Amines 1

Level-I
Chapter 14
Amines
Solutions (Set-1)
Very Short Answer Type Questions :

1. Write the IUPAC name of following compound.
CH3
CH3CH2CH2 N
C2H5
Sol. N-Ethyl-N-methylpropan-1-amine
2. What does Kb value for a base stand for?
Sol. Kb stands for dissociation constant of a base. It determines basic strength of a base. Higher the value of Kb,
stronger base is the base.
3. How is phenol obtained from aniline?
NH2 N2Cl OH
+
NaNO2 + dil. HCl Boiling H2O / H
Sol. 273 - 278 K
Aniline Benzenediazonium Phenol

chloride
4. Give a chemical test to distinguish between primary and secondary amines.

Sol. Carbylamine reaction : Primary amine will form offensive smelling isocyanide whereas secondary amine does
not give this reaction.
5. Why do amines behave as nucleophiles?
Sol. They act as nucleophiles because there is a lone pair of electrons on N which it can donate.
6. Why primary amines have higher boiling point than tertiary amines?
Sol. Primary amines are associated due to H-bonding. Tertiary amine have no hydrogen bond.
7. State the reaction taking place when : Bromine water is added to the aqueous solution of aniline.
NH2 NH2
Br Br
Sol. + 3Br2 (aq) + 3HBr
Br
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
54 Amines Solutions of Assignment (Level-I) (Set-1)
8. How is the basic strength of aromatic amines affected by the presence of an electron-releasing group on the
benzene ring?
Sol. Basic strength of aromatic amines is increased by the presence of electron releasing group, due to increase
in electron density on the amino group.
9. Arrange the following in the order of their increasing basic character in solution :
NH3, C2H5NH2, (C2H5)2NH, (C2H5)3N
Sol. NH3 < C2H5NH2 < (C2H5)3N < (C2H5)2NH
10. Account for the following : Ammonolysis of alkyl halide does not give a corresponding amine in pure state.
Sol. This is because the amine formed reacts further with more of the alkyl halide to give 2°, 3° amines and finally
quaternary salt. Thus, a mixture of amines is obtained.
Short Answer Type Questions :

11. (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 of basic strength in gas phase :
C2H5NH2, (C2H5)2NH, (C2H5)3N and CH3NH2
Sol. (i) Out of the amines, aromatic amine C6H5NH2 is the weakest base followed by NH3. For aliphatic amines,
the basic strength is a function of inductive effect, solvation effect and steric effect of the alkyl group.
Increasing order of basic strength, keeping in view all these factors is :
C6H5NH2 < NH3 < (C2H5)3N < (C2H5)2NH (in aqueous solution)
(ii) In the gas phase, only the inductive effect of the alkyl group determines the basic strength of the base.
Greater the number of alkyl groups attached to the nitrogen, greater is the electron density and hence
greater is the basic strength. Methyl group being smaller than ethyl group exerts smaller +I effect,
therefore methylamine is weakest base. The increasing order of basic strength of the given compounds
in the gas phase is :
CH3NH2 < C2H5NH2 < (C2H5)2NH < (C2H5)3N
12. Account for the following :
(i) Amines are basic substances while amides are neutral.
(ii) Aromatic amines are weaker bases than aliphatic amines.
Sol. (i) In amines, alkyl group is electron releasing which increases electron density on nitrogen making them
O
basic whereas in amides R C group is electron withdrawing, therefore, they are neutral.
(ii) It is because aryl group is electron withdrawing which decreases electron density on nitrogen making them
less basic whereas alkyl group is electron releasing which makes alkylamines more basic. Moreover, the
lone pair of electrons on N in aromatic amine is delocalised due to resonance with benzene ring.
13. (a) How will you convert an alkyl halide to a primary amine having one more carbon atom than the parent
alkyl halide?
(b) Why are amines more basic than corresponding alcohols?
Na / C2H5OH
Sol. (a) CH3Cl + KCN CH3C N CH3CH2NH2
4[H]
Chloromethane Ethanenitrile Ethanamine
(b) Oxygen is more electronegative than nitrogen. Therefore, oxygen has less tendency to donate the
electrons compared to nitrogen. That is why amines containing N are more basic than alcohols containing
oxygen.
Solutions of Assignment (Level-I) (Set-1) Amines 55
14. Give reasons for the following observations :
(i) It is difficult to prepare pure amines by ammonolysis of alkyl halides.
(ii) Electrophilic substitution in case of aromatic amines takes place more readily than in benzene.
Sol. (i) It is because primary amines formed react with more alkyl halide to form 2° and 3° amines. That is why
we get mixture of amines, which need to be separated.
(ii) It is because –NH2 group is electron releasing and increases electron density on benzene ring.
15. Identify A and B in the following reactions :
LiAlH4 HNO2
(i) C2H5C N A B
NH2
Br2 NaNO2 / HCl

