Amines 240108 175230

230 CBSE Champion Chemistry Class 12
CHAPTER
9 Amines
TOPICS
9.1 Structure of Amines 9.5 Physical Properties 9.8 Physical Properties
9.2 Classification 9.6 Chemical Reactions 9.9 Chemical Reactions
9.3 Nomenclature 9.7 Method of Preparation of 9.10 Importance of Diazonium
9.4 Preparation of Amines Diazonium Salts Salts in Synthesis of Aromatic
Compounds
Analysis of Last 10 Years’ CBSE Board Questions (2023-2014)
24 MCQ
VSA
SA I
20
SA II
Number of questions
LA
16
12
0
9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 9.10
Topics
Topic 9.6 is highly scoring topic.

Maximum total weightage is of Topic 9.6 Chemical Reactions.
Maximum MCQ, VSA, SA I, SA II type questions were asked from Topic 9.6 Chemical Reactions.
QUICK RECAP
AMINES
Amines : These are alkyl or aryl derivatives of ammonia and are obtained by replacing one, two or three hydrogen
atoms by alkyl/aryl groups.
Nomenclature : In common system, an aliphatic amine is named by prefixing alkyl group to amine, i.e., alkylamine. In
IUPAC system, amines are named as alkanamines. In secondary and tertiary amines, when two or more groups are the
same, the prefix di or tri is added before the name of alkyl group.
Structure : Nitrogen orbitals in amines are sp3‑hybridised and the geometry of amines is pyramidal. Due to the
presence of unshared pair of electrons, the angle C - N - E, (where E is C or H) is less than 109.5°.
sp3 - s sp3 – s
sp3 – sp3 s-bond
s-bond s-bond
s s R
N H N H N
R H s
R R R
R
3 3
3 3
sp – sp s-bond 3 3
sp – sp s-bond sp – sp s-bond
Orbital structure of 1°, 2° and 3° amines
Amines 231
Classification :
Amines
Aliphatic Aromatic
Primary (1°) Amines Secondary (2°) Amines Tertiary (3°) Amines

–NH2 group attached to NH group attached to N group attached to three alkyl groups (R3N)
one alkyl group (R — NH2) two alkyl groups (R2NH)
Simple Mixed Simple Mixed

Both alkyl groups Both alkyl groups All three alkyl Either all three are different or
are same (R2NH) are different groups are same two are same, one is different
(R′NHR) (R3N) (R′RR″N or RRR′N)
Preparation :
Reduction of nitro compounds : Gabriel phthalimide synthesis :
Sn/HCl or Fe/HCl
RNO2 or H /Pd or LiAlH /ether CO
2 4 (i) KOH (alc.)
NH
R–NH2 (ii) RX, D
Hofmann’s ammonolysis method :
NH3, 373 K (iii) H+ or OH–/H2O/D CO
RX NaOH
Mendius reduction :
H2/Ni or LiAlH4/ether Hofmann bromamide degradation :
R-CN or Na(Hg)/C2H5OH Br2
KOH, D
RCONH2
R–CH2NH2
Reduction of amides :
LiAlH4/ether
R-CONH2
or Na/C2H5OH
X Limitations of Gabriel phthalimide synthesis : − Aliphatic amines are stronger bases than ammonia
− It is used for the preparation of only 1° amines. due to +I effect of alkyl groups present in amines.
tert-Butylamine is a 1° amine, but cannot be − Aromatic amines are weaker bases than ammonia
prepared by this method. In this case, elimination due to –I effect of aryl group.
takes place. − Beside inductive effect, there are other effects
− Aromatic 1° amines cannot be prepared by this like steric effect, solvation effect, resonance effect
method because aryl halides do not undergo which affect the basic strength of amines.
nucleophilic substitution reaction with potassium − In gaseous phase, the order of basicity of amines is
phthalimide under mild conditions. 3° amine > 2° amine > 1° amine > NH3.
Physical properties : − In aqueous phase, despite inductive effect, solvation
effect and steric hindrance also play important roles.
X Lower amines are gases and liquids but higher
Thus, the order of basicity of amines is (C2H5)2NH
amines are solids.
> (C2H5)3N > C2H5NH2 > NH3 and (CH3)2NH >
X Primary and secondary amines have higher boiling CH3NH2 > (CH3)3N > NH3
points than alcohols and alkanes of almost the same − Aniline is a weaker base compared to ammonia. This
molar mass due to hydrogen bonding. is because the lone pair of electrons on N-atom of
Order of boiling points of isomeric amines: aniline is less available for protonation due to its
1° > 2° > 3° involvement in conjugation with the π-electrons of
X Primary and secondary amines are soluble in water the benzene ring.
due to hydrogen bonding between —NH2 and H2O NH2 NH2 NH2 NH2 NH2
molecules.
Chemical properties :
X Basic character of amines :

Further the presence of electron withdrawing
− Amines are basic in nature due to the presence of groups like -NO2, -CN, -X, etc., decreases the
lone pair of electrons on nitrogen atom. Larger the basicity while, the presence of electron donating
value of Kb or smaller the value of pKb, stronger is groups like -OCH3, -CH3, -NH2, etc., activates
the base. the benzene ring and also increases the basicity.
X Chemical reactions :
NaOH HCl (R′CO)2O
RNH2 RNH3+Cl– RNHCOR′
–R′COOH
R′X R′X R′X CHCl3/alc. KOH
X–RNR3′ RNR2′ –HX RNHR′ –HX RNC (Carbylamine reaction)
–KCl, –H2O
Quaternary RNH2 (Unpleasent smell)
salt
C6H5COCl HNO2
RNHCOC6H5 –HCl ROH + N2↑ + H2O
R′COCl C6H5SO2Cl
RNHCOR′ –HCl
RNHSO2C6H5 (Hinsberg’s test)
–HCl
(Soluble in NaOH)
X Identification of primary, secondary and tertiary amines :
Test Primary amine Secondary amine Tertiary amine

Reaction with nitrous Gives alcohol with Gives oily nitrosoamine Forms nitrite in cold which is
acid effervescence of N2 gas. which gives Liebermann’s soluble in water and on heating
nitrosoamine test. gives nitrosoamine.
Reaction with benzene Gives N-alkylbenzene- Gives N,N-dialkylbenzene No reaction
sulphonyl chloride sulphonamide which is sulphonamide which is
(Hinsberg’s reagent) soluble in alkali. insoluble in alkali.
Carbylamine test : Forms carbylamine or No reaction No reaction
Reaction with chloroform isocyanide (RNC) with
and alcoholic KOH characteristic unpleasant
odour.
X Electrophilic substitution reactions of arylamines : reactions. -NH2 group is ortho- and para-directing
Aniline undergoes electrophilic substitution and a powerful activating group.
NH2 NH2 NH2

Br Br conc. H2SO4
3Br2
H2O D
Br SO3H
2, 4, 6, Tribromoaniline
Sulphanilic acid
NH2
(i) CH3COCl
or (CH3CO)2O/pyridine N ≡ NCl–
(ii) Br2, CH3COOH
NaNO2 + conc. HCl
(iii) H2O/H+
Br 273-278 K
(Major) Benzene diazonium salt
p-Bromoaniline
NH2 NH2 NH2
NH2 NO2
conc. H2SO4
(i) (CH3CO)2O + +
or CH3COCl/pyridine conc. HNO3
NO2
(ii) HNO3 + H2SO4
NO2
(iii) H2O/H+
NO2 (51%) (47%) (2%)
(Major)
p-Nitroaniline
DIAZONIUM SALTS C6H5NH2 + NaNO2 + 2HCl

0 –5° C
Arenediazonium salts : They have the general formula C6H5N2+Cl–+ NaCl + 2H2O
ArN 2 X , Ar stands for the aryl (-C6H5) group and X is
+ – –
– – – – – Stability : Arenediazonium salts are more stable (for
Cl , Br , NO3 , HSO4 , BF4 etc.
short time) than alkanediazonium salts due to dispersal
Nomenclature : They are named by suffixing diazonium to
of positive charge over the benzene ring.
the name of parent hydrocarbon followed by anion.
Preparation : Benzenediazonium chloride is prepared Physical properties : These are generally colourless,
by the reaction of aniline with nitrous acid (sodium crystalline solids, which are soluble in water. They are
nitrite and hydrochloric acid) at 0-5 °C. unstable and explode in dry state.
Amines 233
Chemical properties :
X Reactions involving displacement of nitrogen (diazo group) :
H3PO2/H2O
ArH
KI
ArI
CH3CH2OH D
ArH ArF
D HBF4 (Balz-Schiemann reaction)
CuCl/HCl ArN2+BF4–
ArCl or NaNO2/Cu
or CuBr/HBr ArN2+X– ArNO2
Sandmeyer D
reaction ArBr or H2O
or CuCN/KCN >278 K
ArOH
ArCN
ArCl Cu/HCl C6H6
or or ArC6H5 (Gomberg reaction)
Cu/HBr NaOH, D
Gattermann ArBr (Biphenyl)
reaction or
or
ArCN Cu/KCN
X Reactions involving retention of diazo group (coupling reactions) :
C6H5NH2/H+ C6H5OH/OH–
ArN=NC6H4NH2 ArN2+X– ArN=NC6H4OH
pH = 4-5, 0-5°C pH = 9-10, 0-5°C
p-Aminoazobenzene p-Hydroxyazobenzene
(Yellow dye) (Orange dye)
ORGANIC COMPOUNDS CONTAINING NITROGEN
Amines Aniline Diazonium Salts
N → sp3, classified as 1°, 2°, 3° depending upon the no. Preparation Preparation
of H atoms replaced by alkyl or aryl groups in NH3. Sn/HCl 0 –5°C
C6H5NH2 + NaNO2 + 2HCl
IUPAC name : alkanamines or arylamines. 5NO2 or, Fe/HCl
C6H5N2+ Cl– + NaCl + 2H2O
Preparation
Chemical Properties
C6H5N2+Cl–
CuCl/HCl
C6H5Cl

Preparation [Sandmeyer reaction]
Cu/HCl
C6H5Cl
[Gattermann reaction]
C6H6
C6H5—C6H5
R NaOH,
[Gomberg reaction]
Phenol
C6H5N NC6H4OH
[Coupling reaction]
H2O/H+
Preparation C6H5OH
Chemical Properties C2H5OH Isocyanides HBF4/
RX + AgCN
C6H5F
POCl3
RNC
RNHCHO Cyanides
Pyridine
Chemical Properties
Chemical Properties Preparation
Separation of 1°, 2° and 3° amines 100 °C
Hofmann's method H2O/H+ RX + KCN
Diethyloxalate +1° + 2°+ 3° amines
RNH2
P2O5 RCN
+4[H] RMgX R — CONH2
Oxamide, solid (1° amine) RNC RNHCH3
Na/C2H5OH
Oxamic ester, liquid (2° amine)
No reaction (3° amine) 250°C
RCN
BRAIN MAP
Amines 235
9.2 Classification 10. CH3CONH2 on reaction with NaOH and Br2 in

alcoholic medium gives
VSA (1 mark) (a) CH3CH2NH2 (b) CH3CH2Br
(c) CH3NH2 (d) CH3COONa
1. Choose the primary amine from the following
compounds : (2020) U
(C2H5)2CHNH2, (C2H5)2NH, (CH3)3N
VSA (1 mark)
(Term II, 2021-22C) U
11. Ammonolysis of alkyl halides is not a good method
9.3 Nomenclature to prepare pure primary amines. Give reason
(1/5, 2020) Ap
VSA (1 mark)
12. Write the structures of A and B in the following
2. Write IUPAC name of the following compound :
reaction :
(CH3CH2)2NCH3 (Delhi 2017) U NH3 NaOBr
CH3COOH A B (1/5, 2020)
3. Write the structure of 2, 4-dinitrochlorobenzene. D
(Delhi 2017) 13. Carry out the following conversion :
4. Write the IUPAC name of the following compound : Benzoic acid to aniline. (1/5, AI 2019)
CH3NHCH(CH3)2 (Delhi 2017) 14. Write the chemical equation involved in the
5. Write IUPAC name of the following compound: following reaction :
(CH3)2N — CH2CH3 (Delhi 2017) Hoffmann bromamide degradation reaction
6. Write the IUPAC name of the given compound : (AI 2019, 1/5, 2018, 1/2, AI 2016)
NH2 15. How do you convert the following :
Br Br Ethanenitrile to ethanamine (1/3, AI 2015)
SA I (2 marks)
Br (Delhi 2016) U 16. Complete the following :

