introduction of an alkyl group into ammonia increases the basic
strength markedly as expected. The introduction of a second alkyl group further increases
the basic strength, but the net effect of introducing the second alkyl group is very much less
marked than the first. The introduction of a third alkyl group to yield a tertiary amine,
however, actually decreases the basic strength in both the series quoted. This is due to the
fact that the basic strength of an amine in water is determined not only by electron -
availability on the nitrogen atom, but also by the extent to which the cation, formed by
uptake of a proton, can undergo solvation, and so become stabilised. The more hydrogen
atoms attached to nitrogen in the cation, the greater the possibilities of powerful solvation
via hydrogen bonding between these and water :

H2O:   H H2O:   H H2O:   H

| | |
R  N  H    OH2 > R  N  R > R  N  R
| | |
H2O:  H H2O:  H R
Decreasing stabilisation by solvation

Thus on going along the series, NH3  RNH2  R2NH  R3N, the inductive effect will tend
to increase the basicity, but progressively less stabilisation of the cation by hydration will
occur which will tend to decrease the basicity. The net replacing effect of introducing
successive alkyl groups thus becomes progressively smaller, and an actual changeover
takes place on going from a secondary to a tertiary amine. If this is the real explanation, no
such changeover should be observed if measurements of basicity are made in a solvent in
which hydrogen - bonding cannot take place; it has, indeed, been found that in
chlorobenzene the order of basicity of the butylamines is

BuNH2 < Bu2NH < Bu3N

Tetralkylammonium salts, e.g. R4N I-, are known, on treatment with moist silver oxide,
AgOH, to yield basic solution comparable in strength with the mineral alkalis. This is readily

understandable for the base so obtained, R4N O H , is bound to be completely ionised as
there is no possibility, as with tertiary amines, etc.,

Rankers-JEE by Saurabh Maurya

 
R3NH + -OH  R3N: + H2O

of reverting to an unionised form.

The effect of introducing electron withdrawing groups, e.g. Cl, NO2, close to a basic centre
is to decrease the basicity, due to their electron withdrawing inductive effect. Thus the
amine

F3C

F3C N:

F3C

is found to be virtually non - basic, due to the three powerfully electron withdrawing CF3
groups.

The change is also pronounced with C=O, for not only is the nitrogen atom, with its electron
2
pair, bonded to an electron withdrawing group through an sp hybridised carbon atom but
an electron withdrawing mesomeric effect can also operate :

O O
|| | 

R  C  NH2  R  C = NH2

Thus amides are found to be only very weakly basic in water [pKa for
ethanamide(acetamide)

is  0.5], and if two C=0 groups are present the resultant imides, far from being basic, are
often sufficiently acidic to form alkali metal salts, e.g. benzene - 1, 2 - dicarboximide :

O O-
OH
:N H N-

O O-

Exercise -1:
O
||
C
N–H    A   B   C
i ) KOH Et 2NH HCl / H2 O
ii ) ( CH ) Br
2 3 2
C
||
O

Rankers-JEE by Saurabh Maurya

Aromatic bases

The exact reverse of the above is seen with aniline, which is a very weak base (pKa = 4.62)
compared with ammonia (pKa = 9.25) or cyclohexylamine (pKa = 10.68). In aniline the
nitrogen atom is again bonded to an sp2 hybridised carbon atom but, more significantly, the
unshared electron pair on nitrogen can interact with the delocalised  orbitals of the
nucleus:
  
:NH2 NH2 NH2 NH2

(a) (b) (c) (d)

If aniline is protonated, any such interaction, with resultant stabilisation, in the anilinium
cation is prohibited, as the electron pair on N is no longer available :

H:NH2

The aniline molecule is thus stabilised with respect to the anilinium cation, and it is therefore
‘energetically unprofitable’ for aniline to take up a proton ; it thus functions as a base with
the utmost reluctance (pKa = 4.62, compared with cyclohexylamine, pKa = 10.68). The base
weakening effect is naturally more pronounced when further phenyl groups are introduced
on the nitrogen atom ; thus diphenylamine, Ph2NH, is an extremely weak base (pKa = 0.8),
while triphenylamine, Ph3N, is by ordinary standards not basic at all.