(ii)
H2O
A B
273 K
LiAlH4 HNO2
Sol. (i) C2H5C N C2H5CH2NH2 C2H5CH2OH
Propanenitrile (A) (B)
Propanamine Propanol
NH2 NH2 N2Cl

Br2 Br Br NaNO2 / HCl Br Br
(ii)
H2O 273 K
Br Br
(A) (B)
2, 4, 6-Tribromoaniline 2, 4, 6-Tribromobenzene
diazonium chloride
16. State the reactions for obtaining benzoic acid from aniline.
NH2 N2Cl CN COOH

+
NaNO2 / HCl CuCN H2O / H
Sol. 273 - 278 K KCN
Aniline Benzene Benzonitrile Benzoic acid

diazonium chloride
17. Before reacting aniline with HNO3 for nitration, it is converted to acetanilide. Why is this done and how is
nitroaniline obtained subsequently?
Sol. It is because aniline gets oxidised, protonated and gives 47% m-nitroaniline on direct nitration. Therefore, it
is converted into acetanilide and then nitrated. Anilide group activates the ring at o- and p-positions. We get
o- and p-nitroacetanilide which on hydrolysis gives o- and p-nitroaniline.
18. For the following conversion reactions write the chemical equations :
(i) Ethylisocyanide to ethylamine
(ii) Aniline to N-phenylethanamide
+
H
Sol. (i) C2H5NC + 2H2O C2H5NH2 + HCOOH
Ethylisocyanide Ethylamine Methanoic acid
NH2 NHCOCH3
NaOH
(ii) + CH3COCl + HCl
Aniline N-Phenylethanamide
19. Give reason :
(i) C 6H 5N (CH 3) 3OH is stronger base than NH4OH.
(ii) Aniline is acetylated to prepare monobromo derivative.
+
Sol. (i) C6H5N (CH3)3 is more stable than NH4 because methyl groups are electron releasing whereas hydrogen
is not.
(ii) Aniline is acetylated to deactivate –NH2 group so as to prepare monobromo derivative. Otherwise, we would
get tribromo derivative.
20. Account for the following :
(i) Aniline is weaker base than methylamine.
(ii) Aryl cyanides can not be formed by the reaction of aryl halides and sodium cyanide.
Sol. (i) Aniline is weaker base than methylamine because C6H5 group is electron withdrawing in aniline whereas
CH3 group is electron releasing in methylamine. Moreover, lone pair of electrons on N in aniline is
delocalised due to resonance with benzene ring. This reduces electron density on amino group in aniline.
(ii) It is due to double bond character between carbon and halides in aryl halides which cannot be broken
easily. Therefore, Cl cannot be easily replaced by –CN to get aryl cyanide.
21. How will you convert :
(i) Nitrobenzene to phenol
(ii) Aniline to chlorobenzene
NO2 NH2 N2Cl OH
Sn / HCl NaNO2 / HCl H2O

Sol. (i) + 6[H]
273 - 278 K boil
Nitrobenzene Aniline Phenol
NH2 N2Cl Cl
273 - 278 K HCl

(ii) + NaNO2 + HCl + N2
CuCl
Aniline Chlorobenzene
22. What is the role of HNO3 in the nitrating mixture used for nitration of benzene?
Sol. HNO3 acts as a base in the nitrating mixture (Conc. HNO3 + Conc. H2SO4). H2SO4 acts on HNO3 to generate
+
the electrophile, NO2 (nitronium ion)
+ –
H2SO4 H + HSO4
H
+
H + +
HONO2 O NO2 NO2 + H2O
H
23. Predict the product of reaction of aniline with bromine in non-polar solvent such as CS2.
Sol. In non-polar solvents, the resonance structures involving separation of +ve and –ve charges are not stabilized
by dipole-dipole interactions with the non polar solvent. As a result, activating effect of the NH2 is reduced and
hence monosubstitution occurs only at o- and p-positions giving a mixture of 2-bromoaniline (minor) and 4-
bromoaniline (major).
24. A compound Z with molecular formula C3H9N reacts with C6H5SO2Cl to give a solid, insoluble in alkali.
Identify Z.
Sol. Since the amine Z on treatment with C6H5SO2Cl gives a product which is insoluble in alkali, therefore, the
product does not have a replaceable hydrogen on the N-atom. In other words, the amine Z is a 2° amine. The
only 2° amine having the molecular formula C3H9N is ethylmethylamine, i.e., the amine (Z) is ethylmethylamine,
CH3CH2NHCH3.
25. A primary amine, RNH2 can be reacted with CH3 – X to get secondary amine, R – NHCH3 but the only
disadvantage is that 3° amine and quaternary ammonium salts are also obtained as side products. Can you
suggest a method where RNH2 forms only 2° amine.
Sol. 1° amines react with CHCl3 in presence of alcoholic KOH to form isocyanides which upon catalytic reduction
give 2° amines.
KOH / CHCl3 H2 / Pt
R NH2 R N C R NH CH3
(Carbylamine reaction) (Catalytic reduction)
1° amine 2° amine
26. Suggest a route by which the following conversion can be accomplished :