KCN LiAlH4
CH3Br A B (Term II, 2021-22C)
9.4 Preparation of Amines
17. How will you convert the following :
MCQ
(i) Nitrobenzene into aniline
7. CH3CONH2 on reaction with NaOH and Br2 in (ii) Ethanoic acid into methanamine
alcoholic medium gives (2/3, Delhi 2014)
(a) CH3COONa (b) CH3NH2
(c) CH3CH2Br (d) CH3CH2NH2 SA II (3 marks)
(2023)
18. (a) Write the IUPAC name for the following organic
8. Assertion : Ammonolysis of alkyl halides is not a compound : (CH3CH2)2NCH3
suitable method for the preparation of pure primary
(b) Write the equations for the following :
amines.
(i) Gabriel phthalimide synthesis
Reason : Ammonolysis of alkyl halides yields mainly
secondary amines. (ii) Hoffmann bromamide degradation
(a) Both Assertion (A) and Reason (R) are true (Term II, 2021-22) R
and Reason is the correct explanation of the
assertion. 19. An aromatic compound ‘A’ (C7H6O2) on reaction
(b) Both Assertion (A) and Reason (R) are true, but with aqueous ammonia and heating forms compound
Reason is not the correct explanation of the ‘B’. ‘B’ on heating with Br2 and alcoholic potash forms
assertion. a compound ‘C’ of molecular formula C6H7N. Write
(c) Assertion (A) is true, but Reason (R) is false. the reactions involved and identify ‘A’, ‘B’, ‘C’.
(d) Assertion (A) is false, but Reason (R) is true. (Term II, 2021-22)
(2023) OR
9. Which of the following would not be a good choice An aromatic compound ‘A’ on treatment with
for reducing nitrobenzene to aniline? aqueous ammonia and heating forms compound
(a) LiAlH4 (b) H2/Ni ‘B’ which on heating with Br2 and KOH forms a
(c) Fe and HCl (d) Sn and HCl (2023) compound ‘C’ of molecular formula C6H7N. Write
the structures and IUPAC names of compounds

(c) NH2 (d) (CH3)3N (2023)
A, B and C. (Delhi 2015C)
20. How will you carry out the following conversions : 29. Assertion (A) : NH2 group is o- and p-directing in
(i) Nitrobenzene to aniline electrophilic substitution reactions.
(ii) Ethanamide to methanamine Reason (R) : Aniline cannot undergo Friedel-Crafts
(iii) Ethanenitrile to ethanamine reaction.
(Term II, 2021-22) Ap (a) Both Assertion (A) and Reason (R) are true and
Reason (R) is the correct explanation of the
9.5 Physical Properties Assertion (A).
(b) Both Assertion (A) and Reason (R) are true, but
VSA (1 mark)
Reason (R) is not the correct explanation of the
21. Out of CH3NH2 and CH3OH, which has higher Assertion (A).
boiling point?(2020) (c) Assertion (A) is true, but Reason (R) is false.
22. Arrange the following compounds in decreasing (d) Assertion (A) is false, but Reason (R) is true.
order of their boiling points : (2023)
Butanol, Butanamine, Butane (1/3, 2020) Ev 30. Assertion (A) : Acetylation of aniline gives a
23. Propanamine and N, N-dimethylmethanamine contain monosubstituted product.
the same number of carbon atoms, even though Reason (R) : Activating effect of NHCOCH3 group
propanamine has higher boiling point than
is more than that of amino group.
N, N-dimethylmethanamine. Why? (AI 2019)
(a) Both Assertion (A) and Reason (R) are true and
OR Reason (R) is the correct explanation of the
Give reasons for the following : Assertion (A).
Primary amines have higher boiling point than (b) Both Assertion (A) and Reason (R) are true, but
tertiary amines. (1/3, AI 2016, 2014)
Reason (R) is not the correct explanation of the
OR Assertion (A).
Out of CH3NH2 and (CH3)3N, which one has higher (c) Assertion (A) is true, but Reason (R) is false.
boiling point? (Delhi 2014C) (d) Assertion (A) is false, but Reason (R) is true.
24. Arrange the following in the increasing order of (2023)
their boiling points :
31. Assertion (A) : (C2H5)2NH is more basic than
C2H5NH2, C2H5OH, (CH3)3N
(C2H5)3N in aqueous solution.
(2019, 1/5, Delhi 2015)
Reason (R) : In (C2H5)2NH, there is more steric
25. Arrange the following compounds in increasing hindrance and +I effect than (C2H5)3N.
order of solubility in water :
(a) Both Assertion (A) and Reason (R) are true and
C6H5NH2, (C2H5)2NH, C2H5NH2
Reason (R) is the correct explanation of the
(Delhi 2014) Cr Assertion (A).
26. Account for the following : (b) Both Assertion (A) and Reason (R) are true, but
Ethylamine is soluble in water whereas aniline Reason (R) is not the correct explanation of the
is not. (1/3, Delhi 2014C) Cr Assertion (A).
(c) Assertion (A) is true, but Reason (R) is false.
SA I (2 marks) (d) Assertion (A) is false, but Reason (R) is true.
27. Arrange the following compounds as directed : (2023)
(i) In increasing order of solubility in water : 32. In the reaction
(CH3)2NH, CH3NH2, C6H5NH2
C6H5NH2 + CHCl3 + 3KOH → A + 3B + 3C
(ii) In increasing order of boiling point :
(C2H5)2NH, (C2H5)3N, C2H5NH2 (2/3, 2020) The product A is
(a) C6H5NC (b) C6H5CN
9.6 Chemical Reactions (Amines) (c) C6H5Cl (d) C6H5NHCH3
(2023)
Basicity of Amines
33. Out of the following, the strongest base in aqueous
MCQ solution is
(a) methylamine (b) dimethylamine
28. Which of the following is least basic?
(a) (CH3)2NH (b) NH3 (c) trimethylamine (d) aniline.(2020) An
Amines 237
VSA (1 mark) (iii) In decreasing order of their pKb values :

C6H5NH2, C2H5NH2, NH3 (Term II, 2021-22)
34. Arrange the following compounds as directed :
46. (i) Arrange the following compounds in an
In decreasing order of basic strength in aqueous increasing order of basic strength :
solution : C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and
(CH3)3N, (CH3)2NH, CH3NH2 (1/3, 2020) Cr CH3NH2
(ii) Arrange the following compounds in a
35. Arrange the following in decreasing order of basic
decreasing order of pKb values :
character : C2H5NH2, C6H5NHCH3, (C2H5)2NH and
C6H5NH2, (CH3)3N, C2H5NH2 (2019) C6H5NH2 (Delhi 2014C)
36. Arrange the following in increasing order of base
Chemical Properties of Amines
strength in gas phase.
(C2H5)3N, C2H5NH2, (C2H5)2NH (Delhi 2019)
MCQ
37. Give reason :
47. Read the passage given below and answer the
(CH3)2NH is more basic than (CH3)3N in an aqueous questions (i to iv) :
solution. (1/5, 2018) Amines can be considered as derivatives of ammonia
38. Arrange the following in the decreasing order of and are usually formed from nitriles, nitro, halides,
their basic strength in aqueous solutions : amides, etc. They show hydrogen bonding which
influences their physical properties. In aromatic
CH3NH2, (CH3)2NH, (CH3)3N and NH3 (1/3, 2018C)
amines, electron releasing and withdrawing groups
39. Arrange the following in increasing order of basic respectively increase and decrease their basic
strength : character.
Aniline, p-nitroaniline and p-toluidine Hinsberg test is used for the identification and
(1/2, AI 2015, AI 2015C) distinction between primary, secondary and tertiary
amines.
40. Arrange the following in increasing order of basic
The following questions are multiple choice questions:
strength : (i) Ethyl amine can be prepared by the action of
C6H5NH2, C6H5NHCH3, C6H5CH2NH2 LiAlH4 on
(1/2, AI 2015, Delhi 2014) (a) CH3NO2 (b) CH3-CN
41. Arrange the following in increasing order of (c) CH3-NC (d) CH3-CH2-CONH2
basic strength : (ii) Which of the following reagents is used for the
Hinsberg test of amines ?
C6H5NH2, C6H5NHCH3, C6H5N(CH3)2 (Delhi 2014)
(a) C6H5COCl (b) CH3COCl
42. Which of the two is more basic and why? (c) C6H5-SO3H (d) C6H5-SO2Cl
NH2 (iii) Out of the following, the strongest base in
aqueous solution is
CH3NH2 or (Foreign 2014) U (a) (CH3)2NH (b) (CH3)3N
(c) CH3-NH2 (d) C6H5-NH2
(iv) The reaction of ammonia with a large excess of
SA I (2 marks)
CH3-Cl will give mainly
43. Explain briefly (a) C2H6 (b) (CH3)2NH
(a) Carbylamine reaction (c) (CH3)4N+Cl– (d) CH3-NH2
(b) Gabriel phthalimide synthesis(2023) OR
Among the following amines, which one is expected
44. (i) Draw the zwitter ion structure for sulphanilic to have the lowest boiling point?
acid. (a) C2H5-NH2 (b) (C2H5)3N
(ii) How can the activating effect of NH2 group in (c) (C2H5)2NH (d) CH3-NH2 (2021C)
aniline be controlled?(2023)
48. CH2 NH2 on heating with CHCl3 and
45. Arrange the following compounds as directed:
(any two) alcoholic KOH gives foul smell of
(i) In decreasing order of basic strength in aqueous
(a) CH2OH (b) CH2NC
solution :
C2H5NH2, (C2H5)2NH, (C2H5)3N
(c) CH2CN (d) CH2Cl
(ii) In increasing order of solubility in water :
(C2H5)2NH, C2H5NH2, C6H5NH2 (2020)
VSA (1 mark) 61. Account for the following :