Introduction of alkyl, e.g. Me groups, on to the nitrogen atom of aniline results in small
increase in pKa :

C6H5NH2 C6H5NHMe C6H5NHMe2 MeC6H4NH2

4.62 4.84 5.15 o-4.38
m-4.67
p-5.10

Unlike on such introduction in aliphatic amines this small increase is progressive :

suggesting that cation stabilisation through hydrogen - bonded solvation, responsible for the
irregular behaviour of aliphatic amines, here has less influence on the overall effect. The
major determinant of basic strength in alkyl-substituted anilines remain mesomeric
stabilisation of the aniline molecule with respect to the cation ; born out by the irregular
effect of introducing Me groups into the o-, m- and p-positions in aniline.

A group with a more powerful (electron - withdrawing) inductive effect, e.g. NO2 is found to
have rather more influence. Electron withdrawal is intensified when the nitro group is in the
o- or p-position, for the interaction of the unshared pair of the amino nitrogen with the
delocalised  orbital sytsem of the benzene nucleus is then enhanced. The neutral molecule

Rankers-JEE by Saurabh Maurya

is thus stabilised even further with respect to the cation, resulting in further weakening as a
base. Thus the nitro - anilines are found to have related pKa values :

:NH2 NH2
PhNH2 NO2C6H4NH2
4.62 o -0.28
m- 2.45
p- 0.95
N

N

O O O O

The extra base - weakening effect, when the substituent is in the o-position, is due in part to
the short distance over which its inductive effect is operating, and also to direct interaction,
both steric and by hydrogen bonding, with the NH2 group. o-Nitroaniline is such a weak
base that its salts are largely hydrolysed in aqueous solution, while 2, 4 - dinitroaniline is
insoluble in aqueous acids, and 2, 4, 6 - trinitroaniline resembles an amide; it is indeed
called picramide and readily undergoes hydrolysis to picric acid (2, 4, 6 - trinitrophenol).

With substituents such as OH and OMe that have unshared electron pairs, an electron -
donating, i.e. base-strengthening, mesomeric effect can be exerted from the o- and p-, but
not from the m-positon, with the result that the p-substituted aniline is a stronger base than
the corresponding m-compound. The m-compound is a weaker base than aniline itself, due
to the electron - withdrawing inductive effect exerted by the oxygen atom in each case. As
so often, the effect of the o - substituent remains somewhat anomalous, due to the
interaction with the NH2 group by both steric and polar effects. The substituted anilines are
found to have related pKa values as follows :

:NH2 NH2
PhNH2 HOC6H4NH2 MeOC6H4NH2
o- 4.72 o- -4.49
m- 4.17 m- 4.20
p- 5.30 p- 5.29
:OMe
:OMe 

Exercise-2: pKa values of o, m & p isomers of nitro-anilines are found to be 0.28, 2.45 &
0.98 respectively – explain

Preparation Of Amines
Alkylation of NH3, RNH2 and R2NH with RX

Step 1 RX + NH3  RNH3+X- (an SN2 reaction)

an ammonium
salt

Step 2 RNH3+X- + NH3  RNH2 + NH4+X-

Di-, tri- and tetralkylation :

Rankers-JEE by Saurabh Maurya

 RX RX RX
RNH2  R2NH  R3N  R4N+ X-
-HX -HX -HX
1° 2° 3° 4°
ammonium salt

When RX = MeI, the sequence is called exhaustive methylation.

Alkylation of Imides; Gabriel Synthesis of 1° Amines

O O O
COO-K+

N- K+ R -X-
-
:N:H OH+ NR 2KOH +RNH2
-H -X H2O
SN2
COO-K+
O O O
Phthalimide Salt

Reduction of N-Containing Compounds

1. Nitro Compounds
1Sn, HCl
C6H5NO2 2.OH
- C6H5NH2
Nitrobenzene Aniline

NO2 NH2
NH4SH (Only one NO2 is
LiAlH4 reduced)

NO2 NO2
m-Dinitrobenzene m-Nitroaniline

2. Nitriles LiAlH4
RCN RCH2NH2

3. Amides RC  NR2  RCH2NR2 (R = H, alkyl, aryl)

||

O NOH NH2

H2NOH Na
C2H5OH
4. Oximes
Oxime Cyclohexylamine

Rankers-JEE by Saurabh Maurya

5. Carbonyl Compounds
NH3.H2/Ni
CH3CH = O CH3CH2NH2 (Reductive amination)
H2/Ni
CH3CH2CHO + CH3CH2NH2 CH3CH2CH2NHCH2CH3 (1°  2° amine)