O
C NH2 NH CH3
C NH2 Br2 / KOH NH2 CHCl3 / KOH N C

Sol.
(Hofmann bromamide reaction)
Cyclohexylamine Cyclohexyl carbylamine
H2 / PCl
NHCH3
N-Methylcyclohexylamine
27. How is classification of amines different from that of alcohols?

Sol. Classification of amines is made on the basis of the nature of nitrogen atom (whether it has one, two or no
hydrogen atom) to which the alkyl groups are attached. The classification of alcohols, on the other hand, is
made on the basis of the nature of carbon atom to which the –OH group is attached.
–NH2 NH N –CH2OH CHOH C OH

1° amine 2° amine 3° amine 1° alcohol 2° alcohol 3° alcohol
28. Although trimethylamine and n-propylamine have the same molecular weight, the former boils at a lower
temperature (276 K) than the later (332 K). Explain.
Sol. n-Propylamine has two H–atoms on the N-atom and hence undergoes intermolecular H-bonding thereby raising
its boiling point.
Trimethylamine, (CH3)3N being a 3° amine does not have a H-atom on the N-atom. As a result, it does not
undergo H-bonding and hence its boiling point is low.
29. Why is it necessary to add excess of mineral acid during diazotisation of amines?
Sol. During diazotisation of arylamines, excess of mineral acid is used. In general, one mole of amine is treated
with approximate three moles of acid : (i) one mole to dissolve the amine, (ii) one mole to liberate HNO2 from
NaNO2 and (iii) one mole to maintain the proper acidity of the reaction mixture to prevent the coupling of
diazonium salt.
30. How will you carry out the following conversion?

NO2
NH2
NO2 NH2 NHCOCH3

Conc. HNO3 + Conc. H2SO4 Sn / HCl (CH3CO)2O / Pyridine
Sol.
(Nitration)
Benzene Nitrobenzene
NH2 NHCOCH3
+
H / H2O Conc. HNO3
Conc. H2SO4
NO2 NO2
p-Nitroaniline p-Nitroacetaniline
Long Answer Type Questions :

31. Account for the following observations :
(i) pKb of aniline is more than that of methylamine.
(ii) Aniline does not undergo Friedel-Crafts reaction.
Sol. (i) Lone pair of electrons on nitrogen in aniline is delocalised due to resonance with benzene ring. Thus,
electron density on the amino group in aniline decreases. Consequently, its basic strength also decreases.
On the other hand, electron density on amino group in methylamine increases due to +I effect of CH3
group. Thus, it has a greater basic strength (Kb). pKb and Kb are inversely related. Therefore, pKb for
aniline is more than that for methylamine.
(ii) AlCl3 is used as a catalyst in Friedel Crafts reaction. AlCl3 is a Lewis acid (electron deficient). AlCl3 gets
attached to the lone pair of electron in aniline. Amino group is thus not able to activate the benzene ring
for electrophilic substitution. Moreover electrophiles like CH3 and CH 3CO are not formed as the catalyst
is consumed in association with amino group. Therefore, aniline does not undergo Friedel Crafts reaction.
32. State the reactions and reaction conditions for the following conversions :
(i) Benzene diazonium chloride to nitrobenzene
(ii) Aniline to benzene diazonium chloride
(iii) Ethanamide to methylamine
+ –
N2Cl N2 BF4 NO2
NaNO2
Sol. (i) + HBF4 + N2 + NaBF4
Cu
Fluoroboric
acid Benzene diazonium
tetrafluoroborate
+ –
NH2 N2 Cl
273 - 278 K
(ii) + NaNO2 + HCl + NaCl + 2H2O
Aniline
(iii) CH3CONH2 + Br2 + 4KOH CH3NH2 + K2CO3 + 2KBr + 2H2O