(a) Gabriel phthalimide synthesis is not preferred
49. Write an isomer of C3H9N which gives foul smell
for preparing aromatic primary amines.
of isocyanide when treated with chloroform and
(b) On reaction with benzene sulphonyl chloride,
ethanolic NaOH. (2020)
primary amine yields product soluble in alkali
50. Give the structures of A and B in the following whereas secondary amine yields product
sequence of reactions :
insoluble in alkali. (2019) U
NaNO2 +HCl
Fe/HCl
C6H5NO2 → A  →B (2/3, 2020)
0 −5°C 62. Write structures of compounds A and B in each of
51. Carry out the following conversion : the following reactions :
Bromomethane to ethanol. (1/5, AI 2019) Cr NH2
52. Describe the following by giving the relevant conc. H2SO4 Heat,453–473K
(a) A B
chemical equation :
Carbylamine reaction (1/3, 2018C) R CONH2
53. Give a simple chemical test to distinguish between Br2/NaOH (CH3CO)2O/pyridine
the following pair of compounds : (b) A B
(CH3)2NH and (CH3)3N (1/5, Delhi 2015) (2019 C)
54. How will you convert the following : 63. Write the structures of the main products of the
Aniline into N-phenylethanamide following reactions :
(Write the chemical equations involved.) NH2
(1/3, Delhi 2014) (CH3CO)2O
55. Which of the two is more basic and why? (i) Pyridine
CH3NH2 or NH3 (Foreign 2014) U (CH3)2NH
(ii) SO2Cl (2/5, 2018) An
56. Which of the two is more basic and why?
NH2 NH2 64. (a)
Give a simple chemical test to distinguish
between aniline and N, N-dimethylaniline.
and (Foreign 2014) U (b) Arrange the following in the increasing order of
their pKb values :
CH3 C6H5NH2, C2H5NH2, C6H5NHCH3 (2/5, 2018)
SA I (2 marks) 65. Give reasons for the following :
57. (a) Write the IUPAC name for the following organic (i) Aniline does not undergo Friedel–Crafts reaction.
compounds: (ii) (CH3)2NH is more basic than (CH3)3N in an
CH3 N CH2CH3 aqueous solution. (2/3, AI 2016, 2014)
66. Illustrate the following reactions giving suitable
example in each case :
(i) Ammonolysis
(b) Complete the following: (ii) Acetylation of amines (2/5, Foreign 2015)
Sn/HCl Br2/H2O
C6H5NO2 A B (2023) 67. Account for the following :
(i) Aniline does not give Friedel–Crafts reaction.
58. How will you distinguish between the following
(ii) pKb of methylamine is less than that of aniline.
pairs of compounds :
(i) Aniline and ethanamine (2/3, Delhi 2014C) U
(ii) Aniline and N-methylaniline (2/3, 2020) Cr
SA II (3 marks)
59. Distinguish between the following :
68. Illustrate the following reactions giving suitable
(i) CH3CH2NH2 and (CH3CH2)2NH
example in each case:
(ii) Aniline and CH3NH2 (2/5, 2020) (i) Gabriel phthalimide synthesis.
60. Give reasons : (ii) Carbylamine reaction.
(i) Although - NH2 group is o/p directing in (iii) Hoffmann bromamide degradation reaction.
electrophilic substitution reactions, yet aniline, (Term II, 2021-22)
on nitration gives good yield of m-nitroaniline. 69. Give reasons :
(ii) (CH3)2NH is more basic than (CH3)3N in an (i)
Ammonolysis of alkyl halides is not a good
aqueous solution. (2/5, 2020) method to prepare pure primary amines.
Amines 239
(ii) Aniline does not give Friedel-Crafts reaction. (b) Arrange the following in the increasing order of
(iii) Although —NH2 group is o/p directing in their pKb values :
electrophilic substitution reactions, yet aniline C6H5NH2, NH3, C2H5NH2, (C2H5)2NH (3/5, 2020)
on nitration gives good yield of m-nitroaniline. 78. Give reasons :
(Term II, 2021-22) Ap (i) Aniline does not undergo Friedel-Crafts’
70. Write equations involved in the following reactions : reaction.
(i) Ethanamine reacts with acetyl chloride. (ii) Aromatic primary amines cannot be prepared
(ii) Aniline reacts with bromine water at room by Gabriel’s phthalimide synthesis.
temperature. (iii)
Aliphatic amines are stronger bases than
(iii) Aniline reacts with chloroform and ethanolic ammonia. (2020) U
potassium hydroxide. (Term II, 2021-22) 79. Describe a method for the identification of
71. Account for the following : C2H5NH2, (C2H5)2NH and (C2H5)3N. Also write the
(i) pKb of aniline is more than that of methylamine. chemical equations for the reactions involved.
(ii) Aniline does not undergo Friedel-Crafts reaction. (2020C)
(iii) Primary amines have higher boiling points than 80. (a) Give one chemical test to distinguish between
tertiary amines. (Term II, 2021-22) Ap the compounds of the following pairs :
72. (i) Arrange the following compounds in the (i) CH3NH2 and (CH3)2NH
increasing order of their basic strength in (ii) Aniline and ethanamine
aqueous solution : CH3NH2, (CH3)3N, (CH3)2NH (b) Why aniline does not undergo Friedel–Crafts
(ii) What is Hinsberg’s reagent ? reaction? (AI 2019) Cr
(iii) What is the role of pyridine in the acylation 81. (a) Identify X and Y in the following :
reaction of amines ? (Term II, 2021-22) NH2
73. A compound ‘A’ on reduction with iron scrap and NaNO2 + HCl CuCN
hydrochloric acid gives compound ‘B’ with molecular X Y
0–5°C
formula C6H7N. Compound ‘B’ on reaction with
CHCl3 and alcoholic KOH produces an obnoxious (b) Amino group is o, p-directing for aromatic
smell of carbylamine due to the formation of electrophilic substitution reactions. Why does
‘C’. Identify ‘A’, ‘B’ and ‘C’ and write the chemical aniline on nitration give m-nitroaniline?
reactions involved. (Term II, 2021-22) Cr (2019C)
82. Give reasons :
74. Write reasons for the following : (i) Acetylation of aniline reduces its activation
(i) Ethylamine is soluble in water whereas aniline effect.
is insoluble. (ii) CH3NH2 is more basic than C6H5NH2.
(ii) Amino group is o- and p-directing in aromatic (iii) Although —NH2 is o/p directing group, yet
electrophilic substitution reactions, but aniline aniline on nitration gives a significant amount
on nitration gives a substantial amount of of m-nitroaniline. (Delhi 2017)
m-nitroaniline.
83. Write the structures of main products when aniline
(iii) Amines behave as nucleophiles. reacts with the following reagents :
(Term II, 2021-22) (i) Br2 water (ii) HCl
75. An organic compound (A) with molecular formula (iii) (CH3CO)2O/pyridine (3/5, Delhi 2015)
C3H7NO on heating with Br2 and KOH forms a 84. Give the structures of products A, B and C in the
compound (B). Compound (B) on heating with following reactions :
CHCl3 and alcoholic KOH produces a foul smelling KCN LiAlH4 HNO2
compound (C) and on reacting with C6H5SO2Cl (i) CH3CH2Br A B C
0°C
forms a compound (D) which is soluble in alkali.
NH3 NaOH + Br2 CHCl3 +
Write the structures of (A), (B), (C) and (D). (ii) CH3COOH A B alc. NaOH C
D
(Term II, 2021-22) Cr
(Delhi 2014) An
76. Account for the following :
(a) Aniline is a weaker base compared to ethanamine. 9.9
Chemical Reactions
(b) Aniline does not undergo Friedel-Crafts reaction.
(c) Only aliphatic primary amines can be prepared
(Diazonium salts)
by Gabriel Phthalimide synthesis. (2020) MCQ
77. (a) Write the chemical reaction of methyl amine 85. In cold conditions, aniline is diazotized and then
with benzoyl chloride and write the IUPAC treated with aniline again to give a coloured product.
name of the product obtained. The structure of the coloured product is
(a) (CH3)2-N NH SA II (3 marks)
95. (a)
Illustrate Sandmeyer’s reaction with an
(b) H2N N=N equation.
(b)
Explain why (CH3)2 NH is more basic than
(c) H2N NH (CH3)3N in aqueous solution. (2023)
96. Write the structures of main products when benzene
diazonium chloride reacts with the following reagents :
(d) HO N=N (2020C)
(i) CuCN (ii) CH3CH2OH
VSA (1 mark) (iii) KI (Delhi 2019) An
86. Write the structures of A and B in the following 97. Complete the following reactions :
reactions : CN
CuCN H2O/H+ H2/Ni
C6H6N+2Cl– A B (1/5, 2020) Ev (a)
87. Carry out the following conversion :
CH3
p-nitrotoluene to 2-bromobenzoic acid.
Br
(1/5, AI 2019) H3PO2 + H2O
(b)
88. Write the structure of the main product of the
following reaction :
N2+Cl–
N2+Cl– CH CH OH
CH2-NH2
3 2
(1/5, 2018) Ap
Ethanolic KOH
(c) + CHCl3
89. Complete the following reaction equation :
(2019)
C6H5N2Cl + H3PO2 + H2O
(Delhi 2015C) 98. How do you convert the following :
(a) N-phenylethanamide to p-bromoaniline
90. The conversion of primary aromatic amines into
(b) Benzenediazonium chloride to nitrobenzene
diazonium salts is known as __________. (AI 2014)
(c) Benzoic acid to aniline (2019)
SA I (2 marks)
99. Write the structures of compounds A, B and C in the
91. (i) Complete the reaction with the main product following reactions :
formed: NH /D Br2/KOH(aq)
N2+Cl– (a) CH3—COOH →
3
A → B
CHCl + alc. KOH
→
3
C
CH3CH2OH NaNO /Cu Fe/HCl
(b) C6H5N+2BF–4 →
D
2
A → B
CH3COCl/pyridine
C
(ii) Convert bromoethane to propanamine. (2023)
(AI 2017)
92. (a) Write the reaction involved in the following :
Diazotisation 100. Write the structures of A, B and C in the following :
(b) Give reason : Br2/aq. KOH
(i) C6H5-CONH2 A
Aromatic diazonium salts are more stable than
KI NaNO2 + HCl
aliphatic diazonium salts. (2/5, 2018) Ap C B 0-5°C
KCN LiAlH4
93. How do you convert the following : (ii) CH3-Cl A B
(i) C6H5CONH2 to C6H5NH2 CHCl3 + alc. KOH
C D
(ii) Aniline to phenol (2/3, AI 2015) Ev
94. Give the structures of A, B and C in the following (Delhi 2016) Cr
reactions : 101. Write the structures of A, B and C in the following
Sn + HCl NaNO2 + HCl reactions :
(i) C6H5NO2 A B
273 K Sn/HCl NaNO2 + HCl H2O
H2O (i) C6H5NO2 A B D C
C
H2O/H+ NH3 Br2 + KOH KCN LiAlH4 HNO2
(ii) CH3CN A B C (ii) CH3Cl A B C
D 273 K
(2/3, Delhi, AI 2014) An (3/5, Foreign 2015) Ev
Amines 241
LA (5 marks) NO2
102. Read the following passage and answer the Sn + HCl Br2 water
(I) A B
questions that follow :
Br2/alc. KOH CH3COCl
Amines constitute an important class of organic (II) CH3CH2CONH2 A B
Pyridine
compounds derived by replacing one or more OR
hydrogen atoms of ammonia molecule by alkyl/ (b) How will you convert the following
aryl groups. Amines are usually formed from nitro (I) Benzoic acid to aniline
compounds, halides, amides, etc. They exhibit (II) Aniline to p-bromoaniline (Term-II, 2021-22)
hydrogen bonding which influences their physical
103. An aromatic compound ‘A’ of molecular formula
properties. Alkyl amines are found to be stronger
C7H7ON undergoes a series of reactions as shown
bases than ammonia. In aromatic amines, electron
below. Write the structures of A, B, C, D and E in the
releasing and withdrawing groups, respectively following reactions :
increase and decrease their basic character. Br2 + KOH
Reactions of amines are governed by availability of (C7H7ON) A
the unshared pair of electrons on nitrogen. Influence CH3CH2OH NaNO2 + HCl
C B C6H5NH2
of the number of hydrogen atoms at nitrogen atom 273 K
CHCl3
on the type of reactions and nature of products KI +
NaOH
is responsible for identification and distinction
E D
between primary, secondary and tertiary amines.
Reactivity of aromatic amines can be controlled by (Delhi 2015) Cr
acylation process. 104. (i) Write the structures of main products when
(i) Why does aniline not give Friedel-Crafts benzenediazonium chloride (C6H5N2+Cl–)
reaction ? reacts with the following reagents :
(ii) Arrange the following in the increasing order of (a) HBF4/D (b) Cu/HBr
their pKb values : (ii)
Write the structures of A, B and C in the
C6H5NH2, NH3, C2H5NH2, (CH3)3N following reactions :
Sn + HCl NaNO2 + HCl H2O
(iii) How can you distinguish between CH3CH2NH2 (a) C6H5NO2 A B C
273 K D
and (CH3CH2)2NH by Hinsberg test ?
KCN LiAlH4 HNO2
(iv) (a)
Write the structures of A and B in the (b) CH3Cl A B C
following reactions : (Foreign 2015) U
9.4 Preparation of Amines 9.6 Chemical Reactions (Amines)

MCQ MCQ
1. Propanamide on reaction with bromine in aqueous 3. Which of the following statements is not correct for
NaOH gives amines?
(a) propanamine (b) ethanamine (a) Most alkyl amines are more basic than ammonia
(c) N-methylethanamine (d) propanenitrile. solution.
(2020-21) (b) pKb value of ethylamine is lower than benzylamine.
(c) CH3NH2 on reaction with nitrous acid releases
9.5 Physical Properties NO2 gas.
(d) Hinsberg’s reagent reacts with secondary
MCQ amines to form sulphonamides. (2022-23)
2. Arrange the following in the increasing order of 4. Given below are two statements labelled as
their boiling points: Assertion (A) and Reason (R).
A : Butanamine, B : N,N-Dimethylethanamine, Assertion (A) : Tertiary amines are more basic than
C : N-Ethylethanamine corresponding secondary and primary amines in
(a) C < B < A (b) A < B < C gaseous state.
(c) A < C < B (d) B < C < A Reason (R) : Tertiary amines have three alkyl groups
(2022-23) Ap which cause +I effect.
Select the most appropriate answer from the options (i) Aniline, ethanamine, 2-ethylethanamine
given below: (solubility in water)
(a) Both A and R are true and R is the correct (ii) Ethanoic acid, ethanamine, ethanol (boiling point)
explanation of A. (iii) Methanamine, N,N - dimethylmethanamine
(b) Both A and R are true but R is not the correct and N-methylmethanamine (basic strength in
explanation of A. aqueous phase) (2020-21) Ap
(c) A is true but R is false. 9. (i) ive a chemical test to distinguish between
G
(d) A is false but R is true. (2022-23) N-methylethanamine and N, N-dimethylethanamine.
5. IUPAC name of product formed by reaction of (ii) Write the reaction for catalytic reduction of
methyl amine with two moles of ethyl chloride is nitrobenzene followed by reaction of product
(a) N,N-dimethylethanamine so formed with bromine water.
(b) N,N-diethylmethanamine (iii) Out of butan-1-ol and butan-1-amine, which
(c) N-methylethanamine will be more soluble in water and why?
(d) N-ethyl-N-methylethanamine. (2020-21) U (2020-21)
SA II (3 marks) 9.9
Chemical Reactions
6. Account for the following : (Diazonium salts)
(a) Aniline cannot be prepared by the ammonolysis
of chlorobenzene under normal conditions. SA II (3 marks)
(b) N-ethylethanamine boils at 329.3 K and 10. Give reasons for any 3 of the following observations:
butanamine boils at 350.8 K, although both are (a) Aniline is acetylated before nitration reaction.
isomeric in nature. (b) pKb of aniline is lower than the m-nitroaniline.
(c) Acylation of aniline is carried out in the (c) Primary amine on treatment with
presence of pyridine. benzenesulphonyl chloride forms a product
which is soluble in NaOH however secondary
OR
amine gives product which is insoluble in NaOH.
Convert the following : (d) Aniline does not react with methyl chloride
(a) Phenol to N-phenylethanamide in the presence of anhydrous AlCl3 catalyst.
(b) Chloroethane to methanamine
(2022-23) Ap
(c) Propanenitrile to ethanol (Term II, 2021-22)
7. What happens when reactions : 11. (a) Write the IUPAC name for the following organic
(a) N-ethylethanamine reacts with benzenesulphonyl compound :
chloride. CH3 N CH2CH3
(b) Benzyl chloride is treated with ammonia
followed by the reaction with chloromethane.
(c) Aniline reacts with chloroform in the presence
of alcoholic potassium hydroxide. (b) Complete the following :
(Term II, 2021-22) An Sn/HCl Br /H O NaNO /HCl HBF
C6H5NO2 → A 
2 2
→ B 273
 2
− 278 K
→ C 
∆
4
→D
8. Arrange the following in increasing order of property
specified : (Term II, 2021-22)
Cl
Previous Years’ CBSE Board Questions
NO2
3.
1. (a) (C2H5)2CHNH2 is a primary amine.
H3CH2C
2. N—CH3 NO2
H3CH2C 2, 4-Dinitrochlorobenzene
IUPAC name : N-Ethyl-N-methylethanamine 4. N-Methylpropan-2-amine (2° amine)
Answer Tips H3C
5. N CH2CH3
Â The largest alkyl group forms a part of the aminoalkane H3C
while the smaller alkyl groups are considered as N,N-Dimethylethanamine
substituents.
6. 2, 4, 6-Tribromoaniline
Amines 243
7. (b) : When amide is treated with NaOH or KOH and 14. R-CONH2 + Br2 + 4NaOH R-NH2 + Na2CO3
Br2, amine with one less carbon atom is obtained. The Acid amide 1° amine
reaction is called as Hoffmann bromamide reaction. + 2NaBr + 2H2O
CH3CONH2 + 4NaOH + Br2 → CH3NH2 + Na2CO3 Na + C2H5OH
+ 2NaBr + 2H2O 15. CH3CN + 4[H] CH3CH2NH2
Ethanenitrile Ethanamine
8. (c) : Alkyl halides when treated with ethanolic
solution of NH3 give a mixture of primary, secondary and KCN LiAlH4
16. CH3Br CH3CN CH3CH2NH2
tertiary amines. A B
NH3 R—X R—X
R—X R—NH2 R2NH R3N Key Points
pri-amine sec-amine tert-amine
Thus it is not a suitable method. Â In this reaction, the alkyl halide is converted to primary
amine having one carbon atom more than the parent
9. (a) : LiAlH4 reduces aliphatic nitro compounds to
alkyl halide.
amines, but converts aromatic nitro compounds such as
nitrobenzene to produce azo compounds. NO2 NH2
NO2
Fe/HCl
LiAlH4 17. (i) + 6[H] + 2H2O
N N
Nitrobenzene Azo benzene Nitrobenzene Aniline
O
10. (c) : CH3CONH2 + Br2 + 4NaOH PCl5
CH3NH2 + Na2CO3 + 2NaBr + 2H2O (ii) CH3COOH CH3 C Cl
Ethanoic acid NH3
11. The ammonolysis of alkyl halides with ammonia is a (Acetic acid)
O
nucleophilic substitution reaction in which ammonia acts Br2/KOH
as a nucleophile by donating the electron pair on nitrogen CH3 NH2 CH3 C NH2
atom to form primary amine as the initial product. Now, Methanamine
the primary amine can act as a nucleophile and combine H3CH2C
with alkyl halide (if available) to give secondary amine and 18. (a) N—CH3
H3CH2C
the reaction continues in the same way to form tertiary
IUPAC name : N-Ethyl-N-methylethanamine
amine and finally quaternary ammonium salt. Thus, a
mixture of products is formed and it is not possible to CO CO –
KOH (alc.)
separate individual amines from the mixture. NH –H2O
NK+
NH2 -
R X R X - (b) (i) CO CO
R-X R-NH2 R2NH –KI C2H5I
–HX –HX –HX
R-X
R3N R4N+X–
COONa+ NaOH( aq) CO
NH3 NaOBr
12. CH3COOH D CH3CONH2 CH3NH2 (Hydrolysis) NC2H 5
(A) (B) COONa+ CO
Phthalic acid
Key Points +
Â In Hoffmann degradation, there is one carbon atom C2H 5NH2
less in product. Ethylamine
COOH COONH4+ (ii) R-CONH2 + Br2 + 4NaOH → R-NH2 + Na2CO3