RNH2 + 2H2C = O + 2HCOOH  RN(CH3)2 + 2H2O + 2CO2 (Dimethylation of 1°

amine)

Hofmann Degradation of Amides

RCONH2 + Br2 + 4KOH  RNH2+K2CO3+2KBr + 2H2O

(The amine has one less C than the amide)

.. OBr- ..
R  C  NH2  R  C  N Br + OH-
Step 1 || (Br2.OH-) || |
O O H
N-bromoamide

Step 2 H _
| ..
RCN -
..  Br + OH  R  C  N..  Br  R  C = N.. Br + H2O
|| || |
O O: :O:
.. -
N-bromoamide anion

Step 3
..- .. .. -
R  C  N..  Br
.. : R  C  N..+ Br
|| ||
O O
electron - deficient N

Step 4 -
R:
R  C  N:
..  O = C = N:
.. R
O alkyl
isocyanate
Step 5 H2O
2OH- + R  N = C = O  R  NH2 + CO32-
amine

Exercise-3: How you prepare each of the following compounds from benzene
i)
NH2

NO2
ii)
NH2

Br

Rankers-JEE by Saurabh Maurya

Reactions of Amines
Reaction with Nitrous Acid, HONO

1. Primary Amines

a) Aromatic (Ar NH2)

HONO
C6H5NH2  (C6H5  +N  N:)Cl Benzenediazonium chloride
–

HCl,O°C

b) Aliphatic (RNH2)-
HONO
CH3CH2CH2NH2  [CH3CH2CH2N2]+ Cl- 
HCl
(unstable
) + +
N2 + Cl- + CH3CH2CH2  CH3CHCH3

H2O Cl- -H+ -H+ H2O Cl-

CH3 CH2CH2OH CH3CH2CH2Cl CH3CH = CH2 CH3CHCH3 CH3CHCH3

| |
OH Cl
1-Propanol 1-Chloropropane Propene 2-Propanol 2-
Chloropropane
This reaction of RNH2 has no synthetic utility, but the appearance of N2 gas signals
indicates the presence of NH2.

2. Secondary Amines

Ar(R)NH (or R2NH) + HONO  Ar(R) NNO (or R2N  NO) + H2O
an N - nitrosoamine
(insoluble in acid)

3. Tertiary Amines

No reaction except for N, N - dialkyl arylamines.

HONO +
(CH3)2 N (CH3)2 N NO (attack by NO )

Reaction with Carboxylic Acid Derivatives

RCONHR + HCl

(RCO)2O
RNH2 RCONHR + RCOOH

RCOOR

RCONHR + ROH

Rankers-JEE by Saurabh Maurya

Reactions with other Electrophilic Reagents
RCH = O + RNH2 -H2O R CH = NR (Schiff base or azomethine)

O O
|| ||
Cl  C  Cl +2RNH2  2HCl + RNH  C  NHR (symmetrical disubstituted urea)
O H O
| | || (unsymmetrical
R  N = C = O + H2NR  R  N = C  N+  R  RNH  C  NHR disubstituted urea)
isocyanate |
H
S
||
R  N = C = S + H2NR  RNH  C  NHR (a thiourea)
isothiocyanate

Nucleophilic Displacements

1. Carbylamine Reactions of 1° Amines

+ -
RNH2 + CHCl3 + 3KOH  R  N  C: + 3KCl + H2O
an isocyanide
(foul smelling)

Nucleophilic RNH2 attacks electrophilic intermediate [:CCl2].

2. Hinsberg Reaction

O H O
|| | |
+ -
C6H5  S  NR  H2O + Na C6H5  S  NR
Na OH +

O RNH2 || (acidic) |
|| O O
C6H5  S  Cl
|| O R
O || |
R2NH
Na+OH- (No Reaction)
C6H5  S  NR 
||
(neutral)
O

Reactions of Quaternary Ammonium Salts

1. Formation of 4° Ammonium Hydroxides

2R4N+X- + Ag2O + H2O  2R4N+OH- + 2AgX

very strong
bases like NaOH

2. Hofmann Elimination of Quaternary Hydroxides

[(CH3)3 NCH(CH3)CH2CH3]+OH-  (CH3)3N + H2C = CHCH2CH3 + H2O

s-Butyltrimethylammonium hydroxide 1 - Butene

Rankers-JEE by Saurabh Maurya

 This E2 elimination gives the less substituted alkene (Hofmann product) rather than the
more substituted alkene (Saytzeff product).