Ethanamide Methylamine
33. How would you achieve the following conversions :
(i) Nitrobenzene to aniline
(ii) An alkyl halide to a quaternary ammonium salt
(iii) Aniline to benzonitrile
Write the chemical equation with reaction conditions in each case.
NO2 NH2
Sn / HCl
Sol. (i) + 6[H] + H2O
Nitrobenzene Aniline
C2H5Cl C2H5Cl C2H5Cl + –

(ii) C2H5Cl + NH3 C2H5NH2 (C2H5)2NH (C2H5)3N (C2H5)4N Cl
Chloroethane Ethanamine N-Ethylethanamine N, N-Diethylethanamine Tetraethylammonium
chloride
NH2 N2Cl C N
NaNO2 + HCl CuCN

(iii)
273 - 278 K
Aniline Benzonitrile
34. (i) Stating the necessary reaction conditions write chemical reaction equations to obtain the following :
Chlorobenzene from aniline
(ii) Identify A and B in the following :
CH2Br
–
CN LiAlH4
(a) A B
NH3 Ni / H2
(b) R2CO A B
+ –
NH2 N2 Cl Cl
NaNO2 + HCl CuCl
Sol. (i)
273 - 278 K HCl
Chlorobenzene
CH2Br CH2CN CH2CH2NH2

–
CN LiAlH4
(ii) (a)
Bromomethyl (A) (B)

benzene Benzyl cyanide 2-Phenylethanamine
NH3 Ni / H2
(b) R2CO R C NH R CH NH2
Ketone
R R
(A) (B)
Dialkylethanamine
35. Why is NH2 group of aniline acetylated before carrying out nitration?
Sol. Due to strong activating effect of NH2 group, aromatic amines readily undergo electrophilic substitution reactions
and it is difficult to stop the reaction at the mono substitution stage. Usually the reaction occurs to give 2,
4, 6-trisubstituted amines. For example, aniline on treatment with bromine water gives 2, 4, 6-tribromoaniline.
If, however, we wish to stop the reaction at the monosubstitution stage, the activating effect of the –NH2 group
is reduced by acetylation. The acetyl group being electron withdrawing attracts the lone pair of electrons on
the N-atom towards itself.
–
O O
..
H N C CH3 H N C CH3
As a result, the lone pair of electrons on the N-atom is not exclusively available for donation to the benzene
ring and hence the activating effect of the –NH2 group is reduced. This method is known as protection of the
amino group by acetylation and can be used to stop the reaction at the monosubstitution stage by preventing
the formation of di- and trisubstitution products. For example, acetylation of aniline gives acetanilide. Bromination
of acetanilide with Br2/CH3COOH followed by acid hydrolysis gives p-bromoaniline as the major product.
36. tert-Butylamine can not be prepared by the action of NH3 on tert-butyl bromide. Explain why.
Sol. Tert-butyl bromide a 3° alkyl halide on treatment with a base prefers to undergo elimination rather than
substitution. Therefore, the product is isobutylene rather than tert butylamine.
CH3
NH3
CH3 C Br X
(Substitution)
CH3
tert-Butyl bromide
CH2 H CH3
..
CH3 C Br + NH3 CH3 C CH2
Elimination
CH3 Isobutylene
37. Why does bromination of aniline, even under very mild conditions, gives 2,4, 6-tribromoaniline instantaneously?
Sol. Due to strong electron donating effect of the –NH2 group, the electron density increases at the o-, p-positions.
Further, when aniline is treated with Br2, the Br+ attacks the benzene ring at o- and p-positions to form
carbocation intermediates which are stabilized not only by the usual resonance of the benzene ring but also
by the –NH2 group as shown below :
o-Bromination :
..
NH2 NH2 NH2 NH2 NH2
+
H H H H
Br
Br Br Br Br
(I) (II) (III) (IV)