CONH2
Alkyl amide 1° amine
NH3 Al2O3, D + 2NaBr + 2H2O
13. –H2O
Benzoic acid Ammonium
19. Formula of the compound ‘C’ indicates it is an amine.
Benzamide
benzoate Since it is obtained by the reaction of Br2 and KOH with
NH2 the compound ‘B’ so compound ‘B’ can be an amide. As ‘B’
is obtained from compound ‘A’ by reaction with ammonia
Br2 + KOH
followed by heating so, compound ‘A’ could be an aromatic
acid. Formula of compound ‘C’ shows it to be aniline, then
Aniline ‘B’ is benzamide and compound ‘A’ is benzoic acid. The
Alternative Method
sequence of reactions can be written as follows :
O COOH CONH2 NH2
COOH COCl C-NH2 NH2 NH3 Br2/KOH
∆
SOCl2 NH3 Br2/KOH
A B C
(Benzoic acid) (Benzamide) (Aniline)
NO2 NH2 than even ammonia due to electron withdrawing nature

of aryl group. Thus, aniline is least basic.
20. (i) + 6[H] Fe/HCl + 2H2O 29. (b) : Aniline undergoes electrophilic substitution
reactions. NH2 group is ortho and para directing and a
Nitrobenzene Aniline powerful activating group.
O
Br /KOH
(ii) CH3 - C - NH2 
→ CH3 NH2
2
Ethanamide Methanamine
H2/Ni
(iii) CH3CN → CH3 CH2NH2
Ethanenitrile Ethanamine Aniline is a Lewis base, it reacts with Lewis acid used as
catalyst in alkylation or acylation reaction. Due to the
21. CH3OH has higher boiling point than CH3NH2. The presence of a positive charge on N-atom in the salt, the
hydrogen bonding in alcohols is stronger than that of group –NH2AlCl3– acts as strong deactivating group for
amines because oxygen is more electronegative than electrophilic substitution reaction. Hence, aniline does
nitrogen. not undergoes Friedel—Crafts reaction.
22. Decreasing order of boiling points of given
compounds :
Butanol > butanamine > butane
Concept Applied 30. (c) : Acetylation of aniline gives monosubstituted
Â Boiling point increases with increase in extent of product as the substitution takes place at N-atom.
hydrogen bonding. NH2 NHCOCH3
AlCl3
23. Primary amines (R – NH2) have two hydrogen atoms + CH3COCl
on nitrogen which can undergo intermolecular hydrogen
bonding whereas no such hydrogen bonding is present in –NHCOCH3 has less activating effect than amino
tertiary amines (R3N). So, primary amines boil at a higher group as the lone pair of electrons on nitrogen atom in
temperature than tertiary amines. –NHCOCH3 is less available for donation to benzene ring
due to the presence of electron withdrawing carbonyl
24. Increasing order of boiling points : O
(CH3)3N < C2H5NH2 < C2H5OH
Tertiary amine does not have hydrogen to form hydrogen group C while lone pairs are available in case of
bonding and hydrogen bonding in alcohol is stronger aniline.
than that of primary amines because oxygen is more 31. (c) : (C2H5)2NH is more basic than (C2H5)3N and
electronegative than nitrogen. has less +I effect in aqueous solution due to less steric
25. C6H5NH2 < (C2H5)2NH < C2H5NH2 hindrance as compared to (C2H5)3N.
1° amines are more soluble in water than 2° amines. Aniline Heat
32. (a) : C6H5NH2 + CHCl3 + 3KOH →
due to large hydrophobic benzene ring is least soluble. (Aniline)
26. Ethylamine is soluble in water due to C6H5NC + 3KCl + 3H2O
formation of intermolecular hydrogen bonds with (A) (B) (C)
water molecules. However, in aniline due to large Phenylisocyanide
hydrophobic aryl group the extent of hydrogen It is a carbylamine reaction.
bonding decreases considerably and hence aniline Hence, product A is phenylisocyanide.
is insoluble in water. 33. (b) : The order of basicity of the given compounds is
27. (i) C6H5NH2 < (CH3)2NH < CH3NH2 (CH3)2NH > CH3NH2 > (CH3)3N > C6H5NH2.
1° amines are more soluble in water than 2° amines. Aniline There is a subtle interplay of the inductive effect, solvation
is least soluble due to large hydrophobic benzene ring. effect and steric hindrance of alkyl groups which decides the
(ii) 1° amines have two, 2° amines have one while 3° basic strength of alkyl amines in the aqueous state.
amines have no hydrogen linked to nitrogen. The degree Commonly Made Mistake
of association due to hydrogen bonding and hence
Â Order of basicity :
the boiling point increase as (C2H5)3N < (C2H5)2NH <
In gaseous phase : 3° > 2° > 1° amine > NH3
C2H5NH2.
In aqueous phase : (CH3)2NH > CH3NH2 > (CH3)3N > NH3.
28. (c) : Aliphatic amines are stronger bases than
aromatic amines and ammonia due to +I effect of alkyl 34. In case of small alkyl groups like —CH3 the order of
group leading to high electron density on nitrogen atom. basicity is secondary amine > primary amine > tertiary
On the other hand, aromatic amines are weaker bases amine due to solvation effect and +I effect of —CH3 group.
Amines 245
(CH3)2NH > CH3NH2 > (CH3)3N O

pKb 3.27 3.38 4.22
O S O–
35. Decreasing order of basic strength is
C2H5NH2 > (CH3)3N > C6H5NH2 44. (i)
36. C2H5NH2 < (C2H5)2NH < (C2H5)3N
37. In aqueous solution, 2° amine is more basic than NH3
Sulphanilic acid
3° amine due to the combination of inductive effect,
(Zwitter ion)
solvation effect and steric hindrance.
(ii) Activating effect of —NH2 group in aniline can be
38. The decreasing order of basic strength in aqueous controlled by protecting —NH2 group by acetylation with
solution is acetic anhydride in presence of pyridine.
(CH3)2NH > CH3NH2 > (CH3)3N > NH3 O
NH2 NH2 NH2
NH2 HN
39. < < (CH3CO)2O
Pyridine
Aniline
NO2 CH3
45. (i) Decreasing order of basic strength in aqueous
p-nitroaniline p-toluidine
solution:
Electron withdrawing group (–NO2) on benzene ring (C2H5)2NH > (C2H5)3N > C2H5NH2
decreases the basicity and electron donating group (-CH3) (ii) Increasing order of solubility in water :
on benzene ring increases the basicity of compound. C2H5NH2 > (C2H5)2NH > C6H5NH2
40. C6H5NH2 < C6H5NHCH3 < C6H5CH2NH2 1° amines are more soluble in water than 2° amines.
C6H5NH2 and C6H5NHCH3 are less basic than aliphatic Aniline is least soluble in water due to large hydrophobic
amine C6H5CH2NH2 due to lone pair of nitrogen which is in benzene ring.
conjugation with benzene ring. But due to +I effect of —CH3 (iii) Decreasing order of pKb value :
group in C6H5NHCH3, it is more basic than C6H5NH2. C6H5NH2 > NH3 > C2H5NH2
41. Increasing order of basic strength in gaseous state is Key Points
as follows : Â When the alkyl group is bigger than -CH3 group,
C6H5NH2 < C6H5NHCH3 < C6H5N(CH3)2 there will be some steric hindrance to H-bonding. As
As the number of —CH3 groups (+I effect) attached to a result, stability due to +I effect predominates over
nitrogen increases, its basicity will increase. the stability due to H-bonding, and hence 3° amines
42. CH3NH2 is more basic than C6H5NH2 because in become more basic than 1° amines.
aniline the lone pair of electrons on nitrogen are involved
in resonance. 46. (i) Increasing order of basic strength is
C6H5NH2 < C6H5N(CH3)2 < CH3NH2 < (C2H5)2NH
43. (a) Carbylamine reaction is the reaction in which 1°
(ii) Stronger the base, lower will be its pKb value. Hence,
amines produce a bad smelling compound when treated
the decreasing order of pKb values :
with chloroform in the presence of alkali.
C6H5NH2 > C6H5NHCH3 > C2H5NH2 > (C2H5)2NH
RNH2 + CHCl3 + 3KOH (alc.) R—N C + 3KCl + 3H2O LiAlH4
It is the test for primary amines. 47. (i) (b) : CH3CN CH3CH2NH2
(b) Gabriel phthalimide synthesis is used for the (ii) (d) : C6H5SO2Cl is Hinsberg reagent.
preparation of primary amines. Phthalimide on treatment (iii) (a) : (CH3)2NH is strongest base in aqueous solution.
with ethanolic potassium hydroxide forms potassium salt NH2 -
R X -
R X
of phthalimide which on heating with alkyl halide followed (iv) (c) : R-X R-NH2 R2NH
–HX –HX –HX
by alkaline hydrolysis produces the corresponding R X-
primary amine. R3N R4N+X–
CO CO
NH
KOH (alc.) –
NK+ OR
–H2O
CO CO (b) : Order of boiling points in amines is
–KI C2H5I 1° > 2° > 3°
3° amines have lower boiling point due to branching.
COONa+ NaOH( aq) CO 48. (b) : Primary amines when warmed with chloroform
(Hydrolysis) NC2H 5
COONa +
CO and alcoholic solution of KOH produce isocyanides or
Phthalic acid carbylamines which have foul smell.
+ CHCl3
C2H 5NH2 49. CH3CH2CH2NH2 CH3CH2CH2NC
Ethylamine alc. NaOH (Foul smell)
50. C6H5NO2
Fe + HCl
C6H5NH2 59. (i) When heated with an alcoholic solution of
(A) KOH and CHCl3, ethylamine gives foul smelling ethyl
NaNO2 + HCl isocyanide. Diethylamine does not give this test.
C6H5N2+Cl– (ii) Aniline gives white or brown precipitate with
0-5°C
(B) bromine water.
HCN Ni/H2
51. CH3-Br CH3-CN NH2 NH2
Bromomethane (i) HNO2 Br Br
CH3CH2NH2 CH3CH2OH + 3Br2
(ii) H2O + 3HBr
Ethanol
52. Carbylamine reaction is the reaction in which 1° Br
amines produce a bad smelling compound when treated (white ppt.)
with chloroform in the presence of alkali. Methylamine does not react with bromine water.
RNH2 + CHCl3 + 3KOH (alc.) R—N C + 3KCl + 3H2O
60. (i) Nitration is carried out with conc. HNO3 in
It is the test for primary amines.
the presence of conc. H2SO4. In the presence of these
53. When treated with benzenesulphonyl chloride acids, the –NH2 group of aniline gets protonated and
(Hinsberg’s reagent), (CH3)2NH forms insoluble +
is converted into –NH3 group. This positively charged
N, N-dialkylbenzene sulphonamide which is insoluble in
group acts as a strong electron withdrawing and meta-
KOH whereas tertiary amine does not react at all.
directing group. Hence, the incoming electrophile goes to
Alternative Method m-position.
Â Secondary amine on reaction with nitrous acid gives (ii) In aqueous solution, 2° amine is more basic than
oily nitrosoamine while 3° amine forms water soluble 3° amine due to the combination of inductive effect,
nitrite. solvation effect and steric reasons.
O 61. (a) Aromatic primary amines cannot be prepared
by this method because aryl halides do not undergo
NH2 H-N-C-CH3 nucleophilic substitution with the anion formed by
(CH3CO)2O phthalimide.
54. (b) Primary amines react with benzene sulphonyl
Pyridine
chloride to give sulphonamide which is soluble in alkali.
Aniline N-Phenylethanamide
(Acetanilide) SO2Cl + H2NR SO2HN R + HCl
55. Methyl amine (CH3NH2) is more basic than
ammonia because of the presence of electron donating N-Alkylbenzene
sulphonamide
methyl group (+I effect), which increases the electron
KOH
density on nitrogen atom.
56. CH3(C6H4) NH2 is more basic than C6H5NH2 due to SO2NRK+ + H2O
electron releasing nature of methyl group which pushes
electrons towards nitrogen. It dissolves in alkali due to the presence of acidic
hydrogen on N-atom. Secondary amine reacts with
57. (a) CH3—N—CH2CH3 benzene sulphonyl chloride to give N,N-dialkyl benzene
sulphonamide which is insoluble in alkali due to the
absence of acidic hydrogen.
N-Ethyl-N-methylbenzenamine SO2Cl + HNR2 SO2NR2 + HCl
or
N-Ethyl-N- methylamiline N,N-Dialkylbenzene
NH2 sulphonamide
Br Br
Sn/HCl Br2/H2O
(b) C6H5NO2 C6H5NH2 + 3HBr No reaction
(A)
NH2 NH3+HSO4– NH2
Br
(B) conc. H2SO4 Heat
58. (i) Aniline being an aromatic primary amine on 62. (a)
453–473 K
treatment with HNO2[NaNO2 + HCl (dil.)] at 273–278 K
followed by treatment with an alkaline solution of SO3H
b-naphthol gives an orange coloured azo dye. Ethanamine O
does not give this test.
(ii) Aniline gives carbylamine test, i.e., on treatment with CONH2 NH2 HN-C-CH3
alc. KOH and chloroform followed by heating it gives Br2 (CH3CO)2O
offensive odour of phenylisocyanide but N-methylaniline (b)
NaOH
being secondary amine, does not show this test.
Amines 247
O (ii) Acetylation of amines : The process of introducing