Ring Reactions of Aromatic Amines

NH2,  NHR and -NR2 strongly activate the benzene ring towards electrophilic substitution.

1. Halogenation

For monohalogenation, NH2 is first acetylated, because

CH3  C  N 
|| |
O H
is only moderately activating
NH2 NH2 NHCOCH3 NHCOCH3 NH2
Br Br
Br2 Ac2O Br2 H2O
H2O OH-
Br Br
Br Acetanilide

2. Sulfonation
NH2 NH3+HSO4- NHSO3H NH3+
H2SO4 180°C 180°C
H2O 3 hours

Sulfamic SO-3
Anilinium
Sulfate acid Sulfanilic acid
a dipolar ion

The dipolar ion structure of sulfanilic acid account for its (a) high melting point, (b)
insolubility in H2O and organic solvents, (c) solubility in aqueous NaOH, (d)
insolubility in aqueous HCl.

H3N+ CH2COO- exists at a dipolar ion whereas p-H2NC6H4COOH does not.

+
-COOH is too weakly acidic to transfer an H to the weakly basic - NH2 attached to
the electron withdrawing benzene ring. When attached to an aliphatic C, the NH2 is
sufficiently basic to accept H - from COOH.
+
3. Nitration: To prevent oxidation by HNO3 and meta substitution of C6H5NH3 , amines
are first acetylated.

O O
|| ||
NH2 NHCCH3 NHCCH3 NH2
-
(CH3CO)2O HNO3.H2SO4 OH
heat

Aniline Acetanilide NO2 NO2

p-Nitroacetanilide p-Nitroaniline

Rankers-JEE by Saurabh Maurya

 Aniline-X Rearrangements

NH2 NH2
HNX
X
and

1. Fischer - Hepp NO H
| |
Ph  N  R 1 H+ O=N N R
2 OH-
N-Nitroso- (neutralize p-Nitroso-N-alkylaniline
N-alkylaniline salt)

2. Phenylhydroxylamines H
|
Ph  N  OH 1 H+ p-HO NH2
2 OH-
p-Hydroxyaniline

Zn,NH4+
PhNO2  Ph(NHOH)

3. Sulfamic Acid heat -O S

Ph  NH SO3H  3 NH3+

Sulfanilic acid

Reactions of Aryl Diazonium Salts

Displacement Reactions
+ HPH2O2  Ar  H + N2
+ KI  Ar - I + N2
+ CuCI (CuBr)  ArCl(ArBr) + N2 (Sandmeyer reaction)
+ HBF4  ArN2+BF4-  ArF + N2 + BF3
ArN2+ X– + HOH  ArOH + N2
+ HO  C2H5  ArOC2H5 + ArH + CH3CHO + N2
+ CuCN  ArCN + N2
+ NaNO2 + NaHCO3  ArNO2 +N2
Cu2O
Coupling (G in ArG is an Electron - Releasing Group)

ArN+2 + C6H5G  p - G  C6H4  N = N - Ar (G = OH, NR2, NHR, NH2)

a weak a strongly an azo compound ;
electro activated mainly para
phile ring
Azo compounds undergo reduction as shown :

Rankers-JEE by Saurabh Maurya

ArN = NAr  ArNH  NHAr (mild reduction)
a hydrazo
compound
1. SnCl2, H3O+
ArN = NAr ArNH2 + H2NAr (vigorous reduction)
2. OH-

Hydrazo compounds are also made as follows :

Sn,NaOH
PhNO2  PhNHNHPh
Diaryl hydrazo compounds undergo the benzidine rearrangement
H H
N N 1. H3O+ H2N NH2
Hydrazobenzene Benzidine

Exercise-4:

Me
NaNO2
Me ––– C –––– CMe2 + HCl Me – C – CMe3 , explain the mechanism
O–H NH2 O

Exercise-5: A neutral compound (A) C8H9ON on treatment with NaOBr forms an acid
soluble substance C7H9N. On addition of aqueous NaNO2 to a solution of B in
dilute HCl at 0 – 5C an ionic compound (C) C7H7N2Cl is obtained. (C) gives a
red dye with alkaline  -napthol solution. When treated with potassium
cuprocyanide (C) yields a neutral substance (D) C8H7N. On hydrolysis (D)
gives E (C8H8O2). E liberates CO2 from aqueous NaHCO3. (E) on permanganate
oxidation furnishes (E) C8H6O4. (F) on nitration yields two isomeric mononitro
derivatives (G & H) having molecular formula C8H5NO6. Write the reactions
involved in different steps.

