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AMINES
INTROCUTION
Amines are alkyl derivatives of ammonia obtained by replacing one or more H-atoms by
corrosponding number of alkyl groups. e.g. C2H5NH2 Ethylamine.
Amines are nitrogen containing basic compounds.

CLASSIFICATION
Amines are of three types according to the number of alkyl groups attached to the
nitrogen atom.
1) Primary Amine :
They are the mono alkyl derivatives of ammonia obtained by replacing one H-atom by
an alkyl group.
They are represented as R-NH2.
Functional group : —NH2 (amino).
e.g. CH3NH2 ( methylamine ) ; C2H5NH2 ( ethylamine ).
2) Secondary Amines :
They are the dialkyl derivatives of ammonia obtained by replacing 2-H atoms by two
alkyl groups. They are represented as R2NH
Functional group : ─NH2 ( amino)

e.g. (CH3)2 NH ( dimethylamine ) ; (C2H5)2 NH ( diethylamine).

3) Tertiary Amine :
They are the trialkyl derivatives of ammonia obtained by replacing all the 3 H-atoms
by 3 alkyl groups. They are represented as R3N.
Functional group : ─ N (3o nitrogen)
e.g. (CH3)3N ( trimethylamine ) ; (C2H5)3N ( triethylamine )

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N.B. i) Thus common general formula of 10, 20 & 30 amines is CnH2n+3
ii) Secondary and tertiary amines are called simple amines when the alkyl groups
attached to nitrogen are same, while they are called mixed amines if the alkyl groups are
different.

NOMENCLATURE :
i) Comman Names are obtained by adding the word amine to the name of alkyl group. In
case of mixed 2o and 3o amines the names of alkyl groups are written in alphabetical
order.
e.g. 1° amine    alkylamine
2° amine  dialkylamine
3° amine   trialkylamine

ii) IUPAC Names :

(i) They are obtained from the name of parent alkane by replacing the last letter ─e with
─amine ( i.e. Alkane  Alkanamine).
(ii) The position of functional group is indicated by lowest possible number.
(iii) In case of mixed secondary and tertiary amines the larger alkyl group attached to
nitrogen is taken as parent alkane and the smaller alkyl groups are taken as substituents.
(iv) In such cases the position of smaller alkyl groups are indicated as N- alkyl or N,N -
dialkyl ( this is to show that the alkyl groups are attached to nitrogen and not to carbon ) .

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Diazonium Salts
These have the general formula, ArN2 X, where Ar is abbreviated for
the aryl group and X may be Cr–, Br–, HSO , NO , etc.

Stability
Primary aliphatic amines form highly unstable alkyl diazonium salts.
Primary aromatic amines form arene diazonium salts, which are
stable for a short time in solution at low temperature (0-5°C).
The stability of arene diazonium salt is due to the dispersal of the
positive charge over the benzene ring.

Resonating structures of benzene diazonium salt

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NOTE: Resonance stabilisation is not possible in diazonium salts
of aliphatic amines.
Method of Preparation
Benzene diazonium chloride is prepared by the reaction of aniline
with nitrous acid (which is produced by the reaction of NaNO2 and
HCl) at 273-278 K or 0-5°C.
C6H5NH2 + NaNO2 + 2HCl     C6H5N2Cl + NaCl + 2H2O
273  278 K

The conversion of primary aromatic amines into their diazonium salts

is called diazotisation. Due to its unstability, the diazonium salt is not
generally stored and is used immediately after its preparation.

Physical Properties
Benzene diazonium chloride is colourless and readily soluble in
water. Hence, physical properties of diazonium salts can be described
as follows:
(i) Diazonium salts are generally colourless, crystalline solids.
(ii) These are readily soluble in water and stable in cold water. They
react with water when warmed.
(iii) These are unstable and exploit in dry state, hence used in
solution state.
(iv) Their aqueous solutions are neutral to litmus and conduct
electricity due to the presence of ions.
(v) Benzene diazonium fluoroborate is water insoluble and stable at
room temperature.

Chemical Reactions
The chemical reactions of diazonium salts can be divided into two
categories:
Reactions Involving Displacement of Nitrogen

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Diazonium group being a very good leaving group, is substituted by
other groups such as Cl–, Br–, I–, CN– and OH– from the aromatic
ring. The nitrogen thus formed escapes from the reaction mixture as a
gas.