O
NH2 H-N-C-CH3
an acetyl group (CH3-C-) into a molecule is called
(CH3CO)2O
63. (i) acetylation.
Pyridine O
Base
CH3CH2NH2 + CH3-C-Cl
(Acetanilide)
O Ethanamine O
CH3
–HCl
(ii) S Cl + H N CH3-C-NHC2H5 + HCl
CH3 N-Ethyl acetamide
O O
Benzene sulphonyl CH3
S N 67. (i) In Friedel — Crafts reaction, AlCl3 is added as a
chloride
CH3 catalyst which is a Lewis acid. It forms a salt with aniline
O due to which the nitrogen of aniline acquires positive
N, N-dimethylbenzene
charge. This positively charged nitrogen acts as a strong
sulphonamide
deactivating group, hence aniline does not undergo
64. (a) Aniline undergoes isocyanide test (carbylamine Friedel — Crafts reaction.
reaction) whereas, N, N – dimethylaniline does not.
NH2
NH2 NC
+
+ CHCl3 + 3KOH + 3KCl + 3H2O + AlCl3 NH2 AlCl–3
Aniline Phenyl isocyanide
(foul smell) (ii) In aniline, the lone pair of electrons of N-atom are
Key Points delocalised over the benzene ring. As a result, electron
density on the nitrogen decreases. In contrast, in
Â Only 1° amines give positive carbylamine test.
CH3—NH2, +I effect of —CH3 group increases the electron
(b) Stronger the base, lower will be the pKb value. density on the N-atom.
C2H5NH2 < C6H5NHCH3 < C6H5NH2 Therefore, aniline is a weaker base than methylamine and
hence, its pKb value is higher than that of methylamine.
pKb 3.29 4.63 9.38
68. (i)
Commonly Made Mistake CO CO –
KOH (alc.)
NH –H2O
NK+
Â pKb is inversely proportional to basic strength. CO CO
–KI C2H5I
65. (i) In Friedel — Crafts reaction, AlCl3 is added as a
catalyst which is a Lewis acid. It forms a salt with aniline COONa+ NaOH( aq) CO
(Hydrolysis) NC H
due to which the nitrogen of aniline acquires positive COONa +
CO
charge. This positively charged nitrogen acts as a strong Phthalic acid
+
deactivating group, hence aniline does not undergo C2H 5NH2
Friedel — Crafts reaction. Ethylamine
CHCl3
NH2 (ii) CH3NH2 CH3NC
alc. KOH
+ AlCl3
+
NH2 AlCl–3 (iii) R-CONH2 + Br2 + 4NaOH → R-NH2 + Na2CO3
Alkyl amide 1° amine
(ii) In aqueous solution, 2° amine is more basic than + 2NaBr + 2H2O
3° amine due to the combination of inductive effect, 69. (i) The ammonolysis of alkyl halides with
solvation effect and steric hindrance. ammonia is a nucleophilic substitution reaction in which
ammonia acts as a nucleophile by donating the electron
66. (i) Ammonolysis : Alkyl halides when treated with
pair on nitrogen atom to form primary amine as the
ethanolic solution of ammonia give a mixture of primary, initial product. Now, the primary amine can act as a
secondary, tertiary amines and quaternary ammonium nucleophile and combine with alkyl halide (if available) to
salt. give secondary amine and the reaction continues in the
373 K RX same way to form tertiary amine and finally quaternary
R X NH3 R NH2 R2NH
Primary Secondary RX ammonium salt. Thus, a mixture of products is formed
amine amine and it is not possible to separate individual amines from
R4NX
RX
R3N the mixture.
NH2 -
R X R X - R -X
Quaternary Tertiary R-X R -NH2 R2NH R3N R4N+X–
ammonium salt amine –HX –HX –HX
(ii) In Friedel—Crafts reaction, AlCl3 is added as a deactivating group, hence aniline does not undergo
catalyst which is a Lewis acid. It forms a salt with aniline Friedel – Crafts reaction.
due to which the nitrogen of aniline acquires positive NH 2
+
deactivating group, hence aniline does not undergo + AlCl3 NH2 AlCl3–
Friedel — Crafts reaction.
NH2 (iii) Primary amines (R – NH2) have two hydrogen atoms
on nitrogen which can undergo intermolecular hydrogen
+
+ AlCl3 NH2 AlCl–3 bonding whereas no such hydrogen bonding is present in
tertiary amines (R3N). So, primary amines boil at a higher
(iii) Nitration is carried out with conc. HNO3 in the temperature than tertiary amines.
presence of conc. H2SO4. In the presence of these 72. (i) Basic strength in aqueous solution
acids, the –NH2 group of aniline gets protonated and
+ (CH3)3N < CH3-NH2 < (CH3)2NH
is converted into –NH3 group. This positively charged There is a subtle interplay of the inductive effect,
group acts as a strong electron withdrawing and meta- solvation effect and steric hindrance of alkyl groups
directing group. Hence, the incoming electrophile goes to which decides the basic strength of alkyl amines in the
m-position. aqueous state.
O
(ii) Benzenesulphonyl chloride is Hinsberg’s reagent
70. (i) CH3CH2NH2 + CH3 - C - Cl →
and it is used for the distinction and separation of
Ethylamine Acetyl chloride O primary, secondary and tertiary amines from a mixture.
C
CH3CH2 - N CH3 + HCl SO2Cl
H
N–Ethylacetamide Benzenesulphonyl chloride
(ii) Aniline gives white precipitates of 2,4,6-tribromo- (iii) Acylation of amines is a nucleophilic substitution
aniline on reaction with bromine water. reaction. This reaction occurs in the presence of a base
NH2 NH2 stronger than amine like pyridine. It removes HCl formed
Br2/H2O
Br Br in the reaction and shifts the equilibrium to the right
+ 3Br2 + 3HBr hand side.
Pyridine
Aniline
Br C6H5NH2 + CH3COCl → C6H5NHCOCH3 + HCl
(White ppt.) Aniline Ethanoyl N-Phenylethanamide
2,4,6-Tribromoaniline Chloride
(iii) Aniline react with chloroform and ethanolic KOH 73. Nitro group (–NO2) is reduced to –NH2 group by
to give phenyl isocyanide. This reaction is known as treatment of iron scrap with HCl.
carbylamine reaction. Molecular formula of B is C6H7N, so it may be aniline.
NH2 NO2 NH2
∆
+ CHCl3 + 3KOH
Fe/HCl
NC + 6[H]  → + 2H2O
Aniline
+ 3KCl + 3H2O Nitrobenzene Aniline
(A) (B)
Phenyl isocyanide
(foul smell ) Aniline on reaction with CHCl3 and alcoholic KOH,
produces phenyl isocyanide.
71. (i) In aniline, the lone pair of electrons on N-atom
is delocalised over benzene ring due to resonance. As a NH2 N C
result, electron density on the nitrogen atom decreases.
In contrast, in methylamine, +I-effect of —CH3 group + CHCl3 + 3KOH → + 3KCl + 3H2O
increases electron density on the nitrogen atom.
Therefore, aniline is a weaker base than methylamine (B) (C)
hence, its pKb value is more than that for methylamine.
(ii) In Friedel – Crafts reaction, AlCl3 is added as a 74. (i) Ethylamine forms intermolecular hydrogen
catalyst which is a Lewis acid. It forms a salt with aniline bonding with water which makes it soluble in water.
due to which the nitrogen of aniline acquires positive Aniline has a hydrophobic part C6H5 - which makes it
charge. This positively charged nitrogen acts as a strong insoluble in water.
Amines 249
(ii) Nitration is carried out with conc. HNO3 in the (c) Aromatic 1° amines such as aniline, toluidine, etc.
presence of conc. H2SO4. In the presence of these acids, cannot be prepared by this method because aryl halides
the –NH2 group of aniline gets protonated and is converted do not undergo nucleophilic substitution reaction with
+
into –NH3 group. This positively charged group acts as a potassium phthalimide under mild conditions.
strong electron withdrawing and meta-directing group.
77. (a) CH3NH2 + C6H5COCl
Hence, the incoming electrophile goes to m-position. O
(iii) Amines behave as nucleophiles due to the presence
of unshared electron pair. CH3NH C C6H5
75. N-Methylbenzamide
O (b) Stronger the base, lower will be its pKb value. Hence
Br2/KOH
H3C - CH2 - C - NH2 → H3C - CH2 - NH2
 increasing order of pKb values is,
D
(A) (B) (C2H5)2NH < C2H5NH2 < NH3 < C6H5NH2
(Hofmann degradation) 78. (i) In Friedel – Crafts reaction, AlCl3 is added as a
As, ‘B’ reacts with CHCl3/alc. KOH this means it is a catalyst which is a Lewis acid. It forms a salt with aniline
primary amine.
CHCl3/ due to which the nitrogen of aniline acquires positive
H3C - CH2 - NC
alc.KOH
(C)
H3C - CH2 - NH2 Foul smelling Friedel – Crafts reaction.
(B) C6H5SO2Cl NH 2
O +
+ AlCl3 NH2 AlCl3–
S N CH2 CH3
(ii) Aromatic 1° amines such as aniline, toluidine, etc.
O H
(D)
cannot be prepared by this method because aryl halides

