1

AMINES Reasoning Questions

.Account for the following:
1. pK
b
of aniline is more (less basic) than that of methylamine.(or)
Aliphatic amines are stronger bases than aromatic amines.
In aniline, lone pair of electrons on nitrogen is involved in resonance (+R effect), hence less
electrons are available for donation, less protonated, less basic.

On the other hand, in methylamine due to the +I effect of methyl group (CH
3
gp is EDG), the
electron density on the N-atom is increased, hence more basic.
As a result, aniline is less basic than methylamine. Thus, pK
b
of aniline is more than that of
methylamine.

2. Ethylamine is soluble in water whereas aniline is not.
Ethylamine forms intermolecular Hbonds with water. Hence, it is soluble in water.
But aniline does not undergo Hbonding with water due to the presence of a large hydrophobic
C
6
H
5
group. Hence, aniline is insoluble in water.

3. Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.

Due to the +I effect of CH
3
group, methylamine is more basic than water. Therefore, methylamine
reacts with water to produce OH

ions by accepting H
+
ions from water.

Ferric chloride (FeCl
3
) dissociates in water to form Fe
3+
and Cl

ions.

Then, OH

ion reacts with Fe

3+
ion to form a precipitate of hydrated ferric oxide.


4. Although amino group is o, p directing in aromatic electrophilic substitution reactions,
aniline on nitration gives a substantial amount of m-nitroaniline.
Nitration is carried out in an acidic medium. In strongly acidic medium, aniline is protonated to give
anilinium ion which is meta-directing.


5. Aniline does not undergo Friedel-Crafts reaction.
Friedel-Crafts reaction is carried out in the presence of AlCl
3
. But AlCl
3
is acidic in nature, while
aniline is a strong base. Thus, aniline reacts with AlCl
3
to form a salt in which nitrogen acquires a
positive charge, hence acts as a strong deactivating group.
C
6
H
5
NH
2
+ AlCl
3
C
6
H
5
NH
2
+
AlCl
3
-


6. Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
Aromatic diazonium salts are more stable because of resonance, there is dispersal of positive charge.

2

7. Gabriel phthalimide synthesis is preferred for synthesising primary amines.
Gabriel phthalimide synthesis gives pure 1 amine without the contamination of 2 or 3 amines. [2
or 3 amines are not formed in this synthesis].

8. Aromatic primary amines cannot be prepared by Gabriel phthalimide synthesis.
Gabriel phthalimide synthesis is used for the preparation of aliphatic primary amines. Aromatic
primary amines cannot be prepared by this process because aryl halides do not undergo nucleophilic
substitution with the anion formed by the phthalimide.

9. Amines are less acidic than alcohols of comparable molecular masses.
Amines undergo protonation to give amide ion.

Similarly, alcohol loses a proton to give alkoxide ion.

Since O is more electronegative than N, the R-O
-
is more stable than R-NH
-
ion. Hence, alcohols
are more acidic than amines of comparable molecular masses.

10. Primary amines have higher boiling point than tertiary amines.
In tertiary amine, there are no Hatoms, hence there is no intermolecular hydrogen bonding
whereas in primary amines, two hydrogen atoms are present and hence undergo extensive
intermolecular Hbonding. Hence, primary amines have higher boiling points than tertiary amines.

11 . It is difficult to prepare pure amines by ammonolysis of alkylhalides.
Ammonolysis yields a mixture of primary, secondary, tertiary amines and quaternary ammonium salts
which is difficult to separate

12. Alcohols are more soluble in water than amines.
O is more electronegative than N, hence alcohols are more polar than amines and form stronger
intermolecular H-bonds than amines.

13. Tertiary amines do not undergo acylation. (or)
Tertiary amines do not react with Hinsberg reagent.
It does not have replaceable hydrogen.

14. Acetylation is carried out in the presence of base pyridine.
Base pyridine removes HCl formed and shifts the equilibrium to the right hand side.

15. How can the activating effect of NH
2
group in amines be controlled? (or) Why does the
reactivity of NH
2
get reduced in acetanilide?
This can be done by protecting the NH
2
group by acetylation. In acetanilide, the lone pair of es- on
nitrogen is involved in resonance with oxygen atom. Thus, N acquires positive charge which reduces
the activating effect of NH
2
group.

Basic strength- Order of basic strength
Aliphatic amine > NH
3
>Aromatic amine
In aliphatic amine due to the +I effect of methyl group, it is more basic.
In aniline, lone pair of electrons on nitrogen is involved in resonance (+R effect), it is less basic.

In gas phase, 3
0
>2
0
>1
0
amine > NH
3

As the no. of EDG increases, +I effect of alkyl group increases, basic strength increases.

