16

1. IIT–JEE Syllabus
2. Introduction and Nomenclature
Amines
2.1 Structure of Amines
2.2 Classification of Amines
2.3 Nomenclature of Amines
2.4 Physical Properties
3. Basicity
3.1 Aliphatic bases
3.2 Aromatic bases Amines play a vital role in medicinal
4. Preparation of Amines
4.1 From Alkyl Halides chemistry. As our body is having a lot of
4.2 From Nitrogen Containing
Compounds
4.3 From Carbonyl Compounds amino acids, these amines help in the
4.4 Curtius Reaction
4.5 Schmidt Reaction
4.6 By Reduction of Alkyl Isocyanide
4.7 Preparation of Tertiary Amines
regulation of our body. It is also believed that,
5. Chemical Reaction
5.1 Basic Nature vitamins were named keeping vital-amines in
5.2 Acylation
5.3 Benzoylation
5.4 Carbylamine Reaction mind (though many vitamins don't have
5.5 Action with Aldehyde & Ketone
5.6 Hofmann mustard oil reaction
5.7 Reaction with Carbonyl Chloride nitrogen at all). Similarly to produce several
5.8 Reaction of Quaternary Ammonium salt
5.9 Reaction of Amines with Nitrous Acid
5.10. Coupling Reactions of Arene
Diazonium Salts
synthetic dyes, pigments the amines are used.
5.11. Ring Substitution of Aromatic
Amines Therefore, the amines are very important in
5.12. Aniline - X rearrangement
6. Separation of Mixture of Amines
6.1 Hinsberg’s Method our everyday life. Let us see how this is.
6.2 Hofmann’s Method
7. Test for Amines
7.1 Test for Primary Amines
7.2 Test for Secondary Amines
8. Solutions to Exercises
9. Solved Problems
9.1 Subjective
9.2 Objective
10. Assignments
(Subjective Problems)
11. Assignments
(Objective Problems)
12. Answers to Objective
Assignments
1. IIT-JEE Syllabus
Basicity of aniline and aliphatic amine, preparation from nitro compounds,
reaction with nitrous acid, formation and reactions or diazonium salts, and its
coupling with phenols, carbylamine reaction.

2. Introduction and Nomenclature

2.1 Structure of amines

Amines are the alkyl (or) aryl derivatives of NH3. The general formula of amine is R3N,
where R is an alkyl (or) aryl group or hydrogen.
CH 3NH 2 (CH 3 ) 2 NH (CH 3 ) 3 N
(Methylamine) (Dimethylamine) (Trimethylamine)

In amines one or more Hydrogen atoms of ammonia are replaced by Alkyl or aryl groups.
Here nitrogen atom of amines is like that of NH3, it is sp3 hybridised. The three Alkyl
groups (or hydrogen atoms) occupy corners of a tetrahedron, one of sp3 orbital
occupying the unshared electron pair directed towards the other corner. We say shape of
amine as “Trigonal Pyramidal”.

N
R R
R

2.2 Classification of amines

Amines are classified as primary, secondary (or) tertiary according to the number of
groups attached to the nitrogen atom. If one alkyl group has replaced one hydrogen
atom of ammonia, it is primary amine. Similarly, if two hydrogens are replaced, it is
secondary amine and if all the three are replaced, it is tertiary amine.

We can also replace all the 4 hydrogens in NH 4 with alkyl groups to get a quaternary
tetra alkyl ammonium ion.
H
NH2 N )3N

(Aniline;1°) (Diphenyl aniline;2°) (Triphenyl amine;3°)

)4NCl–

(Tetraphenyl ammonium
chloride;4°)
2.3 Nomenclature of amines

Nomenclature of amines is quite simple. Aliphatic amines are named by naming the alkyl
group (or) groups attached to nitrogen , and following that by the word amine.

H CH3

(CH3)3C—NH2 CH3CH2—N—CH3 CH3—CH2—CH—N—CH3

(tert-butyl amine) (Ethyl methyl amine)
CH3
(sec-Butyl dimethyl amine)

More complicated amines are often named as prefixing amino - (or-N-methylamino -, N-

N, diethyl amino -, etc) to the name of the parent chain.

H CH3
H2NCH2CH2CH2CO2H H2NCH2CH2OH CH3—N—CH—(CH2)4 —CH3
(4-Aminobutyric acid) (2-Amino ethanol) 2-(N-methyl amino) heptane

Aromatic amines - those in which nitrogen is attached to an aromatic ring - are generally
named as derivatives of the simplest aromatic amine, aniline.
Br
CH3
NH2 N
C2H5

Br Br
(N-ethyl-N-methyl aniline)
(2,4,6-Tribromo aniline)

CH3

H2N
(p-toludine)

Salts of amines are generally named by replacing - amine by - ammonium (or - aniline by
- anilinium), and adding the name of the anion.
NH3Cl–

(CH3)3NHNO3–
(Trimethylammonium nitrate) (Anilinium chloride)

2.4 Physical Properties

Amines are moderately polar substances; they have boiling points that are higher than
those of alkanes but generally lower than alcohols of comparable molecular weight.
Molecules of primary and secondary amines can form strong hydrogen bonds to each
other and to water. Molecules of tertiary amines can not form hydrogen bonds to each
other, but they can form hydrogen bonds to molecules of water or other hydroxylic
solvents. As a result, tertiary amines generally boil at lower temperatures than primary
and secondary amines of comparable molecular weight.
3. Basicity
3.1 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 :

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 with 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 stabilized.
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 –OH, is bound to be completely
ionised as there is no possibility, as with tertiary amines, etc.,

 -
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 center is to decrease the basicity, due to their F3C
electron withdrawing inductive effect. Thus the amine is found to be F3C N:
virtually non - basic, due to the three powerfully electron withdrawing
CF3 groups. This can well be explained on the basis of more ‘s’ F3C
character on lone pair of N.

The change is also pronounced with C=O, for not only is

the nitrogen atom, with its electron pair, bonded to an O O
electron withdrawing group through an sp2 hybridised ||

| 
carbon atom but an electron withdrawing mesomeric R  C  NH2  R  C = NH2
effect can also operate :

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 N
-
H

O
-
O

3.2 Aromatic Bases:

The exact reverse of the above is seen with

aniline, which is a very weak base (pKa = 4.62)   
:NH2 NH2 NH2 NH2
compared with ammonia (pKa = 9.25) or
cyclohexylamine (pKa = 10.68). In aniline the
nitrogen atom is again bonded to a sp2 hybridised
carbon atom but, more significantly, the unshared
electron pair on nitrogen can interact with the (a) (b) (c) (d)
delocalised  orbitals of the nucleus :
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 C6H5NMe2 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 behavior of aliphatic amines, here has less influence on the overall effect.
The major determinant of basic strength in alkyl-substituted anilines remains mesomeric
stabilisation of the aniline molecule with respect to the cation ; borne 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 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-position, 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-1 : i) Amines are stronger bases than ammonia. Why?

ii) Aniline is a weak base than ethylamine. Why?

4. Preparation of Amines
Now, that we have learnt something about amines, we shall now get into the methods of
their preparation.

4.1 From Alkyl halides

Many organic halogen compounds are converted into amines by treatment with aqueous
(or) alcoholic solution of ammonia. This reaction is generally carried out either by
allowing the reactants to stand together at room temperature (or) by heating them under
pressure. Displacement of halogen by NH3 yields the amine salt, from which free amine
can be liberated with hydroxide ion.

OH 
CH3Cl + NH3  CH 3 N H3 Cl   
 CH3NH2 + Cl– + H2O

The above reaction is a class of substitution reaction, which we know as nucleophilic

substitution.

Ammonia can act as a nucelophile and it can also act as a base.

If ammonia acts a nucleophile substitution takes place,

CH3CH2CH2Br + NH3  CH3CH2CH2NH2 + HBr

And, if ammonia acts as a base, elimination takes place.

 CH3
H3C CH3
CH3—C—CH3 NH3 C

Br CH2

It is very evident that primary alkyl halides under go substitution very easily than tertiary
alkyl halides, which undergo elimination very easily.

Look at the sequence of reactions below,


NH RX RX RX
RX 
3
 RNH 2  R 2NH  R3NH  R 4 NHX 
(1o ) (2o ) (3o ) ( 4o )

The reaction is quite simple and we can convert alkyl halide into all class of amines.