Reactions Involving Retention of Diazo Group

(Coupling Reactions)
Benzene diazonium chloride reacts with phenol in which phenol
molecule at its para-position is coupled with diazonium salt to give
the product p-hydroxy azobenzene, hence the reaction is known as
coupling reaction. The azo products obtained have both the aromatic
rings joined through the —N = N— bonds, are coloured and used as
dyes.
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Similarly, the reaction of diazonium salt with aniline gives p-

aminoazobenzene (yellow dye).

Importance of Diazonium Salts in the Synthesis

of Aromatic Compounds
These are important in the synthesis of aromatic compounds due to
the following facts:
(i) These are very good intermediates for the introduction of —F, —
Cl, —OH, —CN, —NO2, etc., into the aromatic ring.

(ii) Similarly, aryl fluorides and iodides cannot be prepared by the

direct halogenation. Cyano group cannot be introduced by
nucleophilic substitution reaction but cyanobenzene can be prepared
from diazonium salts.

(iii) Thus, replacement of diazo group by the other group is helpful in

preparing those aromatic compounds which cannot be prepared by
the direct substitution in benzene.

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1. Write IUPAC name of the following compound: (CH3CH2)2NCH3
2. Write the structure of 2,4-dinitrochlorobenzene.
3. Write the JUPAC name of the following compound:
CH3NHCH(CH3)2
4. Write IUPAC name of the following compound:
(CH3)2N―CH2CH3
5. Write the IUPAC name of the given compound:

6. Write the structure of N-methylethanamine.

7. Write the structure of 2-aminotoluene.
8. Give the IUPAC name of H2N―CH2―CH2―CH=CH2
9. Write the structure for N, N-ethylmethylamine.
10. Give IUPAC names of the following compounds:

11. Write the chemical equation involved in the following reaction :

Hofmann bromamide degradation reaction
12. How do you convert the following: Ethanenitrile to ethanamine
B. State and illustrate the following : Gabriel synthesis
14. Write chemical equations for the following conversion : Benzyl
chloride to 2-phenylethanamine.
15. Why cannot primary aromatic amines be prepared by Gabriel
phthalimide synthesis?
16. Write the chemical reaction to illustrate the following:
Ammonolysis
17. How will you convert the following:
(i) Nitrobenzene into aniline
(ii) Ethanoic acid into methanamine

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18. How are the following conversions carried out?
(i) CH3CH2Cl to CH3CH2CH2NH2
(ii) Benzene to aniline.
19. Illustrate the following reactions giving a chemical equation in
each case:
(i) Gabriel phthalimide synthesis
(ii) Hofmann's bromamide reaction.
20. How would you achieve the following conversions :
(i) Nitrobenzene to aniline.
(ii) An alkyl halide to a quaternary ammonium salt
Write the chemical equation with reaction conditions in each case.
21. Give reasons for the following :
Primary amines have higher boiling point than tertiary amines.
22. Arrange the following in the increasing order of their boiling
point ;
C2H5NH2, C2H5OH, (CH3)3N
23. Account for the following : Primary amines (R―NH2) have
higher boiling point than tertiary amines (R3N).
24. Out of CH3NH2 and (CH3)3N, which one has higher boiling point'
25. Account for the following : Ethylamine is soluble in water
whereas aniline is not.
26. Account for the following : Nitro compounds have higher boiling
points than the hydrocarbons having almost the same molecular
mass.
27. State reasons for the following :
(i) Ethylamine is soluble in water whereas aniline is not soluble in
water.
(ii) Primary amines have higher boiling points than tertiary amines.
28. Give a simple chemical test to distinguish between the following
pair of compounds :
(CH3)2NH and (CH3)3N
29. Arrange the following in increasing order of basic strength :

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Aniline, p-nitroaniline, and p-toluidine
30. Arrange the following compounds in increasing order of
solubility in water:
C6H3NH2, ( C2H5)2NH, C2H5NH2
31. How will you convert the following : Aniline into N-
phenylethanamide (Write the chemical equations involved.)
32. Arrange the following in increasing order of basic strength :
C6H5NH2, C6H5NHCH3, C6H5CH2NH2
33. Arrange the following in increasing order of basic strength :
C6H5NH2, C6H3NHCH3, C6H5N(CH3)2
34. Which of the two is more basic and why? CH3NH2 or NH3
35. Which of the two is more basic and why?