p-Bromination :
NH2 NH2 NH2 NH2 NH2
+
+ Br
H Br H Br H Br H Br
(V) (VI) (VII) (VIII)
In case of o-bromination, the carbocation intermediate is stabilized not only by usual resonating structure (I,
III and IV) but is also stabilized by resonance structure (II) in which the lone pair of electrons on the N-atom
interacts with the positively charged carbon of the ring. Similarly, in case of p-bromination, the carbocation is
stabilized not only by the usual resonating structures (V, VI and VIII) but is also stabilized by the resonance
structure (VII) in which the lone pair of electrons on the N-atom interacts with the positively charged carbon
of the ring. These additional resonating structures (II and VII) increase the stability of the carbocation to such
an extent that bromination occurs instantaneously at p- and two o-positions giving 2, 4, 6-tribromoaniline.
38. Arrange the following amines in order of decreasing basicity :
N N N N
H H H
(I) (II) (III) (IV)
Sol. (i) In compound II (pyridine), the lone pair of electrons on N is present in a sp2 orbital while in compounds
I (piperidine) and III (morpholine), the lone pair of electrons on N is present in a sp3 orbital. Since a sp2-
orbital has more s-character (33.33%) than a sp3 orbital (25%), therefore, the lone pair of electrons on
N is more readily available for protonation in I and III than in II. In other words, compound (II) is less basic
than I and III. Among I and III, III contains an oxygen atom which has –I effect. As a result, it will attract
the lone pair of electrons on N towards itself. Consequently, the lone pair of electrons on N in III is less
readily available for protonation than in I. In other words, compound I is more basic than III.
(ii) Compound IV (pyrrole) is aromatic in character. Therefore, in accordance with Huckel’s rule it has a cyclic
cloud of six-π electrons. Out of these, four are contributed by two double bonds while the remaining two
are the lone pair of electron on the N-atom.
In other words, the lone pair of electrons on N-atom is contributed towards the aromatic sextet formation
and hence is not at all available for protonation. Therefore, compound IV is the least basic. In fact, it is
such a weak base that it is weakly acidic in character and thus reacts with K metal when heated to form
the corresponding potassium salt.
Thus, the basicity of the above four compounds decreases in order.
I > III > II > IV
39. Identify A and B in the following reactions :
NO2
NaNO2, HCl CuCl

(i) A B
NH2 273 K
NaCN LiAlH4
(ii) CH3CH2CH2Br A B
NO2
H2SO4 / SO3 Fe / HCl

(iii) 373 K
A B
NO2 NO2 NO2
NaNO2, HCl CuCl

Sol. (i) + –
NH2 273 K N Cl
2 Cl
(A) (B)
3-Nitrobenzene 3-Chloronitrobenzene
diazonium chloride
NaCN LiAlH4
(ii) CH3CH2CH2Br CH 3CH 2CH 2C N CH3CH2CH2CH2NH2
(A) (B)
Butanenitrile Butanamine
NO2 NO2 NH2
H2SO4 / SO3 Fe / HCl

(iii)
333 K SO3H SO3H
Nitrobenzene (A) (B)

m-Nitrobenzene m-Aminobenzene
sulphonic acid sulphonic acid

Level-I
Chapter 14
Amines
Solutions (Set-2)
[Method of preparation]
1. Which of the following reagent converts nitrobenzene to aniline?
(1) Sn/HCl (2) Zn/NH4OH (3) Zn/NaOH (4) LiAlH4
Sol. Answer (1)
NO 2 NH2
Sn/HCl
–
OH
2. Final product of the following sequence of reactions would be

O
⊕
NH2OH H LiAlH4
[A] [B] Product
O OH
N
(1) (2) H2N
N
(3) H2N (4)
Sol. Answer (4)
HO H
H
|
O N O |
|| || N
N C
NH2OH H+ LiAlH4
Beckmann
Rearrangment
(A) (B)
3. Consider the following sequence of reaction.
O
Cl C
OOH
NaN3 H2 / Pd
[A] [B] [P]
CH2Cl2
The product [P] would be
H NH2 N3 NH2
NH2 H H H
(1) (2) (3) (4)
OH OH OH NH2
H H H H
Sol. Answer (2)
O
H N3 NH2
–
–
Cl C–O–O–H
NaN3 H H /Pd H
O
2
CH2Cl2 OH OH
[A] H [B] H [C] H
NaCN Ni/H Acetic

4. CH3 CH2Cl ⎯⎯⎯⎯
→ X ⎯⎯⎯⎯
2
→ Y ⎯⎯⎯⎯⎯
anhydride
→Z.
Z in the above reaction sequence is

(1) CH3CH2CH2 NHCOCH3 (2) CH3CH2CH2NH2
(3) CH3CH2CH2CONHCH2 (4) CH3CH2CH2CONHCOCH3
Sol. Answer (1)
NaCN Ni/H 2
CH3CH2Cl CH3CH2CN CH3CH2CH2NH2
(X) (Y)
O
CH3COOCOCH 3
CH3 COOH + CH3CH2 CH2NH C CH3
5. Which of the following is most basic?
(1) CH 3O NH2 (2) O 2N NH2 (3) Cl NH2 (4) NH2
Sol. Answer (1)