N-ethylbenzenesulphonamide do not undergo nucleophilic substitution reaction with
76. (a) Ethanamine is more basic than aniline because potassium phthalimide under mild conditions.
in aniline lone pair of electrons on nitrogen are involved (iii) Amines and ammonia are Lewis bases due to the
in resonance. presence of lone pair of electrons on them. As aliphatic
(b) In Friedel – Crafts reaction, AlCl3 is added as a amines have alkyl group which shows +I effect and
catalyst which is a Lewis acid. It forms a salt with aniline increases electron density on amines hence and behave
due to which the nitrogen of aniline acquires positive as stronger bases.
charge. This positively charged nitrogen acts as a strong R R R
Friedel – Crafts reaction. R N R N H N NH3
NH 2 R H H
+ 79. Primary, secondary and tertiary amines can be
+ AlCl3 NH2 AlCl3–
distinguished by Hinsberg reagent.
, ,
80. (a) (i) Methylamine gives carbylamine test, i.e., on H2O +

treatment with alc. KOH and chloroform, followed by
(ii) NH2 + HCl NH3Cl–
heating it gives offensive odour of methyl isocyanide. O
Dimethylamine does not give this test.
(ii) Aniline being an aromatic primary amine on treatment NH2 H-N-C-CH3
with HNO2[NaNO2 + HCl (dil.)] at 273–278 K followed by (CH3CO)2O
treatment with an alkaline solution of b-naphthol gives an (iii)
Pyridine
orange coloured azo dye. Ethylamine does not give this test.
(b) In Friedel — Crafts reaction, AlCl3 is added as a (Acetanilide)
catalyst which is a Lewis acid. It forms a salt with aniline
LiAlH4
due to which the nitrogen of aniline acquires positive 84. (i) CH3CH2Br KCN CH3CH2CN
charge. This positively charged nitrogen acts as a strong (A)
deactivating group, hence aniline does not undergo CH3CH2CH2OH 273 K
CH3CH2CH2NH2
Friedel — Crafts reaction. HNO2
(C) (B)
NH2 NH3 Br2 + NaOH
(ii) CH3COOH D CH3CONH2
+
+ AlCl3 NH2 AlCl–3 (A)
CHCl3 + NaOH
CH3NC CH3NH2
NH2 N2+Cl– CN (C) (B)
NaNO2 + HCl CuCN

85. (b) :
81. (a) + N2 NaNO2 + HCl C6H5NH2/H+
0–5°C C6H5NH2 0-5°C
ArN2+X–
pH = 4-5, 0-5°C
(X) (Y)
ArN=NC6H4NH2
(b) Nitration is carried out with conc. HNO3 in the
p-Aminoazobenzene
presence of conc. H2SO4. In the presence of these (Yellow dye)
acids, the –NH2 group of aniline gets protonated and H2O/H+
+
is converted into –NH3 group. This positively charged 86. C6H5N2+Cl– CuCN C6H5CN
group acts as a strong electron withdrawing and meta- Benzonitrile
(A) C6H5COOH
directing group. Hence, the incoming electrophile goes to
Benzoic acid
m-position. (B)
82. (i) After acetylation of aniline, acetanilide is CH3 CH3
O Br Sn/HCl
Br2
formed in which due to the presence of -C-CH3 group 87.
having –I effect, electron density on N-atom decreases
and hence, activation effect of aniline gets reduced. NO2 NO2
Answer Tips CH3 CH3
Br Br H PO /H O
O NaNO2/HCl 3 2 2
Â -C-CH3 group exerts –I-effect on adjacent -NH2 273-278 K
group. NH2 N2+Cl–

(ii) CH3NH2 is more basic than C6H5NH2 because in COOH CH3
aniline the lone pair of electrons on nitrogen are involved Br KMnO4—KOH Br
in resonance. D
(iii) Nitration is carried out with conc. HNO3 in the
presence of conc. H2SO4. In the presence of these
acids, the –NH2 group of aniline gets protonated and Commonly Made Mistake
+
is converted into –NH3 group. This positively charged Â -CH3 is o- and p- directing while -NO2 is m-directing
group acts as a strong electron withdrawing and meta- and deactivating group. So, the product is formed in
directing group. Hence, the incoming electrophile goes to accordance with these conditions.
m-position.
Reduction
NH2 88. C6H5N2+Cl– + C2H5OH
Br Br
Benzenediazonium C6H6 + CH3CHO + N2↑ + HCl
chloride Benzene Ethanal
83. (i) C6H5NH2 + Br2(aq) + 3HBr
89. C6H5N2+Cl– + H3PO2 + H2O
Br C6H6 + N2 + H3PO3 + HCl
Amines 251
90. Diazotisation reaction. 95. (a) The replacement of group of benzene

N2Cl – diazonium chloride by the nucleophiles Cl–, Br– and
CN– in the presence of Cu(I) ion as catalyst is called
CH3CH2OH
91. (i) + CH3CHO + N2 + HCl Sandmeyer reaction.
Example, benzene diazonium chloride when treated with
Benzene KCN in presence of CuCN gives cyanobenzene.
alc.KOH aq. KCN
(ii) CH3CH2Br CH2 CH2
Bromoethane
H2/Pd
CH3 — CH2 — C N CH3 — CH2 — CH2 — NH2
Propanamine
(b) In aqueous solution, 2° amine is more basic than
92. (a) Diazotisation :
3° amine due to the combination of inductive effect,
273-278 K solvation effect and steric hindrance.
NH2 + NaNO2 + 2HCl
N2+Cl– CN
Aniline
N NCl NaCl 2H2O CuCN
Diazonium salt 96. (i)
(b) Diazonium salts carry a nitrogen atom with a positive Benzonitrile
charge. This positive charge is well dispersed in aromatic
Reduction
diazonium salts through resonance as shown below : (ii) C6H5N2+Cl– + C2H5OH
Benzenediazonium
chloride C6H6 + CH3CHO + N2 + HCl
N N N N N N Benzene Ethanal

N2+Cl– I
(iii) + KI
Iodobenzene
N N N N Answer Tips
Â In benzene diazonium chloride salt, -N2+Cl– group is
attacked by incoming nucleophile.
CN CH2NH2
Such a charge delocalisation is not possible in aliphatic H2/Ni
97. (a)
diazonium salts and hence they are less stable than
aromatic diazonium salts. CH3 CH3
CONH2 NH2 Br Br
Br2 + KOH H3PO2 + H2O
93. (i) (b)
Benzamide Aniline
N2+Cl–
NH2 N+2Cl– OH (c)
NaNO2
CH2-NH2 CH2NC
H2O alc. KOH
(ii) + HCl Warm + N2 + HCl + CHCl3
Aniline Phenol O O
94. (i) C6H5NO2

Sn + HCl
C6H5NH2
NaNO2 + HCl HN-C-CH3 H-N-C-CH3 NH2
A
Br2 OH– or H+
H2O 98. (a)
C6H5OH C6H5N2+Cl– CH3COOH
C B
H2O/H+ NH3 Br Br
(ii) CH3CN CH3COOH CH3CONH2
A B
N2+Cl– N2+BF4– NO2
Br2 + KOH NaNO2

CH3NH2 (b) + HBF4 + N2 + NaBF4
Cu, D
C
COOH COONH4+ CONH2 CONH2 NH2

NH3 Al2O3, D Br2 0-5°C
(iii) 100. (i)
–H2O aq. KOH NaNO2 + HCl
Benzoic acid Ammonium Benzamide (A)
benzoate
I N2+Cl–
NH2
KI
Br2 + KOH
(C) (B)
Aniline KCN LiAlH4
NH3 Br2 + NaOH (ii) CH3—Cl CH3CN CH3CH2NH2
99. (a) CH3COOH D CH3CONH2 (A) (B)
(A) CHCl3 + alc. KOH
CHCl3 + alc. KOH CH3CH2NC
D
CH3NC CH3NH2 (C)
(C) (B)
Sn + HCl NaNO2 + HCl
(b) + – NaNO2/Cu
C6H5N2BF 4 → C6H5NO2 101. (i) C6H5NO2 C6H5NH2
D A
Nitrobenzene H2O
(A) C6H5OH C6H5N2+Cl–
C B
(Reduction) Fe/HCl
KCN LiAlH4
(ii) CH3Cl CH3CN CH3CH2NH2
CH3COCl
C6H5NHCOCH3 C6H5NH2
→
A B
Pyridine HNO2
Acetanilide Aniline CH3CH2OH
273 K
(C) (B) C
102.
Amines 253
[Topper’s Answer, 2022]
COOH COONH4+ CONH2 N2+Cl– F

NH3 Al2O3, D HBF4/D
(b) (I) 104. (i) (a)
–H2O
Benzoic acid Ammonium Benzamide Benzenediazonium Fluorobenzene
benzoate chloride
NH2 + – Br
N2Cl
Br2 + KOH
Cu/HBr
(b)
Aniline Benzenediazonium Bromobenzene
Alternative Method chloride
O Sn + HCl NaNO2 + HCl
(ii) (a) C6H5NO2 C6H5NH2
273 K
COOH COCl C-NH2 NH2 A
H2O
SOCl2 NH3 Br2/KOH C6H5OH C6H5N2+Cl–
C B
(II) KCN LiAlH4

NH2 NHCOCH3 NHCOCH3 NH2 (b) CH3Cl CH3CN CH3CH2NH2
A B
(CH3CO)2O Br2 H+ HNO2
Pyridine CH3COOH H2O CH3CH2OH
273 K
C
Br Br
CBSE Sample Questions
CONH2 NH2 N2+Cl–
Br2/KOH NaNO2 + HCl 1. (b) : CH3CH2CONH2 + Br2 + 4NaOH
103.
273 K Propanamide
(A) CHCl3 (B) CH3CH2NH2 + 2NaBr + K2CO3 + H2O
+ CH3CH2OH Ethanamine (1)
NaOH
2. (d) : B < C < A
NC
(C) In primary amine, intermolecular association due to
H-bonding is maximum while in tertiary, it is minimum.
KI
(1)
(D) 3. (c) : CH3NH2 on reaction with nitrous acid releases
(E) N2 gas, not NO2 gas. (1)
4. (a)(1) of alcoholic potassium hydroxide, phenyl isocyanide or