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

4.2 From nitrogen containing compounds

4.2.1 Nitro compounds

Nitro alkanes can be reduced quantitatively to their corresponding amines.

NO2
NH2
Reduction

Nitro compound can be reduced in two general ways: (A) by catalytic hydrogenation
using molecular hydrogen, or (B) by chemical reduction, usually by a metal and acid.

This method cannot be used when the molecule also contains some other easily
hydrogenated group, such as a Carbon carbon double bond. Chemical reduction is most
often carried out by adding hydrochloric acid to a mixture of the nitro compound and
metal, usually granulated tin or iron.
CH3 CH3 CH3


 
Sn, HCl

OH
+SnO3
heat

2
NO2 NH 3 SnCl 6 NH2

p-Nitrotoluene p-Toluidine

4.2.2 Nitriles

Alkyl and aryl cyanides can be reduced to their corresponding amines using LiAlH4

CN
CH2NH2
LiAlH4
4.2.3 Amides

Amides can directly be converted into their corresponding amines. This reaction is
carried out by treating the amide with a mixture of base and bromine (KOH + Br2). This
reaction is called as Hofmann Bromamide reaction.

The reaction is as follows,

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

Here we can see that the amine formed has one carbon less than that of the
corresponding amide. Due to the loss of carbon atom, this reaction is also called as
Hofmann degradation of amides.

The mechanism of the reaction is as follows:

.. OBr- ..
R  C  NH2  R  C  N Br + OH-
Step 1 || (Br2.OH-) || |
O O H
N-bromoamide
(one of the hydrogen attached to nitrogen is substituted by a bromine atom)
H _
| ..
-
RCN..  Br + OH  R  C  N..  Br  R  C = N.. Br + H2O
|| || |
O O: :O:
.. -
N-bromoamide anion
Step 2

(The N-bromamide anion thus formed as a result of proton by base is stabilized by

resonance)

..- .. .. -
R  C  N..  Br
.. : R  C  N..+ Br
|| ||
Step 3 O O
electron - deficient N
(Bromine leaves and we have an electron deficient nitrogen)

R:
R  C  N:
..  O = C = N:
.. R
O alkyl isocyanate
Step 4
(There is a shift of alkyl group to the nitrogen)
Step 5 -
2OH + R  N = C = O 
2 HO
R  NH2 + CO3
2-

amine
(A simple hydrolysis of an imine gives us the amine)

Apart from this, amides can be dehydrated by P2O5 to their corresponding nitriles and
nitriles can then be reduced.
 O
||
PO LiAlH4
R  C NH 2 2 
5
 R—C  N   R—CH2NH2

By this method you are retaining the number of carbon atoms in both amide and the
amine.

4.3 From carbonyl compounds

While studying carbonyl compounds we have seen that carbonyl compounds can be
converted into any other functional group. How are we converting carbonyl group into
amino group?

See, the following sequence,

H2 / Ni
CH3CH = O + NH3  CH 3CH  NH   CH 3 CH 2NH 2
(an imine) (an amine)

The reactions are clear and simple so that, we can get an amine from carbonyl
compound just by reductive amination (amination and reduction).

Using this reductive amination we can go from 1° amine to 2° amines. How? Look at the
following reaction.
CH3CH2CH = O + H2NCH 2CH 3  CH3CH2CH=NCH2CH3
(1o amine)

H2/Ni
CH 3CH 2CH 2NHCH 2CH 3
( 2 o amine)

4.4 Curtius reaction

Amines can be prepared by treating acid chloride with sodium azides the isocyanate thus
formed is decomposed with treatment of water and amines are obtained.
O O
|| ||  
R – C – Cl + NaN3  R – C – N – N  N
Acid chlorides Sodium Acyl azides
azides


CO 32  2OH
–

+ RNH2  R – N = C = O + N2
H2O Isocynate

4.5 Schmidt reaction

Hydrozoic acid reacts with carboxylic acid in presence of a mineral acid to give amines.
RCO 2H  HN3   RNH 2  CO 2
conc. H2 SO4

4.6 By the reduction of an alkyl isocyanide

RNC + 4[H]  R – NH – CH3

4.7 Preparation of Tertiary Amines

3RX + NH3    R3N + 2HX

Ethanolic solution

(in excess)

Exercise 3: In the presence of base, acyl derivatives of hydroxamic acids undergo the
Lossen rearrangement to yield isocyanates or amines.
O O
|| ||
R  C  N 0  C  R   RNCO 
Base
 RNH
H2 O
2
|
H
Write mechanism for the reaction.

5. Chemical Reaction
5.1 Basic Nature

Amines turn red litmus blue and also combine with water and mineral acids to form
corresponding salts.
 
R–NH2 + H2O  R –NH3 OH [RNH2 aliphatic or aromatic amine]

R – NH2 + HCl  R – NH3Cl –
R–NH2 + H2SO4  [RNH 3 ]2 SO24

When the amine salts are treated with strong bases like NaOH, the parent amines are
regenerated.

RN+H3Cl– + OH–  RNH2 + H2O + Cl–

Amine salt Amine

(Soluble is water) (insoluble in water)

Further, due to basic character amines react with auric and platinic chlorides in presence
of HCl to form double salts.

RNH 2  PtCl 4  2HCl (RNH 3 )2 PtCl 26

Chloroplatinic acid

These double salts decompose on ignition to pure metal, therefore, the formation and
decomposition of the double salts is used for determining the molecular weight of
amines.

5.2 Acylation (Reaction with Acyl Chlorides or Acid Anhydrides)

Primary and secondary amines can react with acid chlorides or acid anhydrides to form
substituted amides.

RNH2 + RCOCl  RCO NHR an N-substituted amide

R2NH + RCOCl  RCO.NR2 an N,N disubstituted amide

5.3 Benzoylation (Schotten Baumann Reaction)

Primary amine reacts with benzoyl chloride to give the acylated product.

R  NH 2  Cl  COC 6H5  R  NH  COC 6H5  HCl

NaOH

(Benzoyl chloride) Benzoyl alkyl amine

5.4 Carbylamine Reaction (Given Only by Primary Amines)

Primary amines when heated with chloroform and alcoholic caustic potash give
isocynaides (carbylamines) having very unpleasant smell, which can be easily detected

C2H5NH2 + CHCl3 + 3KOH  C2H5NC + 3KCl + 3H2O

Ethylamine Ethyl isocyanide

C6H5 NH2 + CHCl3 + 3KOH  C6H5NC + 3KCl + 3H2O

Aniline Phenyl isocyanide

5.5 Action with Aldehyde and Ketone

Both primary aliphatic and aromatic amines react with aldehydes and ketones to form
schiff’s bases also called anils.

C2H5NH2 + CH3CHO  C2H5N = CHCH3 + H2O

Ethylamine Acetaldehyde Ethylidene ethylamine
(Schiff’s base)

5.6 Hofmann Mustard Oil Reaction

Primary amines when warmed with alcoholic carbon disulphide followed by heating with
excess of mercuric chloride form isothiocyanates having pungent smell similar to
mustard oil.

NHC2H5
C2H5NH2 + S = C = S  S = C
SH
HgCl2

C2H5N = C = S + HgS + 2HCl

Ethylisothiocyanate

C6H5NH2 + S = C = S   C6H5NCS + 2HCl + HgS

HgCl 2

5.7 Reaction with Carbonyl Chloride

This reaction is given only by primary amines.

C2H5 – NH2 + COCl2  C2H5NCO + 2HCl

Ethylisocyanate

5.8 Reaction of Quaternary Ammonium Salts

5.8.1 Hofmann Elimination

When a quaternary ammonium hydroxide is heated strongly (125° or higher) it

decomposes to yield water, a tertiary amine and an alkene

This reaction is called as the Hofmann elimination. The formation of quaternary

ammonium salts followed by an elimination of the kind just described and identification of
the alkene and tertiary amine formed was once used in the determination of the structure
of complicated amines.
CH3 CH3
 – 
CH3 – N – CH2 – CH2 – CH3 OH   CH – N + CH = CH – CH + H O
3 2 3 2
 
CH3 CH3

5.9 Reaction of Amines with Nitrous Acid

5.9.1 The diazonium salts of amines

What are these diazonium salts? Let us look at the name. The name suggests that, the
compound has two nitrogen atoms (diazo) and the whole group has a positive charge
(ium). There is also an anion to balance it (It is a salt)

So, the possible structure can be

R  N2 X
How to prepare them? The preparation is quite simple if we adhere to the experimental
conditions.