When connected with o- or p- carbon of benzene –o–Me group is electron releasing.
6. The order of nucleophilicity among Ph—NH2, Et-NH2, Ph—NH—NH2, NH2—C—NH—NH2

I II III IV
(1) I > II > IV > III (2) II > III > I > IV (3) II > III > IV > I (4) III > IV > I > II
Sol. Answer (3)
7. Which is more basic?
(1) Benzylamine (2) Aniline (3) Acetamide (4) o-methyl aniline
Sol. Answer (1)
CH2NH2
In Benzylamine , lone pair of electrons on nitrogen atom remain localised, therefore it is more
basic than other.

8. The correct increasing order of basic strength for the following compounds is
NH2 NH2 NH2
NO2 CH3
(I) (II) (III)
(1) II < III < I (2) III < I < II (3) III < II < I (4) II < I < III
Sol. Answer (4)
Presence of EDG, increases and EWG, decreases the basic strength of aniline.
9. Which one is the most volatile?
CH2
(1) CH3CH2CH2NH2 (2) (CH3)3N (3) NH (4) CH3OH
CH 3
Sol. Answer (2)
(CH3)3N does not form hydrogen bond due to unavailability of hydrogen atom attached with nitrogen. Due to
absence of hydrogen bonding, (CH3)3N is more volatile.
[Reactions]
10. Which of the following give isocyanide test?
NH2
NH CH3
(1) (2) (3) CH3 N CH3 (4) (CH3)2NH
Sol. Answer (1)

Only primary amine can give iso cyanide test i.e. carbyl amine reaction.
11. A mixture containing primary, secondary and tertiary amine is treated with diethyl oxalate. Choose the correct
statement
(1) The distillate of the mixture after treatment mainly contains 1° amine
(2) 3° amine do not react with diethyl oxalate
(3) This is Hinsberg method of separating 1°, 2° & 3° amines
(4) 3° amine is removed by filtration
Sol. Answer (2)
3° amine do not react with diethyl oxalate. This is the Hofmann’s method not Hinsberg’s method.
( CH CO ) O
12. CH3CH2NH2 ⎯⎯ ⎯
3
⎯2⎯→ A + B. (A) and (B) are
Δ
(1) CH3CH2NHCOCH3 + CH3CH2N ≡ C (2) CH3CH2NO2 + CH3COOH

(3) CH3CH2NHCOCH3 + CH3COOH (4) CH3CH2NO2 + CH3CH2NHCOCH3
Sol. Answer (3)
( CH3 CO )2 O
CH3CH2-NH2 ⎯⎯ ⎯Δ⎯ ⎯→ CH3CH2NHCOCH3 + CH3COOH. This is the acetylation of ethyl amine.
13. End product of the given reaction sequence is
(i) CHCl3/KOH (ii) H2 / Pd

— NH2 Δ 100ºC,
High pressure
(1) — NH — CH3 (2) — CH2 — NH2
(3) — NH — CH3 (4) NH2
CCl3
Sol. Answer (3)

(i) CHCl3/KOH ⊕ –
N—
H2/Pd
NH2 Δ —C NH — CH3
100°C
H2/Pd removes all the double bonds even in the ring at high temperature and high pressure.
14. Among the following compounds, which one will produce an enamine on reaction with cyclohexanone?
CH3
N N—H NH2 NH2
(1) (2) (3) (4)
CH3
Sol. Answer (2)