CH3CH2Cl phenyl isonitrile is formed. (1)
5. (d) : CH3NH2 (CH3CH2)NHCH3
(–HCl) 8.(i) Aniline < 2-ethylethanamine < ethanamine
Methyl amine (CH3CH2Cl)
(solubility in water) (1)
(–HCl) (ii) Ethanamine < ethanol < ethanoic acid
CH3CH2 N CH2 CH3 (boiling point) (1)
(iii) N,N-Dimethylmethanamine < methanamine <
CH3 N-methylmethanamine
N-Ethyl-N-methylethanamine (basicity strength in aqueous phase). (1)
(1)
9. (i) N-methylethanamine is a secondary amine.
6. (a) Under the normal conditions, ammonolysis of When it reacts with benzenesulphonyl chloride, it forms
chlorobenzene does not yield aniline as in chlorobenzene, N-ethyl-N-methylsulphonamide while N,N-dimethyl
the C—Cl bond is quite difficult to break as it acquires a ethanamine is a tertiary amine, it does not react with
partial double bond character. (1) benzenesulphonyl chloride. (1)
(b) Primary and secondary amines are engaged in
intermolecular association due to hydrogen bonding NO2 NH2 NH2
between nitrogen and one of the hydrogen of another Br Br
molecule. Due to the presence of two hydrogen atoms, (ii) Sn + HCl Br2/H2O
the intermolecular association is more in primary amines
than in secondary amines where only one hydrogen atom
is available for hydrogen bond formation in it. Hence, Br
butanamine being primary amine has a higher boiling (1)
point as compared to N-ethyl ethanamine which is a (iii) Butan-1-ol is more soluble in water because
secondary amine. (1) electronegativity of oxygen (3.5) is more than that of
(c) During the acylation of aniline, a stronger base nitrogen (3.0) and therefore, alcohols form stronger
pyridine is added to remove the HCl formed during the hydrogen bonds as compared to amines. (1)
reaction and to shift the equilibrium to the product side
10. (a) Aniline is acetylated before nitration reaction in
to get the better yield. (1)
OR order to avoid formation of tarry oxidation products and
(a) Phenol into N-phenylethanamide protecting the amino group, so that p-nitro derivative can
be obtained as major product. (1)
Zinc dust conc. HNO3
OH NO2 (b) pKb of aniline is lower than the m-nitro aniline. The
conc.H2SO4
basic strength of aniline is more than m-nitroaniline.
Phenol Benzene Presence of electron withdrawing group decreases basic
Sn/HCl
strength. pKb value is inversely proportional to basic
CH3COCl, Pyridine strength. (1)
NHCOCH3 NH2 (c) Due to the presence of acidic hydrogen in the
Aniline (1) N-alkylbenzenesulphonamide formed by the treatment
(b) Chloroethane to methanamine of primary amines, it is soluble in NaOH. Secondary
amine forms N,N-dialkybenzenesulphonamide which due
Aq. NaOH KMnO4
C2H5Cl C2H5OH CH3COOH to the absence of acidic hydrogen on N-atom does not
Chloroethane dissolve in NaOH. (1)
NH3/Heat
(d) Aniline does not react with methylchloride in the
Br2/NaOH
CH3NH2 CH3CONH2 presence of AlCl3 catalyst, because aniline is a base and
Methanamine
AlCl3 is Lewis acid which lead to formation of salt. (1)
(1)
11. (a) N-Ethyl-N-methylbenzamine or
(c) Propanenitrile to ethanol
Br2/ N-Ethyl-N-methylaniline (1)
H3O+ NaOH NO NH NH2
CH3CH2CN NH , D CH3CH2CONH2 CH3CH2NH2 2 2
3
Br Br
Propanenitrile (i) HNO2 (ii) H2O Sn/HCl Br2/H2O NaNO2/HCl
(b) 273-278 K
CH3CH2OH
Ethanol (A)
Br
(1) (B)
7. (a) When N-ethylethanamine reacts with benzenesul‑ F N2+Cl–
phonyl chloride, N, N-diethylbenzenesulphonamide is formed.
(1) Br Br HBF4
Br Br
(b) When benzyl chloride is treated with ammonia, benzyl D
amine is formed which on reaction with chloromethane
yields a secondary amine, N-methylbenzylamine. (1) Br Br
(c) When aniline reacts with chloroform in the presence (D) (C) (2)
Amines 255
Self Assessment
Case Based Questions (5 marks) A & R Questions (1 mark)
In the following questions a statement of assertion
1. Read the passage given below and answer the
followed by a statement of reason is given. Choose the
following questions :
correct answer out of the following.
A mixture of two aromatic compounds (A) and (B) (a) Assertion and reason both are correct statements
was separated by dissolving in chloroform followed and reason is correct explanation for assertion.
by extraction with aqueous KOH solution. The (b) Assertion and reason both are correct statements
organic layer containing compound (A), when heated but reason is not correct explanation for assertion.
(c) Assertion is correct statement but reason is wrong
with alcoholic solution of KOH produce C7H5N (C)
statement.
associated with unpleasant odour.
(d) Assertion is wrong statement but reason is correct
(i) What is A? statement.
(a) C6H5NH2 (b) C6H5CH3
2. Assertion : Hoffmann bromamide reaction is given
(c) C6H5CHO (d) None of these by primary amide.
(ii) The reaction of (A) with alcoholic solution of Reason : Primary amines are more basic than
KOH to produce (C) of unpleasant odour is secondary amines.
called 3. Assertion : Acetanilide is less basic than aniline.
(a) Sandmeyer reaction Reason : Acetylation of aniline results in decrease of
(b) Carbylamine reaction electron density on nitrogen.
(c) Ullmann reaction Multiple Choice Questions (1 mark)
(d) Reimer-Tiemann reaction.
(iii) The alkaline aqueous layer (B) when heated 4. Which of the following methods of preparation of
amines will not give same number of carbon atoms
with chloroform and then acidified give a
in the chain of amines as in the reactant?
mixture of isomeric compounds of molecular
(a) Reaction of nitrile with LiAlH4.
formula C7H6O2. (B) is (b) Reaction of amide with LiAlH4 followed by
(a) C6H5CHO (b) C6H5COOH treatment with water.
(c) C6H5CH3 (d) C6H5OH (c) Heating alkyl halide with potassium salt of
(iv) In the chemical reaction, phthalimide followed by hydrolysis.
CH3CH2NH2 + CHCl3 + 3KOH (X) + (Y) (d) Treatment of amide with bromine in aqueous
solution of sodium hydroxide.
+ 3H2O,
the compounds (X) and (Y) are respectively 5. The correct increasing order of basic strength for
the following compounds is
(a) C2H5NC and KCl
NH2 NH2 NH2
(b) C2H5CN and KCl
(c) CH3CH2CONH2 and KCl
(d) C2H5NC and K2CO3
(v) Direct nitration of an aromatic compound (A) is
NO2 CH3
not feasible because
(I) (II) (III)
(a) the reaction cannot be stopped at the
(a) II < III < I (b) III < I < II
mononitration stage (c) III < II < I (d) II < I < III
(b) a mixture of o, m and p-nitroaniline is always
6. The best reagent for converting 2–phenylpropanamide
obtained
into 2-phenylpropanamine is .
(c)
nitric acid oxidises most of the aromatic
(a) excess H2
compound to give oxidation products along (b) Br2 in aqueous NaOH
with only a small amount of nitrated products (c) iodine in the presence of red phosphorus
(d) all of the above. (d) LiAlH4 in ether
7. Which of the following is the weakest Brönsted 16. Give increasing order of electrophilic substitution of
base? the following compounds :
NH2 CH3
(a) (b) N—H CH 3 + +
CH3 N CH3 N CH 3 CH2 N(CH3)3
CH3
NH2
(c) (d) CH3NH2

SA II Type Questions (3 marks)
OR
Reaction of aniline with HNO2 followed by treatment 17. Complete the following with appropriate structure :
1. NaNO and HCl at 5°C
of dilute acid gives (i) 2,4-dinitroaniline 
2

→ ( A)
2. anisole
(a) C6H5NHOH (b) C6H5OH HNO2
(c) C6H5NHNH2 (d) C6H6 (ii) N(CH3)2 (B)
VSA Type Questions (1 mark) 18. State the reason for the following :
(i) Acetylation of aniline reduces its activation
8. State reasons for the following : effect.
pKb value for aniline is more than that for ethylamine. (ii) Methylamine is more basic than aniline.
(iii) How is the basic strength of aromatic amines
9. Why is an alkylamine more basic than ammonia?
affected by the presence of an electron
10. How will you bring about the following conversion : releasing group on the benzene ring?
Aniline to chlorobenzene?
19. (a) Arrange the following in increasing order of
Write the chemical equation involved. basic strength : Aniline, p-nitroaniline and
11. How is the following conversion carried out : p-toluidine.
Aniline to p-hydroxyazobenzene ? (b) Account for the observation that like ammonia,
amines are good nucleophiles.
SA I Type Questions (2 marks)
OR
12. Suggest chemical reaction for the following Accomplish the following conversions :
conversions : (i) Benzyl chloride to 2-phenylethanamine
(i) Aniline to benzoic acid (ii) Aniline to p-bromoaniline
(iii) Benzamide to toluene
(ii) n-Hexanenitrile to 1-aminopentane
20. Explain the following observations :
13. Account for the following :
(i) In aqueous solution, the Kb order is
(i) Aqueous solution of methylamine reacts
Me2NH > MeNH2 > Me3N.
with iron(III) chloride to precipitate iron(III)
(ii) Why cannot primary aromatic amines be
hydroxide.
prepared by Gabriel phthalimide synthesis?
(ii) The boiling points of amines are lower than (iii) Tertiary amines do not undergo acylation
those of corresponding alcohols. reaction.
14. (i) Give reason : Silver chloride dissolves in
methylamine solution. Case Based Questions (4 marks)
(ii) Write the chemical reaction for the reduction 21. Read the passage given below and answer the
of nitroethane by LiAlH4. following questions :
15. (a) The diazonium ion acts as an electrophile. Give Amines are alkyl or aryl derivatives of ammonia
reason. formed by replacement of one or more hydrogen
(b) Write short note on Sandmeyer reaction. atoms. Alkyl derivatives are called aliphatic amines
and aryl derivatives are known as aromatic amines.
OR
The presence of aromatic amines can be identified by
(a) Complete the following series of reaction :
H performing dye test. Aniline is the simplest example
of aromatic amine. It undergoes electrophilic
PhNH2 A PhN2 Cl B
PhCN C Ph C NH2 substitution reactions in which —NH2 group strongly
H activates the aromatic ring through delocalisation of
(b) How is aminoethane obtained from ethanal? lone pair of electrons of N-atom. Aniline undergoes
Amines 257
electrophilic substitution reactions. Ortho and para OR

positions to the –NH2 group become centres of high (a) Write chemical equations for the following
electrons density. Thus, –NH2 group is ortho and conversions :
para-directing and powerful activating group. (i) Nitrobenzene to benzoic acid.
(a) How will you distinguish cyclohexylamine and (ii) Aniline to benzyl alcohol.
aniline? (b) Give the structures of A, B and C in the following
(b) What does oxidation of aniline in presence of reactions :
H O/H+ NH3
MnO2 and H2SO4 produce? (i) C6H5N2+Cl– CuCN A 2 B D C
(c) What is the major product obtained by Sn + HCl NaNO2 + HCl
(ii) C6H5NO2 A B
D 273 K
acetylation of aniline followed by nitration
D
(conc.HNO3 + conc.H2SO4) and then alkaline C
H2O/H+
hydrolysis?
24. (a) An aromatic compound ‘A’ on treatment with
OR
aqueous ammonia and heating forms compound
What does aniline produce in carbylamine ‘B’ which on heating with Br2 and KOH forms
reaction? Write chemical equation of the a compound ‘C’ of molecular formula C6H7N.
reaction involved. Write the structures and IUPAC names of
LA Type Questions (5 marks) compounds A, B and C.
(b) Write tests to distinguish the following pairs of
22. (i) Identify A, B and C in the following reactions : compounds:
KCN LiAlH4 HNO2 (i) Aniline and ethylamine
(a) CH3Br A B C
273 K (ii) Ethylamine and dimethylamine
NH3 Br2 + KOH CHCl3 + NaOH
(b) CH3COOH A B C NaNO2/HCl
D 25. (i) (a) C5H13N(X) Y (tertiary alcohol)
(ii) (a) How are amines prepared from amides? N2
Optically active + other products
(b) Acylation of amines with acid chloride is
Find X and Y. Is Y optically active? Write the
carried out in presence of stronger base.
intermediate steps.
Why?
(b) Which of the following is more acidic and
23. A hydrocarbon ‘A’ (C4H8) on reaction with HCl gives why?
a compound ‘B’ (C4H9Cl), which on reaction with NH3 NH3
1 mole of NH3 gives compound ‘C’ (C4H11N). On
reacting with NaNO2 and HCl followed by treatment
with water, compound ‘C’ yields an optically active
alcohol, ‘D’. Ozonolysis of ‘A’ gives 2 moles of F
acetaldehyde. Identify compounds ‘A’ to ‘D’. Explain (ii) Acetamide is less basic than ethanamine.
the reactions involved. Why?
Detailed SOLUTIONS
CHCl3 OH
1. (i) (a) : Given, mixture of (A) and (B)
+ KOH(aq) OH
Organic layer (A) + Alkaline aqueous layer (B) H+
C6H5OH + CHCl3 + KOH +
Organic layer on treating with KOH (alc.) produces Phenol (B) CHO
o-Hydroxy
(C7H5N) (C) of unpleasant odour and thus (C) is C6H5NC. CHO
benzaldehyde
Therefore, (A) is C6H5NH2. p-Hydroxy
benzaldehyde
(ii) (b) : Carbylamine reaction
(iv) (a) : CH3CH2NH2 + CHCl3 + 3KOH
C6H5NH2 + CHCl3 + 3KOH (alc.) C2H5NC + 3KCl + 3H2O
C6H5NC + 3KCl + 3H2O This is called carbylamine reaction.
Phenyl isocyanide (C)
(v) (c) : Direct nitration of aniline is not a feasible
(iii) (d) : Alkaline layer on treating with CHCl3 followed by process because nitric acid oxidises most of aniline to
acidification gives two isomers having formula (C7H6O2). give oxidation products along with only a small amount
This is Reimer-Tiemann reaction and thus, (B) is C6H5OH. of nitrated products.
2. (c) : Secondary amines are more basic than primary NH2 N2+ Cl–
amines.
NaNO2 + HCl CuCl/HCl
3. (a) : The lone pair of electrons on nitrogen of 10. 0 – 5°C
acetanilide interacts with oxygen atom due to resonance, Diazonium
Aniline Cl
which results in decrease in electron density on nitrogen Salt
hence, it is less basic than aniline.
4. (d) : Treatment of amide with Br2 in aqueous solution
Chlorobenzene
of NaOH will give an amine with one carbon atom less in HNO2 , HCl +
number than in the reactant. 11. NH2 0 – 5°C N NCl–
Br2/NaOH
RCONH2 RNH2 Benzenediazonium
chloride
NH2 NH2 NH2
+ OH
5. (d) : Phenol
CH3 (pH 9 – 10) 273– 278 K, OH–