Rankers-JEE by Saurabh Maurya

Answers to Exercise
Exercise-1: O
||
C
A= N (CH2)3Br
C
||
O

B= N (CH2)3NEt2

O
CO2H
C=
CO2H

Exercise-5: CONH2 NH2 N2+Cl–

A= B= C=
CH3 CH3 CH3
CN CO2H COOH
D= E= F=
CH3 CH3 COOH
CO2H CO2H
G, H are
CO2H CO2H
O2N
NO2

Rankers-JEE by Saurabh Maurya

Assignments
Subjective
LEVEL – I

1. What is the order of bascity of the following compounds

a) CH3NH2, (CH3)2NH, (CH3)3N (in aprotic solvent)
b) C2H5NH2 (C2H5)2NH, (C2H5)3N (in aprotic solvent)
c) CH3NH2, (CH3)2NH, (CH3)3N (in protic solvent)
d) C2H5NH2, (C2H5)2NH, (C2H5)3N (in protic solvent)

2. H3C – NH2 + NaNO2 + HCl  A Reactions proceed in

two different
C6H5 – NH2 + NaNO2 + HCl  B paths - explain

H2O (warm)
3. B
CuCN
C
CuCl
C6H5NH2   A
HONO
D
0 5 C CuBr
E
HBF4/heat
F
H3PO2
G

4. When methyl amine is treated with alcoholic KOH and CHCl3 what will be the
product?

5. When methyl amide reacts with solution of bromine in presence of NaOH what will
be the product? How this reaction is useful to convert acid containing higher carbon
from that containing lower carbon e.g. from CH3CO2H  C2H5CO2H. What is the
structure of intermediate in this reaction.
6. Alkyl cyanides (CH3CN) when treated with hydrogen in presence of Pt or with
LiAlH4 produces same compound. What is the formula of that compound?
7. Identify A to I
CH 3 NH 2   A 
HNO2
 B 
P / I2
 C 
KCN
 D
[ H]
Na / Alcohol

HNO2

I  H  G 
NH3
 F 
PCl5
 E
KMnO 4
NaOBr

8. How you distinguish CH3CONH2 from CH3NH2?

9. 3 amine does not undergo acylation but 1 amine does – explain
10. NO2 NO2

NO2 NH2
For the following conversion what is the reagent used?

Rankers-JEE by Saurabh Maurya

 LEVEL – II

1. Cyclohexylamine is a stronger base than aniline. Why?

2. How does the formation of 2 and 3 amines can be avoided during the preparation
of 1 amines by alkylation?

3. It is necessary to acetylate aniline first for preparing bromoaniline. Why?

4. An organic compound containing carbon, hydrogen and nitrogen was found to

contain
C = 61.03%, N = 23.71%. Its vapour density = 29.5. On treatment with nitrous acid,
it gave out nitrogen. Identify the compound and explain the reaction.

5. Dimethylamine is a stronger base than methylamine but trimethylamine is a weaker

base than both dimethyl amine and methylamine. Why?

6. Two compounds A and B each containing C=63.58%, H=5.96% and N=9.26% gives
benzoic acid on oxidation. Both dissolve in NaOH solution with a red colouration. On
reduction A and B yield amines C and D respectively. C, but not D, can be resolved
into optical isomers. What are A and B?

7. Compound (X) containing chlorine, on treatment with NH3, gives a solid ‘Y’ which is
free from chlorine (Y) analysed as C = 49.3% H = 9.59% and N = 19.18% and reacts
with Br2 and caustic soda to give a basic compound (Z), (Z) reacts with HNO 2 to
give ethanol suggest structures for (X), (Y) and (Z).

8. The reaction of n-butylamine with sodium nitrite and hydrochloric acid yields nitrogen
and the following mixture; n-butyl alcohol, 25%; sec butyl alcohol, 13%; 1 butene
and 2-butene, 37%, n-butyl chloride, 5%; sec butyl chloride, 3% (A) what is the most
likely intermediate common to all of these product, and how is it formed.