Basic strength in aqueous solution.
In aqueous solution basic strength depends on inductive effect, solvation effect and steric hindrance to
H- bonding. These three factors are favarouble for 2
0
amine, hence it is most basic.
3

The order of basic strength in aqueous solution,
For small CH
3
group, 2
0
>1
0
>3
0
>NH
3

Reason: For CH
3
group, there is no steric hindrance to H- bonding. The stability of cation due to
solvation effect > inductive effect, hence 1
0
amine is more basic than 3
0
amine.

For big C
2
H
5
group, 2
0
>3
0
>1
0
>NH
3

Reason: For C
2
H
5
group, there is steric hindrance to H- bonding. The stability of cation due to
inductive effect > solvation effect, hence 3
0
amine is more basic than 1
0
amine.

EDG (CH
3
, -OCH
3
), increases the basic strength [increases the e- density on nitrogen].
EWG (NO
2
, halogen), decreases the basic strength [decreases the e- density on nitrogen]

Order of basic strength

Aliphatic amine > Benzyl amine >NH
3
>Aromatic amine
In gas phase, 3
0
>2
0
>1
0
amine > NH
3

For small CH
3
group, 2
0
>1
0
>3
0
>NH
3

For big C
2
H
5
group, 2
0
>3
0
>1
0
>NH
3
[S > T > P ]
EDG (CH
3
, -OCH
3
), increases the basic strength
EWG (NO
2
, halogen), decreases the basic strength

1. Arrange the following in decreasing order of their basic strength:
C
6
H
5
NH
2
, C
2
H
5
NH
2
, (C
2
H
5
)
2
NH, NH
3

(C
2
H
5
)
2
NH > C
2
H
5
NH
2
> NH
3
> C
6
H
5
NH
2


2. Arrange the following in increasing order of their basic strength:
(i) C
2
H
5
NH
2
, C
6
H
5
NH
2
, NH
3
, C
6
H
5
CH
2
NH
2
and (C
2
H
5
)
2
NH
C
6
H
5
NH
2
< NH
3
< C
6
H
5
CH
2
NH
2
< C
2
H
5
NH
2
< (C
2
H
5
)
2
NH

(ii) C
2
H
5
NH
2
, (C
2
H
5
)
2
NH, (C
2
H
5
)
3
N, C
6
H
5
NH
2

C
6
H
5
NH
2
< C
2
H
5
NH
2
< (C
2
H
5
)
3
N < (C
2
H
5
)
2
NH

(iii) CH
3
NH
2
, (CH
3
)
2
NH, (CH
3
)
3
N, C
6
H
5
NH
2
, C
6
H
5
CH
2
NH
2
.
C
6
H
5
NH
2
< C
6
H
5
CH
2
NH
2
< (CH
3
)
3
N < CH
3
NH
2
< (CH
3
)
2
NH

3. Arrange the following:
(i) In decreasing order of the pK
b
values[ basic strength]:
C
2
H
5
NH
2
, C
6
H
5
NHCH
3
, (C
2
H
5
)
2
NH and C
6
H
5
NH
2
C
6
H
5
NH
2
,C
6
H
5
NHCH
3
,C
2
H
5
NH
2 ,
(C
2
H
5
)
2
NH

(ii) In increasing order of basic strength: C
6
H
5
NH
2
, C
6
H
5
N(CH
3
)
2
, (C
2
H
5
)
2
NH and CH
3
NH
2

C
6
H
5
NH
2
< C
6
H
5
N(CH
3
)
2
< CH
3
NH
2
<

(C
2
H
5
)
2
NH

(iii) In increasing order of basic strength:
(a) Aniline, p-nitroaniline and p-toluidine [CH
3
, B.S ; NO
2
B.S]
p-nitroaniline < Aniline < p-toluidine

(b) C
6
H
5
NH
2
, C
6
H
5
NHCH
3
, C
6
H
5
CH
2
NH
2
.
C
6
H
5
NH
2
< C
6
H
5
NHCH
3
< C
6
H
5
CH
2
NH
2

(iv) In decreasing order of basic strength in gas phase: C
2
H
5
NH
2
, (C
2
H
5
)
2
NH, (C
2
H
5
)
3
N and NH
3

(C
2
H
5
)
3
N > (C
2
H
5
)
2
NH > C
2
H
5
NH
2
> NH
3

(v) In increasing order of boiling point: C
2
H
5
OH, (CH
3
)
2
NH, C
2
H
5
NH
2

(CH
3
)
2
NH < C
2
H
5
NH
2
< C
2
H
5
OH

(vi) In increasing order of solubility in water: C
6
H
5
NH
2
, (C
2
H
5
)
2
NH, C
2
H
5
NH
2
.
C
6
H
5
NH
2
< (C
2
H
5
)
2
NH < C
2
H
5
NH
2