NO2
II I III
Electron withdrawing group decreases the basic strength N N OH + Cl– + H 2O
while electron releasing groups increases the basic p-Hydroxyazobenzene (orange dye)
strength of aniline. NaNO2 + HCl +
12. (i) C6H5NH2 C6H5N2Cl–
CH3 CHCONH 2 CH 3CHCH 2NH2 273 K
Aniline Benzenediazonium
chloride
LiAlH4 +
Cu2(CN)2 H2O/H
6. (d) : + 4[H] + H2O C6H5CN C6H5COOH
ether Pyridine hydrolysis
Benzoic acid
2-Phenylpropanamide 2-Phenylpropanamine H+ / H2O
(ii) CH3CH2CH2CH2CH2CN
7. (a) : Aniline is the weakest base since NH2 is directly NH3
n-Hexanenitrile
attached to benzene ring and the unshared electron Br2/NaOH
CH3CH2CH2CH2CH2CONH2
pair on nitrogen is less available due to delocalisation. Hoffmann degradation
Hexanamide
Anilinium ion obtained by accepting a proton has only two CH3CH2CH2CH2CH2NH2
resonating structures making it less stable than aniline. 1-Aminopentane
OR 13. (i) Methylamine reacts with water to form methyl

ammonium hydroxide which is more basic than NH4OH
(b) : NaNO2 + HCl NaCl + HNO2 and ionizes to give OH– ions.
+
NH2 N +2Cl– CH3NH2 + H2O CH3NH3 + OH–
0 – 5°C FeCl3 + 3OH– Fe(OH)3 ↓ + 3Cl–
+ NaNO2 + 2HCl + 2H2O + 2NaCl Red brown ppt.
∆ H2O, H+ (ii) As oxygen is more electronegative than nitrogen
therefore, hydrogen bonding among alcohol molecules is
OH
stronger than among amine molecules. So, alcohols have
higher boiling points than amines.
Phenol 14. (i) Amines form soluble coordination compounds
with Ag+ ions. Therefore white ppt. of silver chloride is
8. In aniline, the lone pair of electrons on N-atom is
dissolved in methylamine solution.
delocalised over benzene ring due to resonance. As a
AgCl + 2CH3 NH2 [(CH3NH2)2Ag]Cl
result, electron density on the nitrogen atom decreases. Silver chloride Soluble
In contrast, in ethylamine, +I-effect of —C2H5 group (insoluble) complex
increases electron density on the nitrogen atom. LiAlH4
(ii) CH3CH2NO2 + 6[H] CH3CH2NH2 + 2H2O
Therefore, aniline is a weaker base than ethylamine ether
Nitroethane
hence, its pKb value is more than that for ethylamine.
15. (a) Due to positive charge on electronegative
9. Electron density of N-atom increases due to the +I nitrogen atom diazonium ion acts as an electrophile.
effect of the alkyl group. Hence, alkylamines are stronger (b) The Cl–, Br– and CN– nucleophiles can easily be
bases than ammonia. introduced in the benzene ring in the presence of Cu(I)
NH3 , R NH2 ion. This is called Sandmeyer reaction.
Amines 259
+ − Cu Cl due to the presence of COCH3 group, having –R effect,

2 2
ArN2 X → ArCl +N2 and hence, activation effect of aniline gets reduced.
HCl
(ii) In aniline, lone pair of electrons on nitrogen atom is
OR
not free for donation because it is involved in resonance.
NaNO2/HCl CuCN
PhN2Cl–
+
(a) PhNH2 But in case of methylamine, lone pair of electrons on
0 – 5°C
H nitrogen atom is free for donation. So, aniline is less basic
Sn/HCl than methylamine.
PhCN Ph C NH2
(iii) An electron releasing group increases the electron
H
H H density on the amino group. As a result, the electron
D density or the basic strength of the aromatic amine
(b) CH3 C O + NH3 CH3 C NH
–H2O increases.
Ethanal Acetaldimine
e.g. CH3 - C6H4 - NH2 > C6H5 - NH2
H2 / Ni
CH3CH2NH2 19. (a) Electron withdrawing group (–NO2) on benzene
Ethanamine ring decreases the basicity and electron donating group
16. Higher the electron density in the benzene ring, more
(–CH3) on benzene ring increases the basicity of the
reactive is the aromatic compound towards electrophilic
compound. Increasing order of basic strength :
substitution reaction. Now due to the presence of a lone
p-nitroaniline < aniline < p-toluidine
pair of electrons on the N-atom which it can directly
(b) Amines (like ammonia) are good nucleophiles. It is
donate to the benzene ring, —N(CH3)2 is a much stronger
because alkyl group in an amine shows electron releasing
electron donating group than —CH3 group. The remaining
effect. This increases the electron density on ‘N’ of amino
two groups contain a positive charge on the N-atom
group. This makes the amines very good nucleophiles.
and hence, act as electron withdrawing groups. But in
R NH2
—N+(CH3)3 group, the positively charged N is directly
(+I effect)
attached to the benzene ring, therefore, its electron
withdrawing ability is much stronger than —CH2N+(CH3)3. OR
Thus, the electron density in the benzene ring increases (i) CH 2Cl CH2 CN
in the order :
+ + KCN(alc.), Heat
N (CH3 )3 CH 2 N (CH3 )3 CH3 N(CH3 )2
– KCl
< Benzyl chloride

LiAlH4
Therefore, their reactivity towards electrophilic

CH 2CH2 NH 2
substitution reactions also increases in the same order.
17. (i)
NH2 N2Cl
NO2 2-Phenylethanamine
NaNO2/HCl
NO2 O -CH3
NH 2 NHCOCH 3
0-5°
(CH3 CO)2 O/
NO2 NO2 (ii)
CH 3 COOH
O2N N=N OCH3 Aniline Acetanilide
Br2 CH 3 COOH
NO2 (A)
NO NH 2 NHCOCH3
HNO2
(ii) N(CH3)2 H2O /OH –
N(CH3)2
Br Br
18. (i) After acetylation of aniline, acetanilide is p-Bromoaniline p-Bromoacetanilide
formed in which electron density on N-atom decreases (Major product)
(iii) NH 3 Br2 + KOH

CONH 2 NH 2 (b) CH3COOH ∆
CH 3CONH2
(A)
NaNO 2 /HCl
Br2 / NaOH, Heat 273-278K CHCl 3 + NaOH
(Diazotisation) CH3 NC CH3 NH 2
(C) (B)
Benzamide Aniline
+ (ii) (a) Amides on reduction with LiAlH4 or by reaction
CH3 N2Cl–
with Br2 in presence of alkali give amines.
H3PO2-H2O/Cu,
O
Heat
(i) LiAlH4
R C NH2 R CH2 NH2
(ii) H2O
Toluene Benzene
Benzenediazonium O
chloride –
2 Br + OH
R C NH2 R NH2
20. (i) In alkyl amines, a combination of +I effect
of alkyl groups, steric factors and H-bonding factors (b) During acylation reaction HCl acid is formed. In
determine the stability of ammonium cations in aqueous order to remove HCl and shift the equilibrium to the right
solution. All these factors are favourable for 2° amines hand side a stronger base like pyridine is added.
and for smaller alkyl group, stability due to hydrogen Pyridine
R — NH2 + R′COCl R — NHCOR′ + HCl
bonding predominates over the stability due to +I effect.
Consequently, we get the given Kb order : 23. Since A undergoes ozonolysis it means it is an alkene.
Me2NH > MeNH2 > Me3N C gives diazonium salt that liberates N2 and optically
(ii) Aromatic amines cannot be prepared by Gabriel active alcohol. It shows C is an aliphatic amine. Product
phthalimide synthesis because aryl halides do not of ozonolysis is CH3CHO hence A is CH3CH CHCH3.
undergo nucleophilic substitution with the anion formed HCl
by phthalimide. CH3CH CHCH3 CH3CH2CH CH3
(iii) Tertiary amines do not undergo acylation reaction But-2-ene
(A) Cl
because they do not contain any H-atom on the nitrogen 2-Chlorobutane
atom. CH3 (B)
21. (a) Azo dye test is used to distinguish between NaNO2/HCl NH3
CH3CH2 C H CH3CH2CHCH3
cyclohexylamine and aniline. H2O
NH2 O OH NH2
Butan-2-ol 2-Aminobutane
MnO2/H2SO4 optical active alcohol
(b) (D)
(C)
O3
CH3CH CHCH3 2CH3CHO
O Zn + H2O
p-Benzoquinone (A) Acetaldehyde
NH2 NHCOCH3 NHCOCH3 OR

+
(c) CH3COCl HNO3/H2SO4 NO2 NH 2 N2 Cl –
Sn/HCl NaNO 2 / H Cl
Aniline (a) (i)
NH2 NO2 273– 278 K
(Major) Nitrobenzene CuCN
OH–
H2O COOH CN
NO2 H2O/H +
p-Nitroaniline
OR Benzoic acid
Aniline gives phenyl isocyanide in carbylamine reaction. + –
NH 2 l CN
NH2 N C 2
NaNO 2 /HCl CuCN

CHCl3 (ii) 273– 278 K
alc. KOH
Aniline LiAlH4
KCN LiAlH 4
22. (i) (a) CH3 Br CH 3CN CH3 CH 2NH 2 CH 2 OH CH2 NH2
(A) (B)
HNO2
HNO2 273– 278 K
CH 3CH 2OH 273 K
(C) Benzyl alcohol
Amines 261
CuCN H2O/H+ CH3

(b) (i) C6H5N2+Cl– C6H5CN
NaNO2/HCl
Benzonitrile 25. (i) (a) CH3 CH CH CH3
(A)
NH3 (X)
C6H5CONH2 C6H5COOH NH2
D
Benzamide Benzoic acid CH3
(C) (B)
Sn + HCl NaNO2 + HCl CH3 CH CH2 CH3 + N2↑+ NaCl + H2O
(ii) C6H5NO2 C6H5NH2
273 K
(A) OH
H2O Y (rearranged product)
C6H5OH
D
C6H5N2+Cl– CH3 CH3
(C) (B) NaNO2/HCl
24. (a) Formula of the compound ‘C ’ indicates it is an CH3 CH CH CH3 CH3 C CH CH3
–N2
amine. Since it is obtained by the reaction of Br2 and KOH NH2 H
with the compound ‘B’ so compound ‘B’ can be an amide. (X)
As ‘B’ is obtained from compound ‘A’ by reaction with CH3
ammonia followed by heating so, compound ‘A’ could be 1,2-H–shift H2O
an acid. Formula of compound ‘C ’ shows it to be aniline, CH3 C CH2 CH3
+
then ‘B’ is benzamide and compound ‘A’ is benzoic acid. CH3
The sequence of reactions can be written as follows : CH3 C CH2 CH3
COOH CONH 2 NH2
OH
NH3 Br2 /KOH (Y)
∆ optically inactive
A B C NH3+
(b) (i) Aniline gives white or brown precipitate with
bromine water. (b) is more acidic due to the strong electron
NH2 NH2
Br Br F
+ 3Br2 + 3HBr withdrawing power (–I effect) of fluorine.
O O
Br
(white ppt.) (ii) CH3 C NH2 CH2 C NH2 , CH3CH2NH2
Acetamide Ethanamine
Ethylamine does not react with bromine water.
(ii) When heated with an alcoholic solution of KOH and In acetamide, lone pair on nitrogen atom is involved in
CHCl3, ethylamine gives foul smelling ethyl isocyanide. resonance and hence is not free for donation as in the
Dimethylamine does not give this test. case of ethanamine.

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230 CBSE Champion Chemistry Class 12

Analysis of Last 10 Years’ CBSE Board Questions (2023-2014)

Topic 9.6 is highly scoring topic.

Primary (1°) Amines Secondary (2°) Amines Tertiary (3°) Amines

Simple Mixed Simple Mixed

Test Primary amine Secondary amine Tertiary amine

NH2 NH2 NH2

DIAZONIUM SALTS C6H5NH2 + NaNO2 + 2HCl

X Reactions involving retention of diazo group (coupling reactions) :

Amines Aniline Diazonium Salts

9.2 Classification 10. CH3CONH2 on reaction with NaOH and Br2 in

Br  (Delhi 2016) U 16. Complete the following :

the structures and IUPAC names of compounds

VSA (1 mark) (iii) In decreasing order of their pKb values :

VSA (1 mark) 61. Account for the following :

(a) (CH3)2-N NH SA II (3 marks)

9.4 Preparation of Amines 9.6 Chemical Reactions (Amines)

COOH COONH4+ (ii) R-CONH2 + Br2 + 4NaOH → R-NH2 + Na2CO3

NO2 NH2 than even ammonia due to electron withdrawing nature

(CH3)2NH > CH3NH2 > (CH3)3N O

O (ii) Acetylation of amines : The process of introducing

80. (a) (i) Methylamine gives carbylamine test, i.e., on H2O +

NaNO2 + HCl CuCN

Â -C-CH3 group exerts –I-effect on adjacent -NH2 273-278 K

group. NH2 N2+Cl–

90. Diazotisation reaction. 95. (a) The replacement of group of benzene

94. (i) C6H5NO2

Br2 + KOH NaNO2

COOH COONH4+ CONH2 CONH2 NH2

[Topper’s Answer, 2022]

COOH COONH4+ CONH2 N2+Cl– F

(II) KCN LiAlH4

4. (a)(1) of alcoholic potassium hydroxide, phenyl isocyanide or

(c) (d) CH3NH2

electrophilic substitution reactions. Ortho and para OR

CH3 (pH 9 – 10) 273– 278 K, OH–

OR 13. (i) Methylamine reacts with water to form methyl

+ − Cu Cl due to the presence of COCH3 group, having –R effect,

< Benzyl chloride

Therefore, their reactivity towards electrophilic

(iii) NH 3 Br2 + KOH

NH2 NHCOCH3 NHCOCH3 OR

NaNO 2 /HCl CuCN

CuCN H2O/H+ CH3

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Br (Delhi 2016) U 16. Complete the following :

4. (a)(1) of alcoholic potassium hydroxide, phenyl isocyanide or