9. From analysis and molecular weight determination, the molecular formula of (A) is
C3H7NO. The compound gave following reactions.
i) On hydrolysis it gives an amine (B) and a carboxylic acid (C)
ii) Amine (B) reacts with benzene sulphonyl chloride and gives a product which is
insoluble in aqueous sodium hydroxide solution.
iii) Acid (C) on reaction with Tollen’s reagent gives a silver mirror what are A, B and
C. Explain the reactions.

10. An optically active amine (A) is subjected to exhaustive methylation and Hofmann
elimination to yield an alkene (B). (B) on ozonolysis gives an equimolar mixture of
formaldehyde and butanal. Deduce the structures of (A) & (B). Is there any structural
isomer to (A), if yes draw its structure.

Rankers-JEE by Saurabh Maurya

 LEVEL – III
1. O
||
C
N–H    A   B   C
i ) KOH Et 2NH HCl / H2O
ii) ( CH ) Br
2 3 2
C
||
O

2. An optically inactive acid (A), C5H8O5, on being heated lost CO2 to give an acid (B),
C4H8O3 capable of being resolved.
On action of sulphuric acid, B gave an acid C whose ethyl ester gave (D) on the
action of hydrogen and platinum.
(D) with conc. NH3 gave E, C4H9OH which with Br2 & KOH solution gave (F), C3H9N.
F with HNO2 gave G. (G) on mild oxidatioin gave H. Both A & H gave the iodoform
reaction. Elucidate the reaction mechanism and suggest a synthesis of (C).

3. A compound A C14H10N2O when heated with dilute H2SO4 gave (NH4)2SO4, a

compound B, C8H6O4 and a compound C, C6H7N (as its sulphate). Compounds B &
C behaved as follows.
B   C8H4O3(D)
heat
C
Heated with dil. H2SO4 + NaNO2 is 0 – 5C H2O warm
sodalime

Benzene C6H6O (E)

Heated with Zn dust

Benzene
Suggest a formula for A and account for the above reactions.

4. A neutral compound (A) C8H9ON on treatment with NaOBr forms an acid soluble
substance C7H9N. On addition of aqueous NaNO2 to a solution of B in dilute HCl at 0
– 5C an ionic compound (C) C7H7N2Cl is obtained. (C) gives a red dye with alkaline
-napththol solution. When treated with potassium cuprocyanide (C) yields a neutral
substance (D) C8H7N. On hydrolysis (D) gives E (C8H8O2). E liberates CO2 from
aqueous NaHCO3. (E) on permanganate oxidation furnishes (E) C8H6O4. (F) on
nitration yields two isomeric mononitro derivatives (G & H) having molecular formula
C8H5NO6. Write the reactions involved in different steps

5. An organic acid (A) C3H4O3 is catalytically reduced in presence of ammonia to give B

C3H7NO2. (B) reacts with acetyl chloride, hydrochloric acid and alcohol. It can also
react with nitrous acid to give another compound (C), C3H6O3, along with evolution of
N2. What are (A), (B) and (C)

6. An organic compound (A) gave the following data in analysis C = 61.1%, H =

15.25% and N = 23.74%. (SA) on heating with HNO2 gives (B). Which contains C =
60%, H = 13.33% and no nitrogen. (B) on careful oxidation gave (C) which shows
iodoform test and has molecular weight 58. What are (A), (B) and (C).

Rankers-JEE by Saurabh Maurya

7. A neutral organic compound (A) C5H11O2 N when treated with reducing agent forms
a basic compound (B) C5H13N. (B) on treatment with excess of CH3I followed with
moist Ag2O gives (C) C8H21ON. On heating (C) decomposes to give trimethyl amine
and 2-methylbutene-1. What are (A), (B) and (C).

8. An organic compound (A) containing C = 32%, H = 6.66% and N = 18.67% and

vapour density = 37.5. (A) on reduction gave an amine (B) which gave ethanol with
HNO2. (B) gave an offensive smell on warming with CHCl3 and KOH forming (C),
which on reduction gave methyl ethyl amine. What are (A), (B) and (C).

9. One mole of each of bromo derivative (A) and NH3 react to give one mole of an
organic compound (B). (B) reacts with CH3I to give (C). Both (B) and (C) react with
HNO2 to give compounds (D) and (E), respectively. (D) on oxidation and subsequent
decarboxylation gives 2-methoxy -2-methyl propane. Give structures of (A) to (E)
with proper reasoning.