36. Which of the two is more basic and why?

37. Arrange the following in increasing order of their basic strength

in aqueous solution :
CH3NH2, (CH3)3N, (CH3)2NH
38. Arrange the following in the decreasing order of their basic
strength in aqueous solutions :
CH3NH2, (CH3)2NH, (CH3)3N and NH3
39. Describe the following giving the relevant chemical equation :
Carbylamine reaction
40. Complete the following reaction equation :
C6H5NH2 + Br2(aq) →
41. Rearrange the following in an increasing orderof their basic
strengths :
C6H5NH2, C6H5N(CH3)2 , (C6H5)2NH and CH3NH2

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42. State reasons for the following : pKb value for aniline is more
than that for ethylamine.
43. How will you differentiate between aniline and ethylamine?
44. Why is an alkylamine more basic than ammonia?
45. How will you bring about the following conversion : Ethanamine
to ethanoic acid
46. Assign reason for the following : The pKb of aniline is higher
than that of methylamine.
47. Why do amines act as nucleophiles?
48. Account for the following : Amines are basic substances while
amides are neutral.
49. Give reasons for the following :
(i) Aniline does not undergo Friedel-Crafts reaction.
(ii) (CH3)2NH is more basic than (CH3)3N in an aqueous solution.
50. Arrange the following in increasing order of their basic strength :
(i) C6H5-NH2, C6H5-CH2-NH2, C6H5-NH-CH3
(ii)

51. How do you convert the following:

(i) C6H5CONH2 to C6H5NH2
(ii) Aniline to phenol
52. Illustrate the following reactions giving suitable example in each
case :
(i) Ammonolysis
(ii) Acetylation of amines
53. Give the structures of A, Band C in the following reactions:

(i) C6H5NO2 ⎯⎯⎯⎯ A ⎯⎯⎯⎯⎯⎯⎯ B ⎯ C

/ ∆
(ii) CH3CN ⎯⎯⎯⎯ A ⎯ B ⎯⎯⎯⎯⎯ C
54. Account for the following:
(i) Aniline does not give Friedel-Crafts reaction.
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(ii) pKb of methylamine is less than that of aniline.
55. (i) Arrange the following compounds in an increasing order of
bask strength :
C6H5NH2, C6H5N(CH3) 2, (C2H5) 2NH and CH3NH2
(ii) Arrange the following compounds in a decreasing order of pKb
values :
C2H5NH2, C6H5NHCH3), (C2H5)2NH and C6H5NH2
56. Complete the following reactions:
(i) CH3CH2NH2 + CHCl3 +alc. KOH →
(ii)

57. Write the main products of the following reactions:

(i)

(ii)

58. Give chemical tests to distinguish between the following pairs of

compounds :
(i) Aniline and ethylamine
(ii) Ethylarnine and dimethylamine
59. Give reasons : (i) Aniline is a weaker base than cyclohexyl
amine.
(ii) It is difficult to prepare pure arnines by ammonolysis of alkyl
halides.
60. Give reasons :
(i) Electrophilic substitution in aromatic amines takes place more
readily than benzfne.
(ii) CH3CONH2 is weaker base than CH3CH3NH2.
61. How would you account for the following :

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(i) Aniline is a weaker base than cydohexylamine.
(ii) Methylamine in aqueous medium gives reddish-brown precipitate
with FeCl3.
62. Give the chemical tests to distinguish between the following pairs
of compounds :
(i) Ethylamine and aniline
(ii) Aniline and benzylamine
63. Give the chemical tests to distinguish between the following pairs
of compounds :
(i) Methylamine and dimethylamine
(ii) Aniline and N-methylaniline
64. Write one chemical reaction each to illustrate the following:
(i) Carbylamine reaction
(ii) Acetylation reaction
65. Account for the following :
(i) pK, of aniline is more than that of methylamine.
(ii) Aniline does not undergo Friedel-Crafts reaction.
66. Describe a chemical test each to distinguish between the
following :
(i) Ethylamine and aniline
(ii) Methylamine and dimethylamine
67. Assign reason for the following:
(i) Amines are less acidic than alcohols of comparable molecular
masses.
(ii) Aliphatic amines are stronger bases than aromatic amines.
68. (i) Arrange the following in an increasing order of basic strength
in water:
C6H5NH2, (C2H5)2NH, (C2H5)3N and NH3.
(ii) Arrange the following in increasing order or basic strength in gas
phase :
C2H5NH2, (C2H5)2NH, (C2H5)3N and CH3NH2.
69. Account for the following :

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(i) Aniline does not undergo Friedel-Crafts reaction.
(H) Aliphatic amines are stronger bases than aromatic amines.
70. Give one chemical test each to distinguish between the following
pairs of compounds :
(i) Ethylamine and aniline
(ii) Aniline and N-methylaniline
71. Give reasons :
(i) Acetylation of aniline reduces its activation effect.
(ii) CH3NH2 is more basic than C6H5NH2
(iii) Although −NH2 is olp directing group, yet aniline on nitration
gives a significant amount of m-nitroaniline.
72. Write the structures of A, B and C in the following:
∆
(i) C6H5NO2 ⎯⎯⎯⎯ A ⎯⎯⎯⎯⎯⎯⎯ B ⎯
273 𝐾
(ii) CH3Cl ⎯ A ⎯⎯⎯ B ⎯⎯ C
273 𝐾
76. 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.
77. Give the structures of A, B and C in the following reactions:
(i) CH3Br ⎯ A ⎯⎯⎯ B ⎯⎯ C
273𝐾
(ii) CH3COOH ⎯ A ⎯⎯⎯⎯⎯ B ⎯⎯⎯⎯⎯⎯⎯⎯ C
∆
78. Give the structures of products A, B and C in the following
reactions :
(i) CH3CH2Br ⎯ A ⎯⎯⎯ B ⎯⎯ C
0 𝐶
(ii) CH3COOH ⎯ A ⎯⎯⎯⎯⎯ B ⎯⎯⎯⎯⎯⎯⎯⎯ C
∆
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79. Account for the fol1owing observations :
(i) pKb for aniline is more than that for methylamine.
(ii) Methylamine solution in water reacts with ferric chloride solution
to give a precipitate of ferric hydroxide.
(iii) Aniline does not undergo Friedel-Crafts reaction.
80. Complete the following reaction equation :
C6H5N2Cl + H3PO2 + H2O →
81. The conversion of primary aromatic amines into diazonium salts
is known as_________________.
82. Complete the following reactions:
C6H5𝑁 Cl− ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
𝐻 𝑂
83. State and illustrate the following : Coupling reaction
84. How is the following conversion carried out : Aniline to p-
hydroxyazobenzene.
85. How will you bring about the following conversion :
Nitrobenzene to phenol
86. How will you bring about the following conversion : Aniline to
chlorobenzene
Write the chemical equation involved.
87. How will you bring about the following conversion :Aniline to
benzonitrile.
88. Write a chemical reaction in which the iodide ion replaces the
diazonium group in a diazonium salt.
89. How would you achieve the following conversion : Aniline to
benzonitrile.
Write the chemical equation conditions in each case.
90. Write chemical equations for the following conversions :
(i) Nitrobenzene to benzoic acid.
(ii) Aniline to benzyl alcohoL
91. Illustrate the following with an example of reaction in each case :
(i) Sandmeyer's reaction

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(ii) Coupling reaction
92. Write the structures of compounds A, B and C in the following
reactions :
(i) CH3COOH ⎯ A ⎯⎯⎯⎯⎯ B ⎯⎯⎯⎯⎯⎯⎯⎯ C
∆
/ / /
(ii) C6H5𝑁 𝐵𝐹 ⎯⎯⎯⎯⎯⎯ A ⎯⎯⎯ B ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ C
∆
93. Give the structure of A, Band C in the following reactions:
/
(i) C6H5𝑁 Cl− ⎯⎯ A ⎯⎯⎯⎯ B ⎯ C
∆
/
∆
(ii) C6H5NO2 ⎯⎯⎯⎯ A ⎯⎯⎯⎯⎯⎯⎯ B ⎯⎯⎯⎯ C
273 𝐾
94. An aromatic compound 'A’ of molecular formula C7H7ON
undergoes a series of reactions as shown below. Write the structures
of A, B, C, D and E in the following reactions:

95. (i) Write the structures of main products when benzenediazonium

chloride C6H5𝑁 Cl− reacts with the following reagents :
(a) HBF4/∆ (b) Cu/HBr
(ii) Write the structures of A, B and C in the following reactions :
/
∆
(a) C6H5NO2 ⎯⎯⎯⎯ A ⎯⎯⎯⎯⎯⎯⎯ B ⎯⎯⎯⎯ C
273 𝐾
(b) (ii) CH3Cl ⎯ A ⎯⎯⎯ B ⎯⎯ C
273 𝐾

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