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G12 NCERT Unit-13 Amines

The document discusses amines and provides solutions to practice problems involving classification, structures, reactions and properties of amines. It classifies sample amines as primary, secondary or tertiary based on their structure. It writes out the IUPAC names and structural isomers for all possible amine structures with the molecular formula C4H11N. It also describes reaction steps to convert benzene to aniline and dimethylaniline, and 1,4-dichlorobutane to hexane-1,6-diamine. Finally, it arranges various amines in order of increasing basic strength based on inductive and resonance effects.

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0% found this document useful (0 votes)
50 views42 pages

G12 NCERT Unit-13 Amines

The document discusses amines and provides solutions to practice problems involving classification, structures, reactions and properties of amines. It classifies sample amines as primary, secondary or tertiary based on their structure. It writes out the IUPAC names and structural isomers for all possible amine structures with the molecular formula C4H11N. It also describes reaction steps to convert benzene to aniline and dimethylaniline, and 1,4-dichlorobutane to hexane-1,6-diamine. Finally, it arranges various amines in order of increasing basic strength based on inductive and resonance effects.

Uploaded by

Md Taquee
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Class- XII-CBSE-Chemistry Amines

CBSE NCERT Solutions for Class 12 Chemistry Chapter 13


Back of Chapter Questions

13.1. Classify the following amines as primary, secondary or tertiary:

(i)

(ii)
(iii) (C2 H5 )2 CHNH2
(iv) (C2 H5 )2 NH
Solution:
Primary: (i) and (iii)
−N atom is attached with one carbon or one alkyl group.
Secondary: (iv)
−N atom is attached with two carbons or two alkyl groups.
Tertiary: (ii)
−N group attached with three carbons or three alkyl group.
13.2. (i) Write structures of different isomeric amines corresponding to the
molecular formula, C4 H11 N.
(ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines?
Solution:
(i), (ii): The structures and their IUPAC names of different isomeric amines
corresponding to the molecular formula, C4 H11 N is given below:
4 3 2 1
(a) CH3 − CH2 − CH2 − CH2 − NH2
Parent carbon chain = 5 membered (pent)

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Class- XII-CBSE-Chemistry Amines

Primary suffix = ane


Secondary suffix = amine
IUPAC name: Butanamine (1o amine)
(b)

Parent carbon chain = 4 membered (but)


Primary suffix = ane
Secondary suffix = amine
IUPAC Name: Butan-2-amine (1o amine)
(c)

Parent carbon chain = 3 (prop)


Primary suffix = ane
Secondary suffix = amine
Substituent = methyl (−CH3 )
IUPAC Name: 2-Methypropanamine (1o amine)
(d)

Parent carbon chain =3 (prop)


Primary suffix =ane
Secondary suffix = amine
Substituent (CH3 ) = methyl

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Class- XII-CBSE-Chemistry Amines

IUPAC Name: 2-Methylpropan-2-amine


(e) CH3 − CH2 − CH2 − NH − CH3
IUPAC Name: N-Methylpropanamine (2o amine)
3         2          1        
(f) CH3 − CH2 − CH2 − NH − CH3
IUPAC Name: N-Ethylethanamine (2o amine)
(g)

IUPAC Name: N-methylpropan -2-amine (2o amine)


(h)

IUPAC Name: N, N-Dimenthylethanamine (3o amine)


(iii) The pairs (a) and (b), (e) and (g) exhibit position isomerism because only
the position of functional group (−NH2 ) is changed.
The pairs (a) and (c), (a) and (d), (b) and (c), (b) and (d) exhibit chain
isomerism because the parent carbon chains are different.
The pairs (e) and (f), (f) and (g) exhibit metamerism.
All primary amines exhibit functional isomerism with secondary and
tertiary amines and vice-versa.
13.3. How will you convert
(i) Benzene into aniline
(ii) Benzene into N, N −dimethylaniline
(iii) Cl– (CH2 )4–Cl into hexan−1, 6 −diamine
Solution:
(i)

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Class- XII-CBSE-Chemistry Amines

Reaction of Benzene with HNO3 ⁄H2 SO4 is an electrophilic substitution


reaction. NO+
2 is a electrophile in the nitration reaction.

In the next step nitrobenzene is reduced by H2 ⁄Pd to aniline.


(ii)

Reaction of Benzene with HNO3 ⁄H2 SO4 is an electrophilic substitution


reaction. NO+
2 is a electrophile in the nitration reaction hence nitrobenzene
formed.
In the next step(second), nitrobenzene is reduced by H2 ⁄Pd to aniline.
In the next two steps (third and fourth) the substitution reaction taking
place and finally N,N-dimethylanilnine formed .
(iii)

Substitution reaction takes place when 1,4-dichlorobutane reacts with


ethanolic NaCN
In the next step, −CN group is reduced to form 1° amine.
13.4. Arrange the following in increasing order of their basic strength:
(i) C2 H5 NH2 , C6 H5 NH2 , NH3 , C6 H5 CH2 NH2 and (C2 H5 )2 NH
(ii) C2 H5 NH2 , (C2 H5 )2 NH, (C2 H5 )3 N, C6 H5 NH2
(iii) CH3 NH2 , (CH3 )2 NH, (CH3 )3 N, C6 H5 NH2 , C6 H5 CH2 NH2 .