10. Two isomeric compounds (A) and (B) have C4H11N molecular formula. Both on
separately treating with HNO2 lose their N2 producing two isomeric alcohols (C) and
(D) respectively of molecular formula C4H10O. (C) reacts with Lucas reagent
immediately and units oxidation. (D) does not react with Lucas reagent in cold but
can be easily oxidised. Complete methylation of either (A) or (B) is made which on
decomposition does not produce butene -1. Identify A to D.

Rankers-JEE by Saurabh Maurya

Objective

LEVEL - I

1. Amines are highly soluble in:

(A) Alcohol (B) Diethyl ether
(C) Benzene (D) Water

2. Which of the following reagents can convert benzene diazonium chloride into
benzene?
(A) Water (B) Acid
(C) Hypophosphorous acid (D) HCl

3. The number of resonating structure of aryl ammonium ion is

(A) 2 (B) 3
(C) 4 (D) 5

4. When methyl iodide is treated with ammonia, the product obtained is

(A) Methylamine (B) Dimethylamine
(C) Trimethylamine (D) None

5. Hinsberg’s reagent is
(A) Phenyl isocyanide (B) Benzenesulphonyl chloride
(C) p. toluenesulphonic acid (D) o. dichlorobenzene

6. Peptide has the functional group

(A) Amino group (B) Carboxylic group
(C) Amide group (D) Ester group

7. The bromination of aniline produces

(A) 2-bromoaniline (B) 4-bromoaniline
(C) 2,4,6 – tribromoaniline (D) 2,6-dibromoaniline

8. The compound, which on reaction with aqueous nitrous acid at low temperature
produces an oily nitrosoamine is
(A) Methyl amine (B) Ethylamine
(C) Diethylamine (D) Triethylamine

9. Carbylamine test is performed in alcoholic KOH by heating a mixture of

(A) Chloroform and silver powder
(B) Trihalogenated methane and a primary amine
(C) An alkyl halide and a primary amine
(D) An alkyl cyanide and a primary amine

10. A colourless, odourless and non-combustible gas is liberated when ethylamine

reacts with:
(A) NaOH (B) CH3COCl
(C) NaNO2 + HCl (D) H2SO4

Rankers-JEE by Saurabh Maurya

 LEVEL - II

1. Acetamide is treated separately with the following reagents. Which one of these
would give methylamine?
(A) PCl5 (B) Sodalime
(C) NaOH+ Br2 (D) Hot concentrated H2SO4

2. Reagent which can convert an alkyl amine into alkyl chloride.

(A) Tilden reagent (B) Lucas reagent
(C) Hisnberg’s reagent (D) None

3. Reagent which is used for estimation of molecular weight of alkyl amine

(A) Oxalic acid (B) Chloroplatinic acid
(C) Picric acid (D) Nitrous acid

4. Sanger’s reagent is:

(A) 2-fluoro 1, 4 dinitrobenzene (B) Phenylisothiocyanate
(C) 1-fluoro 2, 4 dinitrobenzene (D) FDNB

5. Activation of benzene ring by –NH2 in aniline can be reduced by treating with

(A) Dilute HCl (B) Ethyl alcohol
(C) Acetic acid (D) Acetyl chloride

6. At the isoelectric point:

(A) There is a net migration of amino acid towards the anode
(B) There is a net migration of amino acid towards cathode
(C) There is no net migration
(D) Hydrogen ion concentration remains same

7. Dipolar ion structure for amino acid is

– +
(A) NH2 – CH – COOH (B) H3 N – CH – COO
| |
R R
(C) H3 N – CH – COO–
+
(D) None
|
R

8. –NH2 group shows acidic nature while reacts with reagent.

(A) Na (B) CS2
(C) Br2 + NaOH (D) Water

9. Product of Hofmann mustard’s oil reaction’s

(A) Mustard gas (B) Alkyl isocyanate
(C) Alkyl thiocyanate (D) Alkyl isothiocyanate