These diazonium salts are prepared by treating a primary amine with NaNO2 in presence
of con. HCl; the temperature being 0°C. (Here the temperature has to be taken care of
and if the temperature exceeds 5°C, the reaction will not take place.)

Let us take a case of aliphatic amines,

HONO
CH3CH2CH2NH2   CH3CH2CH2 N2 Cl–
HCl;0 C

Mechanism for Diazotization is as follows

 +  +

H – ONO + H3O H2O+ – NO + H2O 2H2O + N= 0

H H
 +
 + 
–H
+ 
Ar  N N = O  Ar  N  N = O  Ar  N  N = O
  
H H H
+ +
–H
+ +H  
 – +H   +
 Ar – N = N – O –H+ Ar – N – N – OH –H+ Ar – N = N – OH2
+   +
Ar – N  N  Ar – N = N + H2O

The diazonium salts of aliphatic amines are generally unstable and they decompose to
give different products.
  – 
 – H~
CH3CH2CH2N2 Cl CH3CHC
2 H2  CH3 C H CH3 H3C
H2O H2O CH—OH
CH3CH2CH2OH H3C
– –
Cl Cl H3C
CH3CH2CH2Cl CH—Cl
+
–H H3C
CH3CH=CH2 +
–H
CH3CH=CH2
Thus we can have a wide range of products. Let us now see some thing about aromatic
amines
NH2 –
N2Cl
HONO
HCl;O°C

These aryl diazonium salts undergo a variety of displacement reaction. The reactions are
simple and are summarised below.
N2Cl–
H3PO2
CuCN
CN KI I
H2O
CuCl/
NaNO2,
CuBr
NaHCO3
OH HBF4 Cl Br
Cu2O
NO2 F

Mechanism of ArN2+ Cl– + H3PO2 reaction takes place through free radical pathway.

Chain initiation

ArN2+Cl– + H3PO2 = HCl + ArN2PH(O)OH


ArN2PH(O)OH  Ar + N2 + P H (O)OH

Chain propagation

Ar + H2PO2  ArH + HP (O)OH

ArN2+ + P H (O)OH  ArN2 + P+H(O)OH
ArN2  Ar + N2 P+H(O)OH + H2O  H3PO3 + H+

5.9.2 Reaction of secondary Amines with Nitrous acid

Secondary amines both aryl and alkyl react with nitrous acid to yield N-nitrosoamines. N-
nitrosoamines usually separate from the reaction mixture as oily yellow liquid.
   
(CH3)2 NH + HCl + NaNO2 (HONO)
 (CH3)2 N – N = O
H2O
Dimethylamine N-nitrosodimethylamine
(a yellow oil)

H N=O
 
N + HCl + NaNO2 (HONO)
 N
H2O
CH3 CH3
3 3
N-Nitroso-N-methyl aniline
(a-yellow oil)
N-nitrosoamines are very powerful carcinogens (cancer causing substances)

5.9.3 Reaction of Tertiary amines with Nitrous acid

When a tertiary aliphatic amine is mixed with nitrous acid, an equilibrium is established
among the tertiary amine, its salt, and an N-Nitrosoammonium compound.
+ – +
2R3N + HX + NaNO3 R3NH X + R3N – N = OX–
Tertiary aliphatic Amine N-Nitrosoammonium
amine salt compound

Tertiary arylamines react with nitrous acid to form C-nitroso aromatic compound.
Nitrosation takes place almost exclusively at the para position if it is open and if not, at
the ortho position. The reaction is another example of electrophilic aromatic substitution.
H3C H3C
  
N 8°C
+ HCl + NaNO2 
H2O
N N=O
H3C H3C
p-Nitroso-N, N–dimethyl
aniline

5.10 Coupling Reactions of Arene Diazonium Salts

Arenediazonium ions are weak electrophiles; they react with highly reactive aromatic
compounds with phenols and tertiary arylamines to yield azo compound. This
electrophilic aromatic substitution is called a diazo coupling reaction occurring mainly at
p-position.
0°C
N 2 Cl  + OH
NaOH,
N=N OH
H2O
Benzene diazonium Phenol p (Phenylazo) phenol
chloride (Orange solid)
O
||
– +
CH3 – CO Na
N2 Cl  + N(CH3)2 N=N N–(CH3)2
8°C
H2O
N-N-Dimethylaniline N-N dimethyl-p (phenylazo) aniline
(yellow solid)
Couplings between arenediazonium cations and phenols take place most rapidly in
slightly alkaline solution. If the solution is too alkaline (pH  10), however, the
arenediazonium salt itself reacts with hydroxide ion to form a relatively unreactive
diazohydroxide or diazotate ion.
– –
+  OH   OH   
Ar – N  N H
+ Ar – N = N – OH +
Ar – N = N – O

:–
H
Arenediazonium ion Diazohydroxide Diazotate ion
(couples) (does not couple) (does not couple)

Mild. red.
Ar—N=N—Ar  Ar—NH—NH—Ar
Vigorous 1. SnCl2, H3+O A hydrozo
reduction 2. OH– compound
2ArNH2
Hydrazo compounds are also made as follows:
Sn,NaOH
Ph—NO2   Ph—NH—NH—Ph

Diaryl hydrazo compounds undero the benzidine rearrangement

H3 O 
N—N   H2N —NH2

H H Benzidine
Mechanism:
NH———NH +
H2N———–NH2
+

2H 
 

H
+ + 2H 
H2N NH2   Benzidine
H

Exercise – 4: A weakly basic solution favours coupling with phenol. Is there any other
explanation?

5.11 Ring Substitution in Aromatic Amines

The –NH2, – NHR and –NR2 are benzene activating groups through resonance effect of
nitrogen where the lone one pair of electron of nitrogen is shifted to the benzene ring
making ortho and para, position available for electrophilic attack.

:NH2 +NH2 +NH2 +NH2

   
–: H H


: –

H
The carbocation formed as intermediate are
 +
NH2 +NH2
 
H
y and

H y

The group – NHCOCH3 is less powerful ortho and para director because of the electron-
withdrawing character of oxygen makes nitrogen a poor source of electrons. This fact is
made use in preparing mono substituted aniline. The –NH2 group is such a powerful
activator, that substitution occurs at all available ortho and para positions of aniline. If,
however, –NH2 group is converted to –NHCOCH3, the molecule becomes less powerful
activator. Hence only mono substitution products are obtained. Finally – NHCOCH3 is
converted back to –NH2 by hydrolyzing with acid. This technique is especially used while
nitrating aniline as strong oxidizing agent destroys the highly reactive ring.

NH2 NHCOCH3 NHCOCH3 NH2

   
+
CH3COCl HNO3 H2O, H
H2SO4
 
NO2 NO2
Exercise-5: Explain the following
i) It is necessary to acetylate aniline first for preparing bromoaniline.
ii) While carrying out an electrophilic substitution reaction on aniline.
Lewis acid is not used
Exercise 6: NMe NMe2
Me Me Me
Why has more basicity than ?

Exercise 7: Why the reagents to prepare

O O
CH2COOEt
from

5.12 Aniline -X rearrangement

R—N—X NHR NHR

X
Acid
 
 +
or Base

Major
X
Such compounds are not much stable so the group X migrates mainly at p-position.

1. Fisher-Hepp rearrangement
 R—N—NO NHR

HCl
 + o - isomer

NO
(Major product)

2. Phenylhydroxylamine - p-aminophenol rearrangement.

NHOH NH2

H 


Phenylhydroxylamine
OH
p-aminophenol

Mechanism

+
H+

+
+
NHOH NH— OH2 NH NH

Nucleophilic attack by H2O at p - position.

 NH HO— —NH2

6. Separation of a Mixture of Amines

6.1 Hinsberg’s Method

Treating a mixture of 3 amines with Hinsbergs reagent (benzene sulfonyl chloride) and
finally treating the product formed with NaOH can separate the 3 class of amines.

6.1.1 Primary amine:

RNH2 + C6H5SO2Cl  C6H5– SO2 – NH – R + HCl
(N-alkyl benzene sulfonamides)
(Dissolves in NaOH due to acidic H-attached to Nitrogen)

6.1.2 Secondary amine

R
R2NH + C6H5SO2Cl  C6H5–SO2–N + HCl
(Insoluble is NaOH) R

6.1.3 Tertiary amine

 Tertiary amines do not react with Hinsberg’s reagent.
After reacting with NaOH the aqueous layer and the second layer [Secondary
and Tertiary) can be separated by ether. Aqueous layer Hydrolysed with conc.
HCl gives primary amine. The ether layer is distilled and tertiary amine is distilled
over. Residue hydrolysed with conc. HCl to recover secondary amine.

6.2 Hofmann’s Method

The mixture of amines is treated with diethyloxalate, which forms a solid oxamide with
primary amine, a liquid oxime ester with secondary amine. The tertiary amine does not
react.
COOC2H5 + 2RNH2  CONHR + 2C2H5OH
 
COOC2H5 CONHR
diethyloxalate dialkyloxamide
(solid)

COOC2H5 + R2NH  CONR2 + C2H5OH

 
COOC2H5 COOC2H5
Oxamic ester
(liquid)

7. Test for Amines

7.1 Test for Primary Amines (Carbyl Amine Reaction):

When a primary amine is treated with a strong base in presence in chloroform, an

isocyanide is formed and this isocyanide thus formed has a very foul smell.

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

Here attacking electrophile is the dichlorocarbene (:CCl2). The primary amine can be
identified with its foul smell.

7.2 Test for Secondary Amines(Libermann Reaction)

The secondary amine is converted into nitrosoamine by treating the amine with nitrous
acid. The resultant solutions warmed with phenol and concentrated H2SO4, a brown or
red colour is formed at first soon it changes to blue and then to green. The colour
changes to red on dilution and further changes to greenish blue on treating with alkali.

Tertiary arylamines react with nitrous acid to form o-nitroso aromatic compound.

8. Solution to Exercises
Exercise 1: i) Amines have electron-repelling groups, which increase the electron
density on nitrogen, while ammonia has no such group.

ii) In aniline the electron pair of nitrogen atom is delocalised due to

resonance and hence lesser available for protonation while ethylamine
does not undergo resonance.

Exercise 2: Use of excess ammonia reduces chances of reaction of 1 amine with

alkyl halide to form 2 and 3 amines.

Exercise 3: O O O O
|| || 
||  ||
R  C  N 0  C  R   R  C  N 0  C  R 
OH
| 
H

O  C  N R  R COO 


 O 
 ||  HO
R  N C  OH  
2
 O  C  NR
 |
H 
 
Carbamic acid
(unstable)
- CO2
R-NH2

Exercise 4: High acidity suppresses the ionisation of C6H5OH to the more reactive
C6H5O–. In presence of weak base, C6H5O– is formed and coupling takes
place.

Exercise 5: i) Amino group, being activating group, activates bromination of aniline

and forms tribromoaniline.

ii) In presence of Lewis acids, aniline undergoes protonation to from

anilinium ion, which being m-directing forms unexpected m-substituted
derivative.

Exercise 6: This is because of strain relief on N atom in former one in its conjugate
acid than the later one.

Exercise 7: Reagents are pyrolidine (any secondary cyclic amine), TsOH,

BrCH2COOEt, H3O+.
Solved Problems
Objective
Problems 1: The correct order of increasing basicity for the following compounds is

NH2 CH3 CN

(I) (II) (III) (IV)

N N N N
(A) IV < I < III < II (B) I < II < III < IV
(C) IV < III < II < I (D) II < IV < I < III
Solution: (A)

Problems 2: How many primary amines are possible for the formula C4H11N
(A) 1 (B) 2
(C) 3 (D) 4

Solution: (D)

Problem 3: When aniline is treated with benzene diazonium chloride at low

temperature in weakly acidic medium, the final product obtained is

(A) NH2 (B)

N N NH2
N N

(C) (D) NH2

N N NH

N N
Solution: Dazonium cation reacts with aniline in weakly acidic medium resulting in N, N-
coupling rather than C-coupling.

N N  HN 
–H
 N N NH
H
 (C)

Problem 4: The end product (Z) of the following reaction is


N2Cl 
CuCN
 (X) 
H / H 2O
 (Y) 
NaOH
CaO, 
 (Z)
(A) a cyanide (B) a carboxylic acid
(C) an amine (D) an arene.
Solution:
N2Cl  

CuCN
CN 
H / H2O
 COOH 
Soda lim e


  (D)

Problem 5: Phenyl cyanide on reduction with Na/C2H5OH yields

(A) C6 H 5 CH 2 NH 2 (B) C6 H 5 NHCH 3

(C) NH2 (D) C6 H 5 NH 2 .

CH3

Solution: C6 H5 — C  N 
Na / C2 H5OH
 C6 H5 — CH2 NH2
 (A)

Problem 6: Consider the following reaction,



C6 H 5 NH 2  CHCl3  KOH   ( A) 
H / H 2O
 ( B)  (C )
The compounds (B) and (C) are:
(A) C6 H 5 COOH and NH 3 respectively
(B) C6 H 5 NH 2 and HCOOH respectively
(C) C6 H 5 NH 2 and H 2 O respectively
(D) None of these.

Solution: C6 H5 NH 2  CHCl3  3KOH 

 C6 H5 N C  3KCl  3H 2O
(A)

C6 H5 N C  2H 2O 
H
 C6 H5 NH 2  HCOOH
(A) (B) (C)

 (B)

Problem 7: Which of the following would react with ozone to form an isocyanate?
(A) CH 3 — CN (B) C6 H 5 — CN
(C) CH 3 — NC (D) C6 H 5 — NH 2 .

Solution: Isocyanides react with O 2 to form isocyanates

CH3 — N  C  O3 
 CH3 N  C  O  O2
 (C)

Problem 8: When benzamide is heated with thionyl chloride, the main product of the
reaction is
(A) C6 H 5 CN (B) C6 H 5 COCl
S

(C) C6 H 5 NH 2 (D) C6H5 C NH2.

Solution: SOCl2 here can only act as a dehydrating agent.

O

C6 H 5 C NH2  SOCl2 
 C6 H 5 — CN  SO 2  2HCl
  (A)

Problem 9: Consider the following ions

(I) + (II) +
M e2N N N O2N N N
(III) + (IV) +
H3C O N N H3C N N
The reactivities of these ions in azo-coupling reactions (under similar
conditions) will be such that
(A) (I) < (IV) < (II) < (III) (B) (I) < (III) < (IV) < (II)
(C) (III) < (I) < (II) < (IV) (D) (III) < (I) < (IV) < (II).

Solution: (B)

Problem 10: In the reaction O  CH 3 CH 2 NH 2 

H 2 / Ni
 (X) .

The product (X) is

(A) (B) OCH3
O CH2 NH2

CH 2NH2
(C) (D)
NCH2CH3 NHCH2CH3

Solution: (D)

R2  N  R 3 forms nitroso amines when the substitutents

R1
Problem 11: The compound
are
(A) R1 = CH3, R2 = R3 = H (B) R1 = R2 = H, R3 = C2H5
(C) R1 = H, R2 = R3 = CH3 (D) R1 = CH3, R2 = C2H5, R3 = C3H7
Solution: (C) R1 = H and R2 = R3 = CH3
R2  N  R 3  CH3  N  CH3
R1 H

sec. Amine reacts with Nitrous acid to form nitroso amine yellow liquid.

Problem 12: Aniline when diazotized in cold and then treated with dimethyl aniline
gives an coloured product. Its structure would be

(a) (CH3)2N N N

(b) (CH3)2N NH
 (c) CH 3NH N N NHCH 3

(d) CH 3 N N NH 2

Solution: (A)

Problem 13: Indicate which nitrogen compound amongst the following would undergo
Hofmann’s reaction (i.e. reaction with Br2 and strong KOH) to furnish the
primary amine (R – NH2)
O O
|| ||
(A) R - C - NH.CH3 (B) R – C  O.NH4
O O
|| ||
(C) R - C - NH2 (D) R - C - NHOH

Solution: (C) Hofmann degradation of amide

R – CONH2 + Br2 + 4KOH  R – NH2 + 2KBr + K2CO3 + 2H2O
primary amine
HNO3/H2SO4 Sn/HCl
Problem 14: Intermediate
Heat
NH 2 NH 2

(a) (b)
NH 2
NH 2
NO 2
(c)
(d)
NH 2 NH2
Solution: (B)
NO 2 NH2
HNO3/H2SO4 Sn/HCl

Nitrobenzene Aniline

Problem 15: Which of the following would be least reactive towards nitration
(A) Benzene (B) Nitro benzene
(C) Toluene (D) Chloro benzene
Solution: (B)
Nitro group deactivates the benzene ring.
Problem 16: Aniline reacts with acetaldehyde to form
(A) Schiff’s base (B) Carbylamine
(C) Immine (D) None of these

Solution: (A)
NH2 N CH CH3

Trace of an acid.
+ CH3 - CHO + H2O

Schiff's base
NO 2 X
Sn + HCl
Problem 17:

In the above reaction ‘X’ stands for

(A) NH2 (B) SnCl2
(C) Cl (D) NH4+Cl
Solution: (A)
NO 2 NH 2

Sn/HCl + 2H2O
+ 6[H]

Nitrobenzene Aniline

NH 2

Problem 18: + CHCl3 + KOH ?

(A) Phenyl isocyanide (B) Benzyl amine

(C) Benzyl chloride (D) none of these
Solution: (A)
C6H5 – NH2 + CHCl3 + 3KOH  C6H5NC + 3KCl + 3H2O

Problem 19: The refluxing of (CH3)2NCOCH3 with acid gives

(A) 2CH3NH2 + CH3COOH (B) 2CH3OH + CH3COOH
(C) (CH3)2NH + CH3COOH (D) (CH3)2NCOOH + CH4
Solution: (C)
(CH3 )2NCOCH3  HCl/H2O

(CH3 )2NH + CH3COOH

Problem 20: RNH2 reacts with C6H5SO2Cl in aqueous KOH to give a clear solution. On
acidification a precipitate is obtained which is due to the formation of
 H
|
(A) R - N + - SO2C6H5OH (B) [R – N SO2C6H5]K+
|
H
(C) R – NHSO2C6H5 (D) C6H5SO2NH2
Solution: (C)
C6H5SO2Cl + RNH2  RNHSO2C6H5  KOH
 [R – N SO2C6H5]K+
 
HCl
 R – NHSO2C6H5

Problem 21: CH3 CH2 NH2 is soluble in

(A) dilute HCl (B) CuSO4 solution
(C) AgNO3 (D) dil. H2SO4

Solution: Amines being basic in nature dissolve in dilute HCl and dil. H2SO4. They can
also coordinate with Cu 2 and Ag  ions to form soluble complexes as they
can act as good ligands.
 (a, b, c, d)

Problem 22: Which of the following can give Hoffmann’s degradation reaction
O O
|| ||
(A) CH3 – C – NH – Ph (B) Ph – C – NH2
O O
|| ||
(C) C2H5 – C – N – Ph (D) C2H5 – C – NH2
|
Me
Solution: (b, d)

Problem 23: Which of the following reactions give RCONH2

(A) R  C  N + H2O  
HCl
 (B) RCOONH4  Heat

(C) R  COCl + NH3   (D) All of these

Solution: (b, c)

Problem 24: p-chloroaniline shows -

(A) Carbylamine test (B) diazotisation reaction
(C) Reaction with AgNO3 (D) None of these

Solution: (a, b)

Problem 25: Which of the following reaction gives are RCH2NH2

KOH  Br2
(A) R – CN   (B) RCONH2  
LiAlH 4

H O
(C) R – CH = N - OH   (D) RCH2NC 
4 LiAlH 3

Solution: (A, C, D)

Problem 26: Match the following

 Column – I (Basic Column II (pKa of ammonium ions)
Compound)
(p) 4.63
(a) NH 2

(B) NH3 (q) 5.25

(r) 9.26
(c) NH

(s) 11.27
(d) N

Solution: (a - p), (b - r), (c - s), (d - q)

Write-Up - I
A cyclic optically active naturally occurring toxic liquid C8H17N (X), in hemlock that was
said to cause Socrates death dissolves in aq. HCl and gives no gas will nitrous acid. It
gives a precipitate with benzenesulphony chloride in presence of NaOH.

1. What conclusion you will draw when we say that the original compound
does not give any precipitate with C6H5SO2Cl in presence of NaOH ?
(A) It may be 10 amine (B) It may be 30 amine
(C) Either of the two (D) Neither of the two

2. The formation of a compound Z take place from the compound X, when X

treated with nitrous acid , Z contains
(A) nitro group (B) nitroso group
(C) amino group (D) none of these

Solution: 1. (C) 2. (B)

Write-Up - II
Primary aliphatic amines also react with nitrous acid to yield aliphatic diazonium salts.
However, aliphatic diazonium salts are quite unstable and decompose spontaneously,
even at low temperatures, by losing nitrogen to form carbocations (hence the reaction is
commonly known as deamination). The carbocations, in turn, produce a mixture of
alkenes, alcohols, and alkyl halides.
CH3CH2CH2CH2  HONO
HCl
 [CH3CH2CH2N2+Cl]   CH3CH2CH2+ + N2 + Cl
 
H H
CH3CH = CH2   CH3CH2CH2+ 
 CH3+CHCH3   CH3CH = CH2
Propene

1. The reaction of CH3CH2CH2NH2 with nitrous acid is used in detecting the

presence of –NH2 group in amino acids and proteins because this test is
 based on the fact
(A) a green colour is obtained
(B) a red colour is obtained in the final stage
(C) a characteristic change in colour is observed
(D) nitrogen is evolved quantitatively

2. Which of the following product is also formed in the above reaction ?

(A) CH3CH2CH2Cl (B) CH3CHOHCH3
(C) CH3CHClCH3 (D) All the three

3. Which type of product is likely to be formed when CH3CH2CH2NH2 in the

above case it replaced by C6H5CH2NH2 ?
(A) An alkene (B) An alcohol
(C) Both (A) and (B) (D) None of the two

Solution: 1. (D) 2. (D) 3. (C)

Subjective
Problem 1: Draw the structures of A and B.
CH3
i) CH3Cl (excess) Heating
A B
ii) Ag2O
N
H

Solution:
H3C

A = B =
+ CH2
N OH N

H3C CH3 H3C CH3

Problem 2: Explaining the mechanism of Hoffmann Bromamide reaction on cyclic

amide.
O

(i) Br 2
NH ?
KOH
(ii) H 2O/H
+
O
 O O
NH2
+
K -OH NH2 Br 2/KOH
Solution: NH
O K+ O K+

O O O
+
H H2O

HO
H2N O

Problem 3: How would you bring about the following conversion (in 3 steps) ?
Aniline 
 Benzylamine
NaNO2  HCl
Solution: PhNH2 
0–5C
  PhN2 Cl– 
CuCN
 PhCN 
H2 / Ni
 PhCH2 NH2

Problem 4: Complete the following reactions with appropriate reagents.

O I
NH C CH3 
?
 
?
 
?
 
?
 NO2

I
Solution: (Conversion of –NH 2 to –NO2 )
O

NH C CH3 
H3O
 NH2 
NaNO2 / HBF4
 N 2 BF4–
NaNO 2

N 2 BF4–
I 2 / HgO or HNO3
I

NO2

Problem 5: Write all the intermediates in the synthesis of m-bromotoluene from p-

toluidine.

Solution: CH3 CH3 CH3 CH3 CH3


(CH3CO)2 O
 (1) Br2
(2) OH – , H O
 
H 2SO4 , NaNO2
H2 O
 
H3 PO2
H2O

2
heat 0–5 C 25 C
Br Br Br
NH2 NH NH2 N2 m-Bromotoluene
p-toluidine (85% from 2-bromo-4-
COCH3 (65% from p-toluidine) methylaniline)
Problem 6: Prepare
a) PhD from PhNH 2
b) Optically active sec butyl benzene from an amine intermediate.

Solution: a) C6 H5 NH2 

HNO2
0–5 C
 C6 H5 N2 
D3PO2
 C6 H5 D
b) C6 H6  CH3CH 2CH(CH3 )Cl 
AlCl3
 PhCH(CH3 )CH 2CH3
(A)

(A) is a hydrocarbon which is not reactive at all. To make it resolvable, we need

to follow the given pathway.
PhCH(CH3 )CH 2CH3  1. HNO3 / H 2SO4
2. Sn / HCl
 rac. p – H2 NC6 H4CH(CH3 )CH2CH3
3. OH –

which is resolved with an optically active carboxylic acid such as tartaric acid.
Then deaminate via diazonium salt and H3PO2 .

Problem 7: Identify (A) through (E) in the following sequence


PhSO2Cl  EtNH2 
–HCl
(A) 
NaOH
(B) 
EtBr
(C) 
H3O
(D)  (E)

Solution: PhSO 2 NHEt 

NaOH
 PhSO2 N – Et 
EtBr
 PhSO2 NEt 2
(A) (B) (C)

H3O  

 PhSO 2 OH  Et 2 NH 2
(D) (E)

Problem 8: Account for the fact that 2-aminoethanoic acid (glycine) exists as a
dipolar ion, as does p-aminobenzenesulfonic acid (sulfanilic acid) but p-
aminobenzoic acid does not.

Solution: The aliphatic NH 2 is sufficiently basic to accept an H  from COOH. The

COOH is not strong enough to donate H  to the weakly basic ArNH 2 , but
SO3H is a sufficiently strong acid to do so.
–
H3 N  — CH 2COO p — H 2 N — C6 H 4 — COOH p — H3 N  — C6H 4 — SO3–
Glycine p  A min obenzoic acid Sulfanilic acid

Problem 9: How will you carry out the following conversions?

a) O

C NH
NH2 CH3



b)
NH2 
 NH2
Solution: a) O

C NH2 NC
NH2

Br2 / KOH
 CHCl3
KOH

NH
CH3

LIAlH 4

b)
NH2   OH  
NaNO H 2SO4 –

KMnO4 / H
2
HCl  

COOH 
BaO
 O 
NH3
 NH 
2

H / Pt
NH2
COOH  

Problem 10: A mixture of two aromatic compounds (A) and (B) was separated by
dissolving in chloroform followed by extraction with aqueous KOH solution.
The organic layer containing compound (A), when heated with alcoholic
solution of KOH produced a compound (C) (C7H5N) associated with an
unpleasant odour. The alkaline aqueous layer on the other hand, when
heated with chloroform and then acidified, gives a mixture of two isomeric
compounds (D) and (E) of molecular formula C7H6O2. Identify the
compounds (A), (B), (C), (D) and (E).

Solution: NH2 OH N=C OH OH

CHO
(A) : (B) : (C) : (D) : (E) :

CHO
Assignments (New Pattern)
SECTION – I Single Choice Questions

Level - I

1. The number of resonating structures of aniline is

(A) 2 (B) 3
(C) 4 (D) 5
2. CH3CH2NH2 is soluble in
(A) dilute HCl (B) CuSO4 solution
(C) AgNO3 (D) All of these.

3. How many isomeric amines with formula C7H9N contain a benzene ring?
(A) two (B) three
(C) four (D) five.

4. Isopropylamine can be obtained by

(A) (CH ) CHO  NH OH  ?  LiAlH4

3 2 2

(B) (CH ) CHO  CH NH  ?  H2 /Ni


3 2 3 2 
(C) H3C
CHOH + CH3NH2
H3C
(D) All of these.

5. Amines are highly soluble in:

(A) CCl4 (B) Diethyl ether
(C) benzene (D) Water.

6. The bromination of aniline in presence of water produces

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

7. Maximum basic in gas phase is?

(A) NH3 (B) CH3CH2NH2
(C) (CH3CH2)NH (D) (CH3CH2)3N

8. Examine the following two structures for the anilinium ion and choose the correct
statement from the ones given below:
NH3 NH3

(I) (II)
 (A) II is not acceptable canonical structure because carbonium ions are less stable than
ammonium ions
(B) II is not an acceptable canonical structure because it is nonaromatic
(C) II is not an acceptable canonical structure because nitrogen has 10 valence electrons
(D) II is an acceptable canonical structure

9. Benzenediazonium chloride on reaction with phenol in weakly basic medium gives

(A) diphenyl ether (B) p-hyroxyazobenzene
(C) chlorobenzene (D) benzene
10. Hydrazobenzene can be obtained by reducing nitrobenzene with
(A) Sn + HCl (B) Zn + NH4 Cl
(C) Na 3AsO3 + NaOH (D) Zn + NaOH.

11. The reduction of a nitrile by LiAlH4 produces

(A) primary amine(B) secondary amine
(C) tertiary amine (D) amide

12. Which of the following compounds will dissolve in an alkali solution after it has
undergone reaction with Hinsberg reagent ?
(A) (C2H5)2NH (B) (CH3)3N
(C) CH3NH2 (D) C6H5NHC6H5

13. Which of the following is Sandmeyer reaction ?

(A) 2C6H5Cl   C6H6 + Cl2
Cu 2Cl2 /HCl

(B) C6H5N2Cl  C6H5Cl + N2

Cu 2Cl2 /HCl

(C) C6H5OH  Zn dust

 C6H6 + ZnO
(s) C6H5NO2 + 6[H]  Sn/HCl
 C6H5NH2 + 2H2O

14. A positive carbylamine test is given by

(A) N, N-dimethylaniline (B) 2, 4-dimethylaniline
(C) N-methyl-o-methylaniline (D) p-methylbenzylamine

15. The product (D) in the following sequence of reactions is,

Na  C2 H5OH
CH3COOH   (A)   (B)   (C)   (D)
NH3 Heat P2O5

(A) ester (B) amine

(C) acid (D) alcohol

16. Ethyl amine reacts with nitrosyl chloride (NOCl) to form :

(A) ethyl chloride (B) ethyl alcohol
(C) ethyl nitrite (D) nitro ethane

17. Treatment of ammonia with excess of ethyl chloride will yield:

(A) diethyl amine (B) methyl amine
(C) tetraethyl ammonium chloride (D) ethane
18. Gabriel phthalimide sysnthesis is used in the preparation of :
(A) primary amine (B) secondary amine
(C) tertiary amine (D) all of these

19. A colourless, odourless and non-combustible gas is liberated when ethylamine reacts
with:
 (A) NaOH (B) CH3COCl
(C) NaNO2 + HCl (D) H2SO4

20. The hydrolysis of isocyanide produces

(A) acid (B) amide
(C) amine (D) ester

Level - II

1. 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

2. Heating of [CH3CH2CH2CH(CH3)N+(CH3)3]OH gives, the major product

(A) CH2 = CH2 (B) CH3CH2CH2CH = CH2
(C) CH3CH2CH = CHCH3 (D) CH2 = CHCH2CH = CH2

3. Secondary amine forms yellow oily liquid with nitrous acid, which on warming with phenol
and conc. H2SO4 gives a brown or red colour and which at once changes into blue-
green. This reaction is called as :
(A) Carbyl amine reaction (B) Liebermann’s nitroso reaction
(C) Gabriel phthalimide reaction (D) Hofmann’s mustard oil reaction

4. The compound that will react most readily with NaOH to form methanol is :
+
(A) (CH3)4 NI - (B) CH3OCH3
(C) (CH3)2 S (D) (CH3)3CCl

5. Which of the following orders regarding the basic strength of substituted aniline is
correct?
(A) p-methylaniline  p-chloroaniline  p-aminoacetophenone
(B) p-methylaniline  p-aminoacetophenone  p-chloroaniline
(C) p-aminoacetophenone  p-methylaniline  p-chloroaniline
(D) p-aminoacetophenone  p-chloroaniline  p-methylaniline

6. Consider the following reaction,

H+ /H2O
C6 H5 NH2 + CHCl3 + KOH  Δ
 (A)   (B) + (C)
The compounds (B) and (C) are:
(A) C6 H5COOH and NH3 respectively (B) C6 H5 NH2 and HCOOH respectively
(C) C6 H5 NH2 and H2Orespectively (D) None of these.
7. When aniline is treated with benzene diazonium chloride at low temperature in weakly
acidic medium, the final product obtained is
 (A) NH2 (B)
N N NH2

N N

(C) (D) NH2

N N NH

N N

8. The end product (Z) of the following reaction is


N2Cl 
Cu / KCN
 (X) 
H / H2O
 (Y) 
NaOH
CaO, 
 (Z)
(A) a cyanide (B) a carboxylic acid
(C) an amine (D) an arene.

9. The increasing order of basicity of RCN, RCN = NR and RNH 2 is

(A) RCN < RCH = NR < RH 2 N (B) RNH 2 < RCN < RCH = NR
(C) RCH = NR < RNH 2 < RCN (D) RH 2 N < RCH = NR < RCN.

10. 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.

SECTION – II More Than One Choice

1. Which of the following statements is correct?

(A) Replacement of halogen by NH2 in alkyl halide is a nucleophilic substitution reaction
(B) Ary halides show more reactivity as compared to alkyl halides in the replacements of
halogen by the NH2 group
(C) During the replacement of halogen by —NH2 group, ammonia is taken in large
excess so as to avoid the formation of 2° and 3° amines
(D) Tertiary alkyl halide generally produces alkene instead of the replacement of halogen
by NH2 group.

2. Which of the following statements is correct?

(A) Primary amines show intermolecualr hydrogen bonding
(B) Secondary amines show intermolecular hydrogen bonding
(C) Tertiary amines show intermolecular hydrogen bonding
(D) Amines have lower boiling points as compared to those of alcohols and carboxylic
acid of comparable molar masses.

3. Which of the following statements is correct?

(A) Aliphatic amines are stronger bases than ammonia
 (B) Aromatic amines are stronger bases than ammonia
(C) The alkyl group in alkyl ammonium ion more stabilizes the ion relative to the amine
(D) The aryl group in aryl ammonium ion less stabilizes the ion relative to the amine

4. Reaction of RCONH2 with a mixture of Br2 and KOH gives RNH2 as the main product.
The intermediates involved in the reaction are
O
(A) (B) R—NHBr
R C NHBr
O Br
(C) R—N=C=O (D) R C N
Br

5. Identify compound (A) in the following oxidation reaction.

(A)   O
K Cr O , H SO
2 2 7 2 4
O
(A) NH2 (B) OH

NH2 NH2
(C) OH (D) None of these.

OH

6. Primary and secondary amiens can be distinguished by the action of:

(A) CS2/HgCl2 (B) NaNO2/HCl
(C) CHCl3/ KOH (D) NaOH

7. Pimary amines may be obtained by :

(A) the reduction of nitroalkanes (B) the reduction of alkyl isocyanide
(C) the decarboxylation of amino acids (D) the hydrolysis of alkyl isocyanate

8. Tertiary amines may be obtained by :

(A) Gabriel phthalimide synthesis
(B) heating an alcoholic solution of ammonia with excess of RX
(C) the hydrolysis of dialkyl cyanamide
(D) thermal decomposition of quaternary ammonium hydroxide

9. C4H11N (X) + HNO2   C4H10O (30 alcohol) hence, X will give :

(A) Carbylamine reaction (B) Hofmann mustard oil reaction
(C) Diazonium salt (as the intermediate) (D) Hofmann’s bromamide reaction

10. The products obtained in the following reaction,

CH3 — NO2  Cl2  NaOH  ?
(A) ClCH2 NO2 (B) Cl2CHNO2
 (C) Cl3CNO2 (D) CH3 NH 2 .

SECTION – III Other Engg. Exams Questions

1. Amides may be converted into amines by reaction named after

(A) Perkin (B) Claisen
(C) Hoffmann (D) Kolbe
[CPMT 1974; MP PET 1992; CBSE PMT 1999]

2. Acetamide is treated separately with the following reagents. Which would give methyl
amine
(A) PCl5 (B) NaOH + Br2
(C) Sodalime (D) Hot conc. H2OS4
[CPMT 1988, 94; MP PET 1993; MP PMT 1996, AIIMS 1998]

3. CH3CN 
Na +C2 H5OH
X
The compound X is
(A) CH3CONH2 (B) CH3CH2NH2
(C) C2H6 (D) CH3NHCH3
[MP PMT 1983, BHU 1984]

4. Chloropicrin is manufactured by the reaction between Cl2, NaOH and

(A) Nitromethane (B) Nitroethane
(C) Nitrophenol (D) Nitrostyrene

O
|| +
5. R  C OH 
H3O
 X 
[H]
 RCH 2 NH 2 ; ‘X’ is
(A) Isonitrile (B) Nitrile
(C) Nitrite (D) Oxime
[MP PMT 1990]

6. Which of the following reactions does not yield an amine

(A) RX + NH3   (B) RCH = NOH + [H] 
Na
C H OH
2 5

H
(C) RCN + H2O  (D) RCONH2 + 4H 
LiAlH 4

7. Identify ‘B’ in the reaction

Acetamide   A  B
P2O5 4H

(A) CH3NH2 (B) CH3CH2NH2
(C) CH3CN (D) CH3COONH4
[MP PET 1995]

8. When aniline reacts with NaNO2 and dil. HCl at 00 – 50C, the product formed is
(A) Nitroaniline (B) Benzene diazonium
(C) Benzene (D) Trinitroaniline
[MP PMT 1996, AIIMS 1996]
9. In the following reaction, X is
NaNO2 HCl
X   Y  Z   Tribromobenzene
Bro min ation H3PO2

(A) Benzoic acid (B) Salicylic acid

(C) Phenol (D) Aniline
[CPMT 1999]
+
N2

CuCN
10. Product

CH3
The product is
NH 2 CN

(a) (b)

CH3 CH3
CN NH 2
(c) (d)

11. Ethyl amine on heating with CS2 in presence of HgCl2 forms

(A) C2H5NCS (B) (C2H5)2S
(C) (C2H5)2CS (D) C2H5(CS)2
[MP PET 2000]

12. In acid medium nitrobenzene is reduced to aniline as shown in the reaction

C6H5 – NO + 6[H]  C6H5 – NH2 + 2H2O
The reducing agent used in this reaction is . . . . . .
(A) LiAlH4 (B) Sn/HCl
(C) Na/alcohol (D) H2/Ni
[Orissa JEE 2003]

Sn  HCl
13. CH3NO2  CH3X, the ‘X’ contain
(A) NH2 (B) COOH
(C) CHO (D) (CH3CO)2O
[CPMT 2003]
14. An organic amino compound reacts with aqueous nitrous acid at low temperature to
produce an oily nitroso amine. The compound is:
(A) CH3NH2 (B) CH3CH2NH2
(C) CH3CH2NH.CH2CH3 (D) (CH3CH2)3
[DCE 2003]
15. Gabriel’s phthalimide synthesis is used for the preparation of
(A) Primary aromatic amine (B) Secondary amine
(C) Primary aliphatic amine (D) Tertiary amine
[CPMT 1982; DPMT 1983]
 SECTION – IV Match the Column

1. Match the following

Compound pKb

(A) NH3 (p) 9.38

(B) C6H5 – NH2 (q) 3.32

(C) C6H11 – NH2 (r) 4.75

O (s) 10.78
||
(D) C6 H5  NH  C H

2. Match the following

Reaction
Product

H O
(A) CH3CH2NC 
3
 (p) CH3CH2CH2NH2

H O
(B) CH3CH2CN 
3
 (q) CH3CH2NHCH3

(C) CH3CH2NO   LiAlH

4
(r) CH3CH2COOH

O (s) CH3CH2NH2
||
(D) CH3CH 2  C NH 2 
LiAlH4

SECTION – V Comprehension Type Questions

 Write-up I

Diazonium salt formation and coupling reactions: When a reaction mixture of phenyl
amine and nitrous acid is kept below 10°C, a diazonium salt is formed. This reaction is
called diazotization reaction.

NH2  HNO 2  HCl 


+
N2 Cl  2H 2 O

Phenyl diazobnium
chloride

The diazonium ion,  N 2 , is rather unstable and decomposes readily to nitrogen.

However, delocalization of the diazonium from -bond electron over a benzene ring
stabilizes phenyl diazonium sufficiently for it to form at low temperatures.
The phenyl diazonium on behaves as an electrophile, and will attack another arene
molecule such as phenol. Electrophilic substitution takes place at the 4 position,
producing 4-hydroxy phenyl azobenzene. The reaction is known as coupling reaction.
 

+
N2  OH N
N OH  H

The compound formed is an energetically stable, yellow azo dye (the azo group is
– N = N –). The stability is due to extensive delocalisation of electrons via the nitrogen –
nitrogen double bonds.

1. The azo dye obtained on reacting 4-aminophenol with nitrous acid (in dilute hydrochloric
acid) below 10°C and coupling the resulting diazonium salt with phenol is:

N N
(A) (B)
N N OH

HO N H2N N
(C) (D)
N OH N OH

2. Benzene diazonium chloride on reaction with phenol with weakly basic medium gives
(A) diphenyl ether (B) p-hydroxy azobenzene
(C) chlorobenzene (D) benzene
3. HO

The product HO N N which is a red azodye obtained on reacting

benzene diazonium chloride with one of the following compounds.

OH

(A) OH (B)

OH
HO OH

(C) (D)

 Write-up II

Amines are derivatives of ammonia and are classified as 1°, 2°, and 3°. Primary and
secondary (but not tertiary amines) form intermolecular hydrogen bonds and thus they
boil at higher temperatures than expected. Like ammonia, all amines are basic, although
they differ in their basic nature. As amines are considered as derivatives of ammonia,
quaternary ammonium salts are considered as derivatives of ammonium salts. Only the
quaternary ammonium salts can show optical activity.

4. Which of the following statement is correct?

(A) All classes of amines form hydrogen bonds with each other
(B) Only primary and secondary amines form hydrogen bonds with water
(C) All classes of amines can form hydrogen bonds with water
(D) All amines are completely soluble in water
5. When nitrogen is bonded to three different groups
(A) The molecule is optically inactive
(B) The molecule is tetrahedral structure
(C) The molecule is not superimposable on its mirror image
(D) The amine boils at nearly similar b.p as the 1° and 2° amine of comparable molecular
weight.

6. Which of the following shows configurational isomerism?

(A) Diethyldimethylammonium iodide
(B) Methylethylpropylamine
(C) Methylallylphenylbenzyl ammonium bromide
(D) None of these

7. Methylethylpropyl amine is optically inactive because

i) It is not tetrahedral
ii) Its molecule is superimposable on its mirror image
iii) The enantiomers are rapidly interconverted
iv) The nitrogen is sp2 hybridized
Which of the above statements(s) is (are) true?
(A) Only (i) (B) Only (iii)
(C) and (iii) (D) All the four

 Write-up III

Consider the two sequence of reaction

NH2

I. (H 2C)5 H+ Se
B
A
NH2

COOH NaNO2 / HCl

NaOH
 
II. 
 D  E
NH2

8. The compound B may be

(A) Pyridine (B) Piperidine
(C) Pyrrole (D) All

9. The Hybridisation of N in compound A is

(A) sp2 (B) sp3
(C) sp (D) None of these

10. The product E is

OH
(A) (B)

(C) Acetone (D)

11. The intermediate D is
(A) Benzene (B) Benzyne
(C) C2H2 (D) CH2

SECTION – VI Subjective Questions

LEVEL – I

1. Give steps involved in the following conversions :

(i) Ethyl cyanide to ethylamine

(ii) H3C NO 2 H2N NO 2

2. Suggest a structural formula for an optically active amine, C8H11N, which evolves
nitrogen on treatment with nitrous acid.

3. Deduce the structures of the following amines from the products obtained from
exhaustive methylation and Hofmann elimination.
(A) Amine of the molecular formula C5H13N reacts with 1 mole of methyl iodide and finally
gives propene.
(B) Amine of the formula C5H13N reacts with 2 moles of methyl iodide and gives ethene
and a 30 amine which in turn reacts with 1 mole of CH3I and give propene.

4. Sulphanilic acid is not soluble in organic solvents. Explain?

5. A carboxylic acid A (C5H10O2) when heated with hydrazoic acid in presence of conc.
H2SO4 gives a compound B which on treatment with alkaline chloroform forms another
compound C. Compound C gives following reactions.
(i) On hydrolysis in presence of acid, it gives compound B and methanoic acid.
(ii) On reduction it gives tert-butylmethylamine.
Identify compound A and give all reactions.

6. Unlike other aromatic amines, why is the following amine stongly basic?
NO2
NM e2

NO2

7. In this compound OH NH2 which site acts as an acid and which as a base?

8. All those both hydroxyl ( NH2 — OH ) amine and keto oxime H3C contain
C N OH
H3C
O—H group but which one contain more acidic H atom.

9. Alkyl cyanides (CH3CN) when treated with hydrogen in presence of Pt or with LiAlH 4
produces same compound. What is the formula of that compound?

10. Write the compound (A) and (B) formed in this

 CH3


NaNH 2
 (A) 
NaOCH3
 (B) (Major)
Cl

LEVEL – II

1. A resolvable amine (A) when subjected to exhaustive methylation, it takes up 3

equivalents of methyl iodide and the product when heated gives an alkene (B). Alkene
(B) on ozonolysis yields an equimolar mixture of methanal and butanal. Suggest the
structure of the amine (A).

2. An organic compound (A) composed of C, H and O gives characteristic colour with ceric
ammonium nitrate. Treatment of (A) with PCl5 gives (B), which reacts with KCN to form
(C). The reduction of (C) with warm Na/ C2 H5OH produces (D), which on heating gives
(E) with evolution of ammonia. Pyridine is obtained on heating of (E) with selenium. Give
structure of compounds (A) to (E) with proper reasoning.

3. One mole of bromoderivative (A) and one mole of 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 compounds (A) to
(E) with proper reasoning.

4*. Compound (A) having M.F. C8 H8O on treatment with NH2OH.HCl gives (B) and (C).
(B) and (C) rearrange to give (D) and (E), respectively on treatment with acid.
Compounds (B), (C), (D) and (E) are all isomers of molecular formula C8 H9 NO . When
(D) is boiled with alcoholic KOH, an oil (F) C6 H7 N separated out. (F) reacts rapidly with
CH3COCl to give back (D). On the other hand, (E) on boiling with alkali followed by
acidification gives a white solid (G), C7 H6O2 . Identify the compounds (A) to (G).

5*. An aromatic compound (A), having M.F C7 H5 NO2Cl2 on reduction with Sn/HCl gives
(B), which on reaction with NaNO2 / HCl gives (C). Compound (B) is unable to form a
dye with  -naphthol. However, (C) gives red colour with ceric ammonium nitrate and on
oxidation gives an acid (D), having equivalent weight 191. Decarboxylation of (D) gives
(E) which forms a single mononitro derivative (F), on nitration. Give the structures of (A)
to (F) with proper reasoning.

6. An optically inactive acid (A), C5 H8O5 , on being heated lost CO2 to give an acid (B),
C4 H8O3 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,
C4 H9OH which with Br2 and KOH solution gave (F), C3H9 N . F with HNO2 gave G. (G)
on mild oxidation gave H. Both A and H gave the iodoform reaction. Elucidate the
reaction mechanism and suggest a synthesis of (C).

7*. A neutral organic compound (A) C5 H11O2 N when treated with reducing agent forms a
basic compound (B) C5 H13 N . (B) on treatment with excess of CH3l followed with moist
 Ag 2O gives (C) C8 H21ON . On heating (C) decomposes to give trimethyl amine and 2-
methylbutene-1 (only product). What are (A), (B) and (C).

8. Two isomeric compounds (A) and (B) have C4 H11N as molecular formula. Both on
separately treating with HNO2 lose their N 2 producing two isomeric alcohols (C) and
(D) respectively of molecular formula C4 H10O . (C) reacts with Lucas reagent
immediately and units oxidation. (D) does not reacts with Lucas reagent in cold but can
be easily oxidized. Identify A to D.

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) and (B). Is there any structural
isomer to (A), if yes draw its structure.
Answers to Assignments
SECTION - I

LEVEL - I

1. (D) 5. (D) 9. (B) 13. (B) 17. (C)

2. (D) 6. (C) 10. (D) 14. (D) 18. (A)
3. (D) 7. (D) 11. (A) 15. (B) 19. (C)
4. (A) 8. (C) 12. (C) 16. (A) 20. (C)

LEVEL - II

1. (B)
2. (B)
3. (B)
4. (A)
5. (A)
6. (B)
7. (C)
8. (D)
9. (A)
10. (C)
 SECTION - II

1. (A, C, D) 2. (A, B, D) 3. (A, C, D) 4. (A, C)

5. (A, B, C) 6. (A, B, C) 7. (A, C, D) 8. (B, D)
9. (A, B, C) 10. (A, B, C)

SECTION – III Other Engg. Exams

1. (C) 2. (B) 3. (B) 4. (A)

5. (B) 6. (C) 7. (B) 8. (B)
9. (D) 10. (B) 11. (A) 12. (B)
13. (A) 14. (C) 15. (C)

SECTION - IV

1. (a – r), (b - p), (c- q), (d – s)

2. (a – s) , (b - r), (c- s), (d – p)

SECTION – V

1. (C) 2. (B) 3. (B) 4. (C)

5. (C) 6. (C) 7. (B) 8. (A)
9. (B) 10. (D) 11. (B)