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Class- XII-CBSE-Chemistry Amines

Solution:
(i) Considering +I effect of alkyl groups, NH3 , C2 H5 NH2 , and (C2 H5 )2 NH
can be arranged in the increasing order of their basic strengths as:
NH3 < C2 H5 NH2 < (C2 H5 )2 NH
Again, in C6 H5 NH2 acceptability of proton is less than NH3 . Thus, we
have:
Aromatic amine < Aliphatic Amine (Basic character)
Also due to the −I effective of C6 H5 group, the electron density on the
N −atom in C6 H5 CH2 NH2 is lower than that on the N −atom in C2 H5 NH2 ,
but more than that in NH3 . Therefore, the given compounds can be arranged
in the order of their basic strengths as:
C6 H5 NH2 < NH3 < C6 H5 CH2 NH2 < C2 H5 NH2 < (C2 H5 )2 NH (overall
basic strength)
(ii) Basic character ∝ +I effect
Due to +I effect −C2 H5 the basic character should be (C2 H5 )3 N >
(C2 H5 )2 NH > C2 H5 NH2 in the gaseous phase. But in aqueous state
hydrogen bonding is also taking place and extent of hydrogen bonding is
1° > 2° > 3° amine

So overall basic character in aqueous medium is result of inductive effect


and hydrogen bonding. So, order is 2o > 3o > 1o amine (Aliphatic).
Considering the inductive effect and the steric hindrance of the alkyl
groups in C2 H5 NH2 , (C2 H5 )3 N and (C2 H5 )2 NH, their basic strengths, can
be arranged as follows:

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Class- XII-CBSE-Chemistry Amines

C2 H5 NH2 < (C2 H5 )3 N < (C2 H5 )2 NH


Again, due to the −R effect of C6 H5 group, the electron density on the
N −atom in C6 H5 NH2 is lower than that on the N atom in C2 H5 NH2 .
Therefore, the basicity of C6 H5 NH2 is lower than that of C2 H5 NH2 i.e.,
aromatic amine is less basic than aliphatic amine. Hence, the given
compounds can be arranged in the increasing order of their basic strengths
as follows:
C6 H5 NH2 < C2 H5 NH2 < (C2 H5 )3 N < (C2 H5 )2 NH (overall order)
(iii) Basic character ∝ +I
Considering the (+I) inductive effect and the steric hindrance of alkyl
groups, CH3 NH2 , (CH3 )2 NH, and (CH3 )3 N can be arranged in the
increasing order of their basic strengths as:
(CH3 )3 N > (CH3 )2 NH > (CH3 )NH2 in gaseous phase.
In aqueous phase H − bonding is also taking place and extent of H − bond
is 1° > 2° > 3° Amine

Resulting overall basic character in aqueous medium is due to inductive


effect as well as hydrogen bonding so order of basic character is 2o >
1o > 3o
In C6 H5 NH2 , N is directly attached to the benzene ring. Thus, the lone pair
of electrons on the N −atom is delocalized over the benzene ring. In
C6 H5 CH2 NH2 , N is not directly attached to the benzene ring. Thus, its lone
pair is not delocalized over the benzene ring. Therefore, the electrons on the
N −atom are more easily available for protonation in C6 H5 CH2 NH2 than in
C6 H5 NH2 .
Again, due to the −I effect of C6 H5 group, the electron density on the
N −atom in C6 H5 CH2 NH2 is lower than that on the N −atom in (CH3 )3 N.
Therefore, (CH3 )3 N is more basic than C6 H5 CH2 NH2 . i.e., Aromatic amines
are less basic than aliphatic amine. Thus, the given compounds can be
arranged in the increasing order of their basic strengths as follows.
C6 H5 NH2 < C6 H5 CH2 NH2 < (CH3 )3 N < CH3 NH2 < (CH3 )2 NH

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Class- XII-CBSE-Chemistry Amines

13.5. Complete the following acid-base reactions and name the products:
(i) CH3 CH2 CH2 NH2 + HCl ⟶
(ii) (C2 H5 )3 N + HCl
Solution:
n-propylamine is basic and HCl is acidic. So, acid-base reaction is taking place
and salt is formed.
(i) CH3 CH2 CH2 NH2 + HCl → CH3 CH2 CH2 NH3+ Cl−
n−Propylamine n−Propylammoniumchloride

(ii) (C2 H5 )3 N + HCl → (C2 H5 )3 NH3+ Cl−


Triethylamine Triemethylammoniumchloride

Triethylamine is basic and HCl is acidic. So, acid-base reaction is taking


place and quaternary ammonium salt is formed.
13.6. Write reactions of the final alkylation product of aniline with excess of methyl
iodide in the presence of sodium carbonate solution.
Solution:
Aniline on reaction with methyl iodide produces N, N-dimethylaniline by
Hoffman degradation reaction.

With excess methyl iodide, in the presence of Na2 CO3 the solution, N, N-
dimethylaniline (quaternary ammonium salt) produces N, N, N-
trimethylanilinium carbonate.

13.7. Write chemical reaction of aniline with benzoyl chloride and write the name of
the product obtained.
Solution:

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Class- XII-CBSE-Chemistry Amines

13.8. Write structures of different isomers corresponding to the molecular formula,


C3 H9 N. Write IUPAC names of the isomers which will liberate nitrogen gas on
treatment with nitrous acid.
Solution:
The structures of different isomers corresponding to the molecular formula,
C3 H9 N are given below:
(a) CH3 − CH2 − CH2 − NH2
Propan-1-amine
(b)

Propan-2-amine
(c) CH3 − NH − C2 H5
N −Methylethanamine
(d)

N, N −Dimethylmethanamine
In (a) and (b), −NH2 group is attached to one – C atom. So, it is primary
amine.

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Class- XII-CBSE-Chemistry Amines

R − NH2 (Primary amine) + HNO2 → R − OH + H2 O


Nitrous acid (HNO2 ) is a mono basic weak acid which is used to
distinguish primary, secondary and tertiary amine.

When secondary amines react with HNO2 , no gas is produced, we get a


yellow oil (nitrosamine).

Concept Insight: Primary aliphatic amines react with nitrous acid to form
diazonium salt which being unstable liberate nitrogen gas.
13.9. Convert
(i) 3 −Methylaniline into 3 −nitrotoluene.
(ii) Aniline into 1,3,5 − tribromobenzene.
Solution:
(i)

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Class- XII-CBSE-Chemistry Amines

(ii)

NH2 group is +M group. So, it is more activating group and ortho/para


directing. Thus Br + attacks at ortho and para positions and forms
trisubstituted bromo derivative compound. 2,4,6-tribromoanline is white
crystalline solid.
13.10. Write IUPAC names of the following compounds and classify them into primary,
secondary and tertiary amines.
(i) (CH3 )2 CHNH2
(ii) CH3 (CH2 )2 NH2
(iii) CH3 NHCH(CH3 )2
(iv) (CH3 )3 CNH2
(v) C6 H5 NHCH3
(vi) (CH3 CH2 )2 NCH3
(vii) m– BrC6 H4 NH2
Solution:
(i) 1-Methylethanamine (1o amine)

(ii) Propan-1-amine (1o amine)

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Class- XII-CBSE-Chemistry Amines

(iii) N −Methyl-2-methylethanamine (20 amine)

(iv) 2-Methylpropan-2-amine (1o amine)

(v) N −Methylbenzamine or N −methylaniline (2o amine)

(vi) N −Ethyl-N-methylethanamine (3o amine)

(vii) 3 −Bromobenzenamine or 3 −bromoaniline (1o amine)

13.11. Give one chemical test to distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine
(ii) Secondary and tertiary amines
(iii) Ethylamine and aniline
(iv) Aniline and benzylamine

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Class- XII-CBSE-Chemistry Amines

(v) Aniline and N-methylaniline.


Solution:
(i) Carbylamine test is used to distinguish between Methylamine and
dimethylamine.
Carbylamine test: Aliphatic and aromatic primary amines when heated with
chloroform and ethanolic potassium hydroxide give foul-smelling
isocyanides or carbylamines. Methylamine is an aliphatic primary amine
that gives a positive carbylamine test, but dimethylamine does not give this
reaction.
Δ
CH3 − NH2 + CHCl3 + 3KOH → CH3 − NC + 3KCl + 3H2
Methylamine(1°) Methyl isocyanide
(foul smell)

Δ
(CH3 )2 NH + CHCl3 + 3KOH → No reaction
(ii) Hinsberg’s reagent (benzenesulphonyl chloride, C6 H5 SO2 Cl) is used to
distinguish between secondary and tertiary amines.
Secondary amines on reaction with Hinsberg’s reagent give a product
which is insoluble in an alkali.
For example, N, N −diethylamine on reaction with Hinsberg’s reagent
forms N, N −diethylbenzenesulphonamide, which is insoluble in an alkali.
Whereas, tertiary amines do not react with Hinsberg’s reagent because
they do not have hydrogen.

(iii) Azo-dye test can be used to distinguish between ethylamine and aniline.
When aromatic amines react with HNO2 (NaNO2 + dil. HCl) at 0 − 5o C,
followed by a reaction with an alkaline solution of 2-naphthol, a dye is
formed. The dye formed is usually yellow, red or orange coloured.

In the above reaction, diazotisation takes place.

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Class- XII-CBSE-Chemistry Amines

At pH 9-10 in the presence of base phenol and diazonium salt, coupling


reaction takes place and forms an azo dye.
Aliphatic amines give a brisk effervescence under similar conditions due
to the evolution of N2 gas.
0-5 °C
CH3 CH2 − NH2 + HONO → C2 H5 OH + N2 ↑ +H2 O
(iv) Nitrous acid can be used to distinguish aniline and benzylamine. Nitrous
acid is prepared in situ from a mineral acid and sodium nitrate. Benzylamine
on reaction with nitrous acid forms an unstable diazonium salt. The unstable
diazonium salt gives alcohol with the evolution of nitrogen gas.

On the other hand, aniline reacts with nitrous acid at a low temperature to
form a stable diazonium salt. Nitrogen gas is not evolved in this case.

(v) Carbylamine test is used to distinguish between aniline and


N −methylaniline. Primary amines, when heated with chloroform and
ethanolic potassium hydroxide, form foul-smelling isocyanides or
carbylamines. Aniline gives positive Carbylamine test because it is a
primary aromatic amine. However, N −methylaniline (secondary amine)
does not.

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Class- XII-CBSE-Chemistry Amines

13.12. Account for the following:


(i) pK b of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated
ferric oxide.
(iv) Although amino group is o, and p– directing in aromatic electrophilic
substitution reactions, aniline on nitration gives a substantial amount of
m −nitroaniline.
(v) Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazonium salts of aromatic amines are more stable than those of aliphatic
amines.
(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.
Solution:
(i) pK b = −logk b
If the basic character is more then k b value is high and pK b value is less.

Aniline undergoes resonance. So, the electrons on the nitrogen atom are
delocalised over the benzene ring. Therefore, the electrons on the nitrogen
atom are less available to donate. So, the basic character is less.

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Class- XII-CBSE-Chemistry Amines

In methylamine, due to the +I effect of the methyl group (electron-donating


group), the electron density on the N −atom increases and lone pair of
nitrogen is not involved in delocalisation. Thus, the basic character
increases.

K b value

pK b value

(ii) Ethylamine, on addition with water, forms intermolecular H −bonds with


water. Hence, it is soluble in water.

But aniline does not form H −bonds with water to a very large extent due
to the presence of a large hydrophobic −C6 H5 group. Hence, aniline is
insoluble in water.

(iii)

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Class- XII-CBSE-Chemistry Amines

Amines are more basic than water because the lone pair donor atom in
amine is nitrogen and in water is oxygen. And nitrogen is less
electronegative atom than oxygen.N can easily donate lone pair and +I
effect of −CH3 group, methylamine is more basic than water. Therefore, in
water, methylamine produces OH − ions by accepting H + ions from water.
+
CH3 − NH2 + H − OH → CH3 − NH3 + OH−
(Base) (Acid) (Salt)

Ferric chloride (FeCl3 ) dissociates in water to form Fe3+ and Cl− ions.
FeCl3 ⟶ Fe3+ + 3Cl−
Then, OH − ion reacts with Fe3+ ion and forms a precipitate of hydrated
ferric oxide.
2Fe3+ + 6OH − ⟶ Fe2 O3 . 3H2 O
Hydrated ferric oxide (ppt)

(iv) Nitration is carried out in an acidic medium. In an acidic medium, the


aniline is protonated to give anilinium ion. +NH3 group shows −I effect
(electron-withdrawing group). So, it is meta directing.

(v) Aniline does not undergo Friedel-crafts reaction:


Friedel-Crafts reaction takes place in the presence of AlCl3 . But AlCl3 is a
lewis acid due to vacant orbital availability while aniline is a strong base.
So, an acid-base reaction will take place. Thus, aniline reacts with AlCl3 to
form a salt.

Due to the positive charge on the nitrogen atom (shows −I effect and it is
meta directing), electrophilic substitution in the benzene ring is deactivated.
Hence, the Friedel-Crafts reaction will not take place in aniline.
(vi) The aromatic diazonium ion undergoes resonance.

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Class- XII-CBSE-Chemistry Amines

This resonance is the reason for the stability of the diazonium ion. While in
aliphatic amine no delocalisation takes place. Hence, the diazonium salts of
aromatic amines are more stable than those of aliphatic amines.
(vii) Only 1o amine is formed by Gabriel phthalimide synthesis. 2° and 3°
amines are not formed in this synthesis. So, a pure 1° amine can be obtained.
Therefore Gabriel phthalimide synthesis is preferred for synthesizing
primary amines.

13.13. Arrange the following:


(i) In decreasing order of the pK b values:
C2 H5 NH2 , C6 H5 NHCH3 , (C2 H5 )2 NH and C6 H5 NH2
(ii) In increasing order of basic strength:
C6 H5 NH2 , C6 H5 N(CH3 )2 , (C2 H5 )2 NH and CH3 NH2
(iii) In increasing order of basic strength:
(a) Aniline, p −nitroaniline and p −toluidine
(b) C6 H5 NH2 , C6 H5 NHCH3 , C6 H5 CH2 NH2 .
(iv) In decreasing order of the basic strength in the gas phase:

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Class- XII-CBSE-Chemistry Amines

C2 H5 NH2 , (C2 H5 )2 NH, (C2 H5 )3 N and NH3


(v) In increasing order of boiling point:
C2 H5 OH, (CH3 )2 NH, C2 H5 NH2
(vi) In increasing order of solubility in water:
C6 H5 NH2 , (C2 H5 )2 NH, C2 H5 NH2 .
Solution:
(i) In decreasing order of the pK b values:
C2 H5 NH2 , C6 H5 NHCH3 , (C2 H5 )2 NH and C6 H5 NH2
pK b = −log K b
If pK b value is less, then more the value of K b and the basic character.
C6 H5 NH2 and C6 H5 NHCH3 are aromatic amine while (C2 H5 )2 NH and
CH3 − NH2 are aliphatic amines.
−C2 H5 group is showing +I effect
In C2 H5 NH2 , only one −C2 H5 group is present while in (C2 H5 )2 NH, two
−C2 H5 groups are present. Thus, the +I effect more in (C2 H5 )2 than in
C2 H5 NH2 . Therefore, the electron density over the N −atom is more in
(C2 H5 )2 NH than in C2 H5 NH2 . Hence, (C2 H5 )2 NH is more basic than
C2 H5 NH2 . Both C6 H5 NHCH3 and C6 H5 NH2 are less basic than (C2 H5 )2 NH
and C2 H5 NH2 due to the delocalization of the lone pair in the former two.
Further, among C6 H5 NHCH3 and C6 H5 NH2 , the former will be more basic
due to the +I effect of −CH3 group.
C6 H5 NH2 < C6 H5 NHCH3 (basic character)
The basic character of aromatic amine is less than aliphatic amine because
lone pair of nitrogen in aromatic amine is involved in delocalisation while
in aliphatic amine it is not involved in delocalisation hence overall basic
character is (K b )
C6 H5 NH2 < C6 H5 − NHCH3 < C2 H5 NH2 < (C2 H5 )2 NH
Hence the order of pK b is
C6 H5 NH2 > C6 H5 NHCH3 > C2 H5 NH2 > (C2 H5 )2 NH
∵ pK b = −log K b
We know that the higher the basic strength, the lower is the pK b values.
C6 H5 NH2 > C6 H5 NHCH3 > C2 H5 NH2 > (C2 H5 )2 NH
(ii) C6 H5 N(CH3 ) is more basic than C6 H5 NH2 due to the +I effect of two
−CH3 groups in C6 H5 N(CH3 )2 . Also, CH3 NH2 contains one −CH3 group

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Class- XII-CBSE-Chemistry Amines

while (C2 H5 )2 NH contains two −C2 H5 groups. Thus, (C2 H5 )2 NH is more


basic than C2 H5 NH2 .
Now, C6 H5 N(CH3 )2 is less basic than CH3 NH2 because of the −R effect
of −C6 H5 group.
Hence, the increasing order of the basic strength of the given compounds
is as follows:
C6 H5 NH2 < C6 H5 N(CH3 )2 < CH3 NH2 < (C2 H5 )2 NH
(iii) (a)

In p −substituted amine, the presence of electron-donating −CH3


group (+H > +I) increases the electron density on the nitrogen
atom. Hence, the basic character increases.
Thus, p −toluidine is more basic than aniline.
On the other hand, due to the presence of electron-withdrawing
−NO2 group (−M > −I) decreases the electron density over the
N −atom in p −nitroaniline. Thus, p −nitroaniline is less basic than
aniline.
Hence, the increasing order of the basic strengths of the given
compounds is as follows:
p −nitroaniline < Aniline < p −Toluidine

(b) C6 H5 NHCH3 is more basic than C6 H5 NH2 due to the presence of


electron-donating −CH3 group (+𝐻 > +𝐼 inductive effect) in
C6 H5 NHCH3 .

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Again, in C6 H5 NHCH3 , −C6 H5 group is directly attached to the


nitrogen atom. However, it is not so in C6 H5 CH2 NH2 . The lone pair
of nitrogen is not involved in delocalisation. Thus, in C6 H5 NHCH3 ,
the −R effect of −C6 H5 group decreases the electron density over
the nitrogen atom. Therefore, C6 H5 CH2 NH2 is more basic than
C6 H5 NHCH3 .
Hence, the increasing order of the basic strength of the given
compounds is as follows:

(iv) The basic strength mainly depends upon the electron-donating group (+I
effect) because there is no solvation effect in the gas phase. More is the +I
effect, stronger is the base. Also, the more the number of alkyl groups, the
higher is the +I effect. Therefore, the given compounds can be arranged in
the decreasing order of their basic strengths in the gas phase as follows:
(C2 H5 )3 N > (C2 H5 )2 NH > C2 H5 NH2 > NH3
(v) The boiling points of compounds depend on the hydrogen bonding present
in the compound. The more extensive the H −bonding in the compound, the
higher is the boiling point. (CH3 )2 NH contains only one H −atom whereas
C2 H5 NH2 contains two H −bonding than (CH3 )2 NH. Hence, the boiling
point of C2 H5 NH2 is higher than that of (CH3 )2 NH.
Boiling point ∝ force of attraction ∝ H- bond
Force of attraction between C2 H5 OH is also H-bond. C2 H5 OH forms
stronger H −bonds than C2 H5 NH2 and (CH3 )2 NH.

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The given compounds can be arranged in the increasing order of their


boiling points as follows:
(CH3 )2 NH < C2 H5 NH2 < C2 H5 OH
(vi) Solubility is directly proportional to the extent of hydrogen bonding.
C2 H5 NH2 contains two H −atoms whereas (C2 H5 )2 NH contains only one
H −atom. Thus, C2 H5 NH2 undergoes more extensive H −bonding than
(C2 H5 )2 NH. Hence, the solubility in water of C2 H5 NH2 is more than that
of (C2 H5 )2 NH.
Further, the solubility of amines decreases with an increase in the molecular
mass. This is because the molecular mass of amines increases with an
increase in the size of the hydrophobic part. The molecular mass of
C6 H5 NH2 is greater than that of C2 H5 NH2 and (C2 H5 )2 NH. Also due to
steric crowding the extent of hydrogen bonding in C6 H5 NH2 decreases.

Hence, the increasing order of their solubility in water is as follows:


C6 H5 NH2 < (C2 H5 )2 NH < C2 H5 NH2

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Class- XII-CBSE-Chemistry Amines

13.14. How will you convert:


(i) Ethanoic acid into methanamine
(ii) Hexanenitrile into 1 −aminopentane
(iii) Methanol to ethanoic acid
(iv) Ethanamine into methanamine
(v) Ethanoic acid into propanoic acid
(vi) Methanamine into ethanamine
(vii) Nitromethane into dimethylamine
(viii) Propanoic acid into ethanoic acid?
Solution:
(i)

(ii)

(iii)

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(iv)

(v)

(vi)

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Class- XII-CBSE-Chemistry Amines

(vii)

(viii)

13.15. Describe a method for the identification of primary, secondary and tertiary amines.
Also, write chemical equations of the reactions involved.
Solution:
Hinsberg’s test is used to identify and distinguish primary, secondary and tertiary
amines. In the Hinsberg’s test, the amines are allowed to react with Hinsberg’s
reagent, benzenesulphonyl chloride (C6 H5 SO2 Cl). Different types of amines react
differently with the Hinsberg’s reagent.
Primary amines react with benzenesulphonyl chloride to form
N −alkylbenzenesulphonyl amide which is soluble in alkali.

Due to the presence of a strong electron-withdrawing sulphonyl group in the


sulphonamide, the H −atom attached to nitrogen can be easily released as a proton.
Therefore, it is acidic and dissolves in an alkali.
Secondary amines react with Hinsberg’s reagent to give a sulphonamide which is
insoluble in alkali.

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Class- XII-CBSE-Chemistry Amines

There is no H −atom attached to the N −atom in the sulphonamide. Therefore, it is


not acidic and is insoluble in an alkali.
Tertiary amines do not react with Hinsberg’s reagent at all.
13.16. Write short notes on the following:
(i) Carbylamine reaction
(ii) Diazotisation
(iii) Hofmann’s bromamide reaction
(iv) Coupling reaction
(v) Ammonolysis
(vi) Acetylation
(vii) Gabriel phthalimide synthesis.
Solution:
(i) Carbylamine reaction
Carbylamine reaction is used as a test for the identification of primary
amines. When aliphatic and aromatic primary amines are heated with
chloroform (CHCl3 ) and ethanolic potassium hydroxide (KOH),
carbylamines (or isocyanides) are formed. These carbylamines have very
unpleasant odours. Secondary and tertiary amines do not respond to this
test.
General reaction:

Where R = Alkyl group


−R Should not be −CH3 because CH3 − NC (Methyl isocyanide) is formed,
which is a poisonous gas.
For example,

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Class- XII-CBSE-Chemistry Amines

Δ
C2 H5 − NH2 + CHCl3 + 3KOH(alc. ) → C2 H5 − NC + 3KCl + 3H2 O
Ethanamine Ethyl carbylamine
( )
or ethyl isocyanide

(ii) Diazotisation
Aliphatic or Aromatic primary amines react with nitrous acid (prepared in
situ from NaNO2 and a mineral acid such as HCl) at low temperatures
(273 − 278 K) to form diazonium salts. The above conversion of primary
aromatic amines into diazonium salts is known as diazotisation.
For example, on treatment with NaNO2 and HCl at 273 − 278 K, aniline
produces the compound benzene diazonium chloride, with NaCl and H2 O
as by-products.

R − NH2 → R − N2 Cl
NaNO2⁄HCl Diazonium chloride

(iii) Hoffmann bromamide reaction


When an amide is treated with bromine in an aqueous or ethanolic solution
of sodium hydroxide, a primary amine with one carbon atom less than the
original amide is produced. This degradation reaction is known as
Hoffmann bromamide reaction. This reaction involves the migration of an
alkyl or aryl group from the carbonyl carbon atom of the amide to the
nitrogen atom.
General reaction

Reaction Mechanism:

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Class- XII-CBSE-Chemistry Amines

For example,

(iv) Coupling reaction:


The reaction in which two aromatic rings are joined through the −𝑁 =
𝑁 −bond is known as coupling reaction. Arenediazonium salts such as
benzene diazonium salts react with phenol or aromatic amines to form
coloured azo compounds.

𝐷𝑖𝑙 𝑁𝑎𝑂𝐻 at 𝑝𝐻 = 8.5 to 9.5 reacts with −𝐻 of phenol group. Due to this
phenoxide ion is formed. It activates the ring. When the phenoxide ion
reacts with a diazonium salt, it results in the formation of azo dye. This
reaction is called coupling reaction.

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Class- XII-CBSE-Chemistry Amines

It is observed that the para-positions of phenol and aniline are coupled


with the diazonium salt. This reaction proceeds through electrophilic
substitution.
(v) Ammonolysis
When an alkyl or benzyl halide is reacted with an ethanolic solution of
ammonia, it undergoes nucleophilic substitution reaction in which the
halogen atom is replaced by an amino group (−NH2 ). This process of
cleavage of the carbon-halogen bond is known as ammonolysis.

This substituted ammonium salt when treated with a strong base such as
sodium hydroxide, amine is obtained.

Though primary amine an as the major product, this process produces a


mixture of primary, secondary and tertiary amines, and also a quaternary
ammonium salt as shown.

(vi) Acetylation
Acetylation (or ethanoylation) is the process of introducing an acetyl
group into a molecule.

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Class- XII-CBSE-Chemistry Amines

Aliphatic and aromatic primary and secondary amines undergo acetylation


reaction by nucleophilic substitution when treated with acid chlorides,
anhydrides or esters. This reaction involves the replacement of the hydrogen
atom of −NH2 or > NH group by the acetyl group, which in turn leads to
the production of amides. To shift the equilibrium to the right-hand side, the
HCl formed during the reaction is removed as soon as it is formed. This
reaction is carried out in the presence of a base (such as pyridine) which is
stronger than the amine.

When amines react with benzoyl chloride, the reaction is also known as
benzoylation. And this is followed by an electrophile substitution reaction
For example,

(vii) Gabriel phthalimide synthesis


Gabriel phthalimide synthesis is a very useful method for the preparation
of aliphatic primary amines. It involves the treatment of phthalimide with

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Class- XII-CBSE-Chemistry Amines

ethanolic potassium hydroxide to form potassium salt of phthalimide. This


salt is further heated with an alkyl halide, followed by alkaline hydrolysis
to yield the corresponding primary amine.

13.17. Accomplish the following conversions:


(i) Nitrobenzene to benzoic acid
(ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline
(iv) Aniline to 2,4,6 −tribromofluorobenzene
(v) Benzyl chloride to 2 −phenylethanamine
(vi) Chlorobenzene to 𝑝 −chloroaniline
(vii) Aniline to p-bromoaniline
(viii) Benzamide to toluene
(ix) Aniline to benzyl alcohol.
Solution:
(i) Nitrobenzene to benzoic acid:

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Class- XII-CBSE-Chemistry Amines

(ii)

(iii)

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Class- XII-CBSE-Chemistry Amines

(iv)

(v)

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Class- XII-CBSE-Chemistry Amines

(vi)

(vii)

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Class- XII-CBSE-Chemistry Amines

(viii)

(ix)

13.18. Give the structures of A, B and C in the following reactions:

(i)

(ii)

(iii)

(iv)

(v)

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Class- XII-CBSE-Chemistry Amines

(vi)
Solution:
(i)

(ii)

(iii)

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Class- XII-CBSE-Chemistry Amines

(iv)

(v)

(vi)

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Class- XII-CBSE-Chemistry Amines

13.19. An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms
compound ‘B’ which on heating with Br2 and KOH forms a compound ‘C’ of
molecular formula C6 H7 N. Write the structures and IUPAC names of compounds
A, B and C.
Solution:
It is given in the question the compound ‘C’ having the molecular formula, C6 H7 N
is formed by heating compound ‘B’ with Br2 and KOH. Reaction with Br2 or KOH
is a Hoffman bromamide degradation reaction and is given by an amide. The
formed product is an amine (one carbon down amide). Therefore, compound ‘B’ is
an amide and compound ‘C’ is an amine. The only amine having the molecular
formula, C6 H7 N is aniline, (C6 H5 NH2 ).
Therefore, compound ‘B’ must be benzamide, (C6 H5 CONH2 )
Further, benzamide is formed by heating compound ‘A’ with aqueous ammonia.
Therefore, compound ‘A’ must be benzoic acid.
The given reaction occurs in the following sequence:

13.20. Complete the following reactions:


(i) C6 H5 NH2 + CHCl3 + alc. KOH ⟶
(ii) C6 H5 N2 Cl + H3 PO2 + H2 O ⟶

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Class- XII-CBSE-Chemistry Amines

(iii) C6 H5 NH2 + H2 SO4 (conc. ) ⟶


(iv) C6 H5 N2 Cl + C2 H5 OH ⟶
(v) C6 H5 NH2 + Br2 (aq) ⟶
(vi) C6 H5 NH2 + (CH3 CO)2 O ⟶
Solution:
(i)
Carbylamine
reaction
C6 H5 NH2 + CHCl3 + 3 KOH(alc. ) → 3H2 O + 3KCl + C6 H5 − NC
Aniline Phenyl
isocyanide

(ii)
C6 H5 N2 Cl + H3 PO2 + H2 O → C6 H6 + N2 + H3 PO3 + HCl
Benzenediazonium Benzene
chloride

The above reaction is a redox reaction.


(iii)
+ −
C6 H5 NH2 + conc. H2 SO4 → C6 H5 NH3 HSO4
Aniline Anilinium hydrogen sulphate

−NH2 group is basic and H2 SO4 is acid. Hence salt is formed by an acid-
base reaction.
(iv)
C6 H5 N2 Cl + C2 H5 OH → C6 H6 + CH2 CHO + N2 ↑ +HCl
Benzene diazonium Ethanol Benzene Ethanol
chloride

This reaction is a redox reaction.


(v)

An aniline−𝑁𝐻2 is +𝑀 group and it is a ring activating group for


electrophilic attack and ortho-para directory. So, electrophile −𝑁𝑂2+ attack
at ortho-para. 2,4,6-Tribromo aniline is formed, which is a white crystalline
solid.

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Class- XII-CBSE-Chemistry Amines

(vi)

(vii)

13.21. Why cannot aromatic primary amines be prepared by Gabriel phthalimide


synthesis?
Solution:
Gabriel phthalimide synthesis is used for the preparation of aliphatic primary
amines. It involves nucleophilic substitution (SN 2) of alkyl halides by the
phthalimide.

But aryl halides do not undergo nucleophilic substitution with the anion formed
by the phthalimide because positive charge on the benzene ring is highly unstable
due to the double bond character.

Hence, primary aromatic amines cannot be prepared by this process.

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13.22. Write the reactions of


(i) aromatic amines with nitrous acid
(ii) aliphatic primary amines with nitrous acid.
Solution:
(i) Aromatic amines react with nitrous acid (prepared in situ from NaNO2 and
a mineral acid such as HCl) at 273 − 278 K to form stable aromatic
diazonium salts due to the double bond character.

(ii) Aliphatic primary amines react with nitrous acid (prepared in situ from
NaNO2 and a mineral acid such as HCl) to form unstable aliphatic
diazonium salts, which further produce alcohol and HCl with the evolution
of N2 gas.

13.23. Give plausible explanation for each of the following:


(i) Why are amines less acidic than alcohols of comparable molecular
masses?
(ii) Why do primary amines have higher boiling point than tertiary amines?
(iii) Why are aliphatic amines stronger bases than aromatic amines?
Solution:
(i) Amines undergo protonation to give amide ion.

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R − NH2 → R + NH-2 + H+
(Acid) Amide ion
(Conjugate base)

Similarly, alcohol loses a proton to give alkoxide ion.


R − OH → R − O− + H+
Alcohol Alkoxide ion
(Acid) (Conjugate base)

Acidic strength ∝ stability of conjugate base or anion


Stability of conjugate base or anion ∝ negative charge density on anion ∝
electronegativity of atom
In an amide, ion, the negative charge is on the N-atom, whereas, in an
alkoxide ion, the negative charge is on the O-atom. Since O is more
electronegative than N, O can accommodate the negative charge more easily
than N. As a result, the amide ion is less stable than the alkoxide ion i.e.,
the conjugate base amide is less stable then alkoxide ion. Hence, amines are
less acidic than alcohols of comparable molecular masses.
(ii) In a molecule of a tertiary amine, there are no H-atoms. Whereas, in the
primary amines, two hydrogen atoms are present. Due to the presence of H-
atoms, primary amines undergo extensive intermolecular H-bonding.

(Tertiary amine)
Very less hydrogen bonding in tertiary amine due to steric hindrance of
alkyl group (-R).
To break the hydrogen bond, extra energy is required to separate the
molecules of primary amines. Hence, primary amines have higher boiling
points than tertiary amines.
(iii) Due to the -R effect of the benzene ring, the electrons on the N-atom are
less available in case of aromatic amines. Therefore, the electrons on the

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N-atom in aromatic amines cannot be donated easily. This explains why


aliphatic amines are stronger bases than aromatic amines.
Aromatic amine:

For aliphatic amine R → NH2 , R exerts +I effect. Charge density on


nitrogen increases; hence, basic character increases.

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