10. Which of the following does not give ethylamine on reduction

(A) Methyl cyanide (B) Ethyl nitrile
(C) Nitro ethane (D) Acetamide

Rankers-JEE by Saurabh Maurya

Answers
Subjective

LEVEL – I

1. a) (CH3)3N  (CH3)2NH  CH3NH2

b) (C2H5)3  (C2H5)2NH  C2H5NH2
c) (CH3)2NH  CH3NH2  (CH3)3N
d) (C2H5)2NH  (C2H5)3N  C2H5NH2

2. A = CH3OH
+ –
B = C6H5N2 Cl
+ –
3. A = C6H5N2 Cl
B = C6H5OH
C = C6H5CN
D = C6H5Cl
E = C6H5Br
F = C6H5F
G = C6H6

4. CH3NH2 + 3KOH + CHCl3 = 3KCl + CH3NC + 3H2O

5. Intermediate should be CH3NCO (methyl isocyanate)

NH3 /  Br2  4NaOH
CH3COOH    CH 3 CONH 2   CH 3 NH 2

6. CH3CH2NH2

7. A = CH3OH
B = CH3I
C = CH3CN
D = CH3CH2NH2
E = CH3CH2OH
F = CH3CO2H
G = CH3COCl
H = CH3CONH2
I = CH3NH2

10. NaHS or Na2S or NH4HS or (NH4)2S

Rankers-JEE by Saurabh Maurya

 LEVEL - II

1. Aniline is a weak bas than cyclohexylamine because of resonance.

2. Use of excess ammonia reduces chances of reaction of 1 amine with alkyl halide to
form 2 and 3 amines.

3. Amino group, being activating group, activates bromination of aniline and forms
tribromoaniline.

4. n-propyl amine

5. Dimethyl amine is stronger base because of inductive effect. Trimethyl amine is a

weaker base because positive charge on nitrogen could be stabilized and due to
crowding by alkyl groups around the nitrogen atom protonation cannot take place.

6. CH2CH2NO2 CH2CH2NH2

(B) (D)
CH3
CH—NO2 CH—NH2
CH3
(A) (C)

7. (X) CH3CH2COCl
(Y) CH3—CH2—CONH2
(Z) CH3—CH2—NH2

8. n-Butyl cation

9. CH3
(A) HCON (N,N – dimethyl formamide)
CH3

CH3
(B) NH
CH3
(C) HCOOH

10. NH2

(A) CH3–CH–CH2–CH2–CH3

(B) CH2=CH–CH2–CH3

Rankers-JEE by Saurabh Maurya

 LEVEL – III
1. O
||
C
A= N (CH2)3Br
C
||
O
O

B= N (CH2)3NEt2

O
CO2H
C=
CO2H
2. CH2OH CH2
CH2OH
A = H3C – C – CO2H B = H3C ––––– CO2H C= H3C – C – CO2H

CO2H H
D = (CH3)2CHCO2C2H5 E = (CH3)2CHCONH2
F = (CH3)2CHNH2 G = (CH3)2CHOH
H = CH3COCH3

3. CN CO2H
CONHC6H5 CO2H NH2
A= B= C=

O
||
C
D= O E = C6H5OH
C
||
O

4. CONH2 NH2 N2+Cl–

A= B= C=
CH3 CH3 CH3
CN CO2H COOH
D= E= F=
CH3 CH3 COOH
CO2H CO2H
G, H are
CO2H CO2H
O2N
NO2

Rankers-JEE by Saurabh Maurya

5. A CH3COCOOH
B CH3CHCOOH

NH2
C CH3CHCOOH

OH

6. A = (CH3)2CHNH2
B = (CH3)2CHOH
C= (CH3)2CO

7. A CH3CH2CHCH2NO2

CH3
B CH3CH2CHCH2NH2

CH3
C + CH3
CH3CH2CH—CH2—N OH–
CH3
CH3 CH3

8. A = C2H5NO2
B = C2H5NH2
C = C2H5NC

9. OCH3 OCH3

A CH3—C—CH2—CH2—Br B CH3—C—CH2—CH2—NH2

CH3 CH3
OCH3 OCH3

C CH3—C—CH2—CH2—NH D CH3—C—CH2—CH2—OH

CH3 CH3 CH3

OCH3

CH3—C—CH2—CH2—N—NO
E
CH3 CH3

10. A = (CH3)2C—NH2
B = (CH3)2CH—CH2—NH2
C = (CH3)3C—OH
D = (CH3)2CHCH2OH

Rankers-JEE by Saurabh Maurya

Objective

LEVEL - I

1. D 2. C

3. A 4. A, B, C

5. B 6. C

7. C 8. C

9. B 10. C

LEVEL - II

1. C 2. A

3. B 4. C, D

5. D 6. C, D

7. C 8. A

9. D 10. B

Rankers-JEE by Saurabh Maurya