Dr. A. Anandhan M.Sc., M.Phil., B.Ed., Ph.D.

,
Mob. No: 9976366388, 9790669474

13. Amines
NCERT TEXTBOOK QUESTIONS SOLVED:

Intext Questions:

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

Ans: (i) 1° (ii) 3° (iii) 1° (iv) 2°

13.2. Write the structuress of different isomeric amines corresponding to the

molecular formula, C4H11N.
(i) Write the IUPAC names of all the isomers
isomers.
(ii) What type of isomerism is exhibited
exhibited by different types of amines?
Ans: Eight isomeric amines are possible

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Isomerism exhibited by different amines
amines.

 Chain isomers : (i) and (ii) ; (iii) and (iv) ; (i) and (iv)
 Position isomers : (ii) and (iii) ; (ii) and (iv)
 Metamers : (v) and (vi) ; (vii) and (viii)
 Functional isomers: All the three types of amines are the functional isomers of
each other.

13.3. How will you convert:

(i) Benzene into aniline
(ii) Benzene into N,N-dimethylaniline
dimethylaniline
(iii) Cl-(CH2)4-Cl into hexan
exan-1,6-diamine.

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Ans:

13.4. Arrange
rrange the following in increasing order of their basic strength :
(i) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2, (C2H5)2NH
(ii) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
(iii) CH3NH2, (CH3)2NH, (CH3)3N, C6HsNH2, C6H5CH2NH2
Ans:
In general, the basic character of ammonia
ammo (NH3) and the amines is linked with the
availability of the lone electrons pair on the nitrogen atom. In other words, these are all
Lewis bases.
Amines act as Lewis bases due to the t presence of lone electron pairr on the nitrogen atom.
Since the nitrogenn atom is sp³ hybridised, its electron attracting tendency is considerably
reduced. It can readily lose its electron pair and acts as a base. For example, amines form
hydroxides with water.

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Here Kt is called dissociation constant for the base. Greater the
th Kb value stronger will be
the base. The basic strength
of amines can also be expressed as pKb value which is related to Kb as :

The Kb values are :

13.5. Complete the following acid

acid-base
base reactions and name the products:
(i) CH3CH2CH2NH2 + HCl ——–>
(ii) (C2H5)3 N + HCl ——––>

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Ans:

13.6. Write reactions of the final alkylation product of aniline with excess of methyl
iodide in the presence of sodium carbonate solution.
Ans:

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

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13.8. Write structures of different isomers corresponding to the molecular formula,
C3H9N. Write IUPAC names of the isomers which will liberate N2 gas on treatment
with nitrous acid.
Ans: In ‘all, four structural isomers are
ar possible. These are:

13.9. Convert:
(i) 3-Methylaniline into 3-nitrotoluene
nitrotoluene
(ii) Aniline into 1,3,5- tribromo
ribromobenzene

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Ans:

NCERT EXRECISES

13.1. Write IUPAC names of the following compounds and classify them into
primary, secondary, and tertiary amines.
amines
(i) (CH3)2CHNH2 (ii) CH3(CH2)2NH2 (iii) CH3NHCH(CH3)2
(iv) (CH3)3CNH2 (v) C6H5NHCH3 (vi) (CH3CH2)2NCH3
(vii) m-BrC6H4NH2
Ans:
(i) Propan-2-amine (1°)
(ii) Propan-1-amine (1°)
(iii) N-Methylpropan-2-amine
amine (2°)
(iv) 2-Methylpropan-2-amine
amine (l°)
(v) N-Methylbenzenamine or N-methylaniline (2°)
(vi) N-Ethyl-N-methylethanamine
methylethanamine (3°)
(vii) 3-Bromobenzenamine
Bromobenzenamine or 3-bromoaniline
3 (1°)

13.2. 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
(v) Aniline and N-Methylaniline.
Methylaniline.

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Ans:

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13.3. Account for the following
(i) pKb of aniline is more than that of methylamine.
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 oo- 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
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.
Ans:
(i) In aniline, the lone pair of electrons on the N atom is delocalised over the benzene
N-atom
ring. As a result, electron
ctron density on the nitrogen atom decreases. Whereas in CH3NH2+
I-effect of -CH3 group increases the electron density on the N-atom.
N atom. Therefore, aniline is
a weaker
ker base than methylamine and hence its pKb value is higher than that of
methylamine.
(ii) Ethylamine dissolves in water due to intermolecular H-bonding.
H bonding. However, in case of
aniline, due to the large hydrophobic part, i.e., hydrocarbon part, the extent of H-bonding
is very less therefore aniline is insoluble in water.

(iii) Methylamine being more basic than water, accepts a proton from water liberating
OH– ions,

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(iv) Nitration is usually carried out with a mixture of cone HNO3 + cone H2SO4. In
presence of these acids, most of aniline
an ilinium ion. Therefore,
gets protonated to form anilinium
in presence of acids, the reaction mixture consist of aniline and anilinium ion. Now, -NH2
groupp in aniline is activating and o, p-directing while the -+NH3 group in aniliniu
anilinium ion is
deactivating and re-directing:
directing: Nitration of aniline (due to steric hindrance at
o-position)
position) mainly gives pp-nitroaniline,
nitroaniline, the nitration of anilinium ion gives
m-nitroaniline.
nitroaniline. In actual practice, approx a 1:1 mixture of p- p-nitroaniline and m-
line is obtained. Thus, nitration of aniline gives a substantial amount of m
nitroaniline m-
nitroaniline due to protonation of the amino group.

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13.4. Arrange the following:
(i) In decreasing order of pKb values:
C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
(ii) In increasingg order of basic strength:
C6H5NH2, C6H5N(CH3)2, (C2H5)2 NH and CH3NH2
(iii) In increasing order of basic strength:
(а) Aniline, p-nitroaniline
nitroaniline and p-toluidine
(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2
(iv) In decreasing order of basic strength in gas phase:
C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
(v) In increasing order of boiling point:
C2H5OH, (CH3)2NH, C2H5NH2
(vi) In increasing order of solubility in water:
C6H5NH2, (C2H5)2NH, C2H5NH2
Ans:
(i) Due to delocalisation of lone pair of electrons of the N-atom
N atom over the benzene
ben ring,
C6H5NH2 and C6H5NHCH3 are far less basic than C2H5NH2 and (C2H,)2NH. Due to +I-
effect of the -CH3 group, C6H5NHCH3 is little more basic that C6H5NH2. Among
C2H5NH2 and (C2H5)2NH, (C2H5)2NH is more basic than C2H5NH2 due to greater +I-
effect of two -C2H5 groups. Therefore correct order of decreasing pKb values is:

(ii) Among CH3NH2 and (C2H5)2NH, primarily due to the greater +I-effect of the
two -C2H5 groups over one -CH3 group, (C2H5)2NH is more basic than CH3NH2.In both
C6H5NH2 and C6H5N(CH3)2 lone pair of electrons present on N-atom
atom is delocalized over
the benzene ring but C6H5N(CH3)2 is more basic due to +1 effect of two-CH
two 3 groups.

(iii) (a) The presence of electron donating -CH3 group increases while the presence of
electron withdrawing -NO2 group decreases the basic strength of amines.

(b) In C6H5NH2 and C6H5NHCH3, N is directly attached to the benzene ring. As a result,
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 N atom is delocalised over the benzene ring. Therefore,
the lone pair of electrons on the N-atom
both C6H5NH2 and C6H5NHCH3 are weaker base in comparison to C6H5CH2NH2. Among
C6H5NH2 and C6H5NHCH3, due to +1 effect of-CH of 3 group C6H5NHCH3 is more basic.

(iv) In gas phase or in non-aqueous

aqueous solvents such as chlorobenzene etc, the solvation
effects i. e., the stabilization of the conjugate
c acid due to H-bonding
bonding are absent.
Therefore, basic strength depends only upon the +I-effect
+I effect of the alkyl groups. The +I
+I-
effect increases with increase in number of alkyl groups. Thus correct order of decreasing
basic strength in gas phase is,

(v) Since the electronegativity of O is higher than that

tha of N, therefore, alcohols form
stronger H-bonds
bonds than amines. Also, the extent
exten of H-bonding
bonding depends upon the number
of H-atoms on the N-atom,
atom, thus the extent of H-bonding
H bonding is greater in primary amine than
secondary amine.

(vi) Solubility decreases with increase in molecular mass of amines due to increase in the
size of the hydrophobic hydrocarbon part and with decrease is the number of H-atoms
H on
the N-atom
atom which undergo H-bonding.
H

13.5. How will you convert:

onvert:
(i) Ethanoic acid into methanamine
(ii) Hexanenitrile into 1-aminopentane
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?

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Ans:

13.6. Describe the method for the identification of primary, secondary and tertiary
amines. Also write chemical equations of the reactions involved.
Ans:
The distinction in the three types of amines ca
cann be done by the following methods :
(i) Hinsberg’s Test:

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This is a very useful test for the distinction of primary, secondary and tertiary amines. An
su phonyl chloride) in the presence of
amine is shaken with Hinsberg’s reagent (benzene sulphonyl
excess of aqueous KOH solution. The reactions taking place are given on the next page.

1. A primary amine forms N – alkyl benzene sulphonamide

phonamide which dissolves in
aqueous KOH solution to form potassium salt and upon acidification with dilute
HCI
CI regenerates the insoluble su
sulphonamide.

2. A secondary amine forms N, N – dialkylbenzene sulphonamide

phonamide which remains
insoluble in aqueous KOH and even after acidification with dilute HCl

3. A tertiary amine does not react with benzene susulphonyl

phonyl chloride and remains
insoluble in aqueous KOH.
K However, on acidification with dilute HCI it gives a
clear solution due to the formation of the ammonium salt.

(ii) Reaction with nitrous acid:

All the three types of amines, aliphatic as well as aromatic, react with nitrous acid under
different conditions
itions to form variety of products. Since nitrous acid is highly unstable, it is
prepared in situ by the action of dilute hydrochloric acid on sodium nitrite.

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(a) Primary aliphatic amines react with nitrouss acid at low temperature
temperatur (cold
conditions) to form primary alcohol and nitrogen gas accompanied by brisk
effervescence. Nitrous acid is unstable in nature and is prepared in situ by reacting
sodium nitrite with dilute hydrochloric acid. For example,

The reaction is used as a primary alipha

aliphatic amines as no otherr amine evolves nitrogen
with nitrous acid.

(b) Primary aromatic amines such as aniline react with nitrous acid under ice cold
conditions (273 – 278 K) to form benzene
benzen diazonium salt. The reaction is known
as diazotisation reaction.

in case, the temperature is allowed to rise above 278 K, benzene diazo

diazonium chloride is
decomposed by water to form phenol.

Aliphatic primary amines also react with nitrous acid to form alkyl diazonium salts in a
similar manner. But these are quite unstable and decompose to form a mixture of
alcohols,
lcohols, alkenes and alkyl halides along with the evolution of N2 gas.

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(c) Secondary amines (both aliphatic and aromatic) react with nitrous acid to form
nitrosoamines which separate as Yellow oily liquids.

(d) Tertiary
y aliphatic amines dissolve in a cold solution of nitrous acid to form salts
which decompose on warming to give nitrosoamine and alcohol. For example,

(e) Tertiary aromatic amines react with nitrous acid to give a coloured
nitrosoderivative.
itrosoderivative. This reaction
reactio is called nitrosation and as a result, a hydrogen atom in
the para position gets replaced by a nitroso ((-NO)
NO) group. For example,

13.7. 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

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Ans: (i) Carbylamine reaction: Both aliphatic and aromatic primary amines when
warmed with chloroform and an alcoholic solution of KOH, produces isocyanides or
lamines which have very unpleasant odours. This reaction is called carbylamine
carbylamines
reaction.

(ii) Diazotisation: The process of conversion of a primary aromatic amino compound

into a diazonium salt, is known as diazotisation. This process is carried out by aadding an
aqueous solution of sodium nitrite to a solution of primary aromatic amine (e.g., aniline)
in excess of HCl at a temperature below 5°C.

(iii) Hoffmann’s bromamide reaction: When an amide is treated with bromine in alkali
solution, it is convertedd to a primary amine that has one carbon atom less than the starting
amide. This reaction is known as Hoffmann’s
Hoff ann’s bromamide degradation reaction.

(iv) Coupling reaction: In this reaction, arene diazonium salt reacts with aromatic amino
compound (in acidicc medium) or a phenol (in alkaline medium) to form brightly coloured
azo compounds. The reaction generally takes place at para position to the hydroxy or
amino group. If para position is blocked, it occurs at ortho position and if both ortho and
para positions
ions are occupied, than no coupling takes place.

(v) Ammonolysis: It is a process of replacement of either halogen atom in alkyl halides

(or aryl halides) or hydroxyl group in alcohols (or phenols) by amino group. The reagent
used for ammonolysis is alcoholic
alcoholic ammonia. Generally, a mixture of primary, secondary
and tertiary amine is formed.

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(vi) Acetylation: The process of introducing an acetyl (CH3CO-)) group into molecule
using acetyl chloride or acetic anhydride is called acetylation.

(vii) Gabriel phthalimide

hthalimide synthesis: It is a method of preparation of pure aliphatic and
aralkyl primary amines. Phthalimide on treatment with ethanolic KOH gives potassium
phathalimide which on heating with a suitable alkyl Or aralkyl halides gives
N-substituted phthalimides,
mides, which on hydrolysis with dil.
dil HCI or with alkali give primary
amines.

13.8. Accomplish the following conversions:

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

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Ans:

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13.9. Give the structures of A, B and C in the following reaction:

Ans:

13.10. 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 C6H7N. Write the structures and IUPAC names of compounds A,
B and C.
Ans:
From
m the available information, we find that ‘B’ upon heating with Br2 and KOH forms a
compound ‘C’. The compound ‘B’ is expected to be an acid amide. Since ‘B’ has been
formed upon heating compound ‘A’ with aqueous ammonia, the compound ‘A’ is an
aromatic acid.

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It is benzoic acid. The reactions involved are given as follows:

13.11. Complete the following reactions:

Ans:

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13.12. Why cannot aromatic primary amines be prepared by Gabriel phthalimide
synthesis?
reaction depends upon the nucleophilic attack
Ans: The success of Gabriel phthalimide reaction
by the phthalimide anion on the organic halogen compound. Since aryl halides do not
undergo nucleophilic substitution reactions easily, therefore, arylamines, i.e., aromatic,
primary amines cannot be prepared by Gab
Gabriel phthalimide reaction.

13.13. Write the reactions of (i) aromatic and (ii) aliphatic primary amines with
nitrous acid.
Ans: Both aromatic and aliphatic primary amines react with HNO2 at 273-278
273 K to form
aromatic and aliphatic diazonium salts respectively.
respectively. But aliphatic diazonium salts are
unstable even at this low temperature and thus decompose readily to form a mixture of
compounds. Aromatic and aliphatic primary amines react with

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13.14. 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?
Ans: (i) Loss of proton from an amine gives an amide ion while loss of a proton from
alcohol give an alkoxide ion.
R—NH2 —> R—NH– +H+
R—O —H —> R— O– +H+ .

Since O is more electronegative than N, so it will attract positive species more strongly in
comparison to N. Thus, RO~ is more stable than RNH®. Thus, alcohols are more acidic
than amines. Conversely, amines are less acidic than alcohols.
(ii) Due to the presence of two H-atoms on N-atom of primary amines, they undergo
extensive intermolecular H-bonding while tertiary amines due to the absence of H-atom
on the N-atom do not undergo H-bonding. As a result, primary amines have higher
boiling points than tertiary amines of comparable molecular mass.
(iii) Aromatic amines are far less basic than ammonia and aliphatic amines because of
following reasons:
(a) Due to resonance in aniline and other aromatic amines, the lone pair of electrons on
the nitrogen atom gets delocalised over the benzene ring and thus it is less easily
available for protonation. Therefore, aromatic amines are weaker bases than ammonia
and aliphatic amines.
(b) Aromatic amines are more stable than corresponding protonated ion; Hence, they are
very less tendency to combine with a proton to form corresponding protonated ion, and
thus they are less basic.

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