Secondary amine reacts with cyclohexanone to give enamine.
O
||
N H+ N
Enamine
15. An optically active compound [A] C5H13N reacts with alkaline CHCl3 to give an optically active compound [B].
[A] also reacts with nitrous acid to give an optically inactive alcohol [C] (C5H11OH) as the major product. What
would be the structure of [A]?
H
(1) N (2)
NH2
NH2
N
(3) (4)
Sol. Answer (2)
–
CHCl3/OH
NH2 NC
(A)–Optically active (B)–Optically active
HNO2 OH
(C)–Optically inactive
16. Methyl orange (an acid-base indicator) can be prepared by following sequence of reactions
Me
(ii) —N
(i) NaNO2 / HCl Me
HO3S — — NH2 Methyl orange
0ºC 0ºC
What would be the structure of methyl orange?
Me Me
(1) HO3S — — —N (2) — N N— —N
Me Me
Me Me
N
Me
(3) HO3S — — N N— —N (4) HO S — — N N—
3
Me
Sol. Answer (3)
Me
N
NaNO2/HCl + – Me
HO3S NH2 0°C
HO3S N2Cl
0°C
Me
HO3S N N N
Me
Methyl orange
17. A nitrogenous compound (X) is treated with HNO2, and the mixture is then made alkaline with dilute NaOH
to give a blue colouration. Among the following, which one can be the compound (X)?
(1) CH3CH2NH2 (2) CH3CH2NO2 (3) CH3CH2ONO (4) (CH3)2CHNO2
Sol. Answer (4)
Secondary nitro compound gives blue colouration in Victor Meyer’s test.
18. Consider the following sequence of reactions
Controlled
NaNO2 / HCl oxidation
[A] (C3H9N) [B] (C3H8O) C3H6O [C]
The compound [A] is
(1) CH3CH2NHCH3 (2) CH3CH2CH2NH2 (3) (CH3)3CNH2 (4) (CH3)3N
Sol. Answer (2)
OH
NaNO2/HCl
CH3 — CH2 —CH2 — NH2 CH3 — CH —CH3 CH3 COCH3
[A] [B] [C]
19. Which of the following will not react with sodiumnitrite and HCl?
Me Me
N
NH2 NO2
(1) (2) (3) N (4)
H
Sol. Answer (4)
Tertiary Aliphatic amine will not react with NaNO2 and HCl.
OH
HNO2
20. X (Major) . X is
CH2NH2
O
OH OH
O
(1) (2) (3) (4)
CH3 CH2OH
CH2
Sol. Answer (4)
OH OH OH – H2O
HNO2 H
0–5°C
CH2NH2 CH2OH CH2OH2
O OH OH
OH
–H Ring
Expansion
CH2
21. An amine reacts with C6H5SO2Cl and the product is soluble in alkali, amine is
(1) 1° amine (2) 2° amine (3) 3° amine (4) All of these
Sol. Answer (1)
R NH 2 + C 6H 5SO 2Cl C 6H 5SO 2 N R + HCl

H
The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the presence of strong electron
withdrawing sulphonyl group. Hence, it is soluble in alkali.
22. Which would not react with benzene sulphonyl chloride in aqueous NaOH?
(1) Aniline (2) N, N-dimethylaniline (3) p-toluidine (4) N-ethyl aniline
Sol. Answer (2)
Tertiary amines do not react with benzene sulphonyl chloride.
23. Which one of the following compounds gives dye test?
(1) Aniline (2) Methylamine (3) Diphenylamine (4) Ethylamine
Sol. Answer (1)
Aniline with diazonium salt yields p-aminoazobenzene.
24. The gas evolved when methylamine reacts with nitrous acid is
(1) NH3 (2) N2 (3) H2 (4) C2H6
Sol. Answer (2)
NaNO2 + HCl + – H2 O
CH3NH 2 + HNO2 [CH 3N 2Cl ] CH3 OH + N 2 + HCl
25. Identify X in the series.
NHCOCH3
HNO3 H2O
Intermediate X
H2SO4 Δ
NH2 NH2 NHCOCH3 NH2

NO2
(1) (2) (3) (4)
NH2 NO2 NO2 NO2

Sol. Answer (2)
NHCOCH3 NHCOCH3 NH2
HNO3 H 2O
H 2SO4 Δ
NO2 NO2
(X)
26. What is the end product in the following sequence of reactions?

HNO PCl NH
C2H5NH2 ⎯⎯⎯⎯
2
→ A ⎯⎯⎯
5
→ B ⎯⎯⎯
3
→C
(1) Ethylcyanide (2) Ethylamine (3) Methylamine (4) Acetamide

Sol. Answer (2)
PCl5 NH 3
C 2H5NH 2 + HNO2 C 2H 5OH C 2H 5Cl C2H 5NH 2
(Ethylamine)
27. Treatment of ammonia with excess of ethyl chloride will yield

(1) Diethylamine (2) Methylamine
(3) Tetra ethyl ammonium chloride (4) Ethane
Sol. Answer (3)
C 2H5Cl C2H5Cl C2H5Cl + –

C2H5Cl + NH3 –HCl
C2H5NH2 (C2H5) 2NH (C2H5) 3N (C2H 5) 4N Cl
–HCl –HCl –HCl
Tetraethylammonium
chloride
28. 2, 4, 6-tribromo aniline is a product of

(1) Electrophilic addition on C6H5NH2 (2) Electrophilic substitution on C6H5NH2
(3) Nucleophilic addition on C6H5NH2 (4) Nucleophilic substitution on C6H5NH2
Sol. Answer (2)
NH2 NH2
Br Br
+ Br2 (aq)
Br
(+NH2 group is highly ring activating and o-, p- directing group for further electrophilic substitution.)
29. Benzenediazonium chloride is reduced to benzene by
(1) Water
(2) Hypophosphorous acid
(3) Hypophosphoric acid
(4) Phosphine
Sol. Answer (2)
N2Cl
+ H3PO2 + H2O + N2 + H 3PO 3 + HCl

Hypophosphorous
acid
30. The end product (Z) of the following reaction is
+ –
N2 Cl
+
CuCN H /H2O NaOH
(X) (Y) CaO, Δ
(Z)
(1) A cyanide (2) A carboxylic acid (3) An amine (4) An arene

Sol. Answer (4)
+ –
N2 Cl x + COOH
CuCN H /H2O NaO H, CaO
+ Na2CO3
Δ
[Miscellaneous]
HBr AgNO2
A(C3H6) B C.
R – O– O – R (alc.)
31.
Br2
colourless
H2O
The product C is
(1) CH3 – CH2CH2 – NO2 (2) CH3CH CH3 (3) CH3CH CH3 (4) CH3CH2CH2ONO
ONO NO2
Sol. Answer (1)
HBr AgNO2
CH3 — CH —
— CH2 R— O—O— R CH 3 — CH2 — CH2 — Br (alc.)
(A) (B)
Br
Br2
|
H 2O CH3 — CH — CH2
| CH 3 — CH2 — CH2 — NO 2
Br
(C)
NO2
fuse . The product is
32. + KOH
NO2 NO2 NO2

OH
(1) (2) (3) Both (1) & (2) (4)
OH
OH
Sol. Answer (3)
NO 2 NO2 NO 2
Fuse
OH
+ KOH +
OH
O H (Nucleophile) attacks on ortho and para position because —NO2 group decreases electron density at
o-s-p-positions.
33. Incorrect statement among the following is
(1) –NO2 is a deactivating group
(2) Causes the substitution to occur at meta-position
(3) Nucleophilic ring substitution in nitrobenzene occurs at ortho and para position
(4) Hydrolysis of picryl chloride requires higher temperature than chlorobenzene
Sol. Answer (4)
Cl
O 2N NO2
(Picryl Chloride) requires room temperature for hydrolysis because —NO2 group increases
NO 2
the rate of nucleophilic substitution.
CONH2 P2O5 H3O

+
34. A B.
Δ Δ
The compound A and B are
CH2NH2 CN CN COOH
(1) , (2) ,
CN CH2NH2 CH2NH2 COOH

(3) , (4) ,
Sol. Answer (2)
CONH2 P2O5
C—
—N
H3O+
COOH
Δ Δ
(A) (B)
35. Choose the false statement.

(1) –NH2 strongly activating while –NHCOCH3 is weak activating
(2) –NO2 is strong deactivating group
(3) –NHCOCH3 and –NO2 are m-directing groups
⊕
(4) − NH3 and –NO2 are m-directing groups
Sol. Answer (3)

— NHCOCH3 group is o and p-directing while — NO2 group is m-directing.
36. Consider the following sequence of reactions
NO2
Cl
HNO3/H2SO4 NH2 — NH2
[A] [P]
20 atm, 20ºC
[P] gives coloured precipitate with benzaldehyde. What would be the structure of [P]?
O2N NO2
NO2
— NH — NH2
(1) — NH — NH2 (2)
O2N
O2N
NO2
— NH — NH2
(3) O2N — — NH — NH2 (4)
O2N
Sol. Answer (3)
NO2 NO2 NO2

Cl Cl NH NH2
HNO3/H2SO4 NH2NH2
20 atm, 20°C
O2N O2N
[A] [P]
[P] gives coloured precipitate of hydrazone with benzaldehyde of hydrazone.

37. Many important penicillin type antibiotics possess a β-lactam unit. Which of the following represents a β-lactam
ring?
H H
C C O
C C N O N O
(1) C C (2) (3) (4)
O
N C N
H H
Sol. Answer (2)
Fact
38. A compound X has the molecular formula C7H7NO. On treatment with Br2 and KOH, X gives an amine Y. The
latter gives carbylamine test. Y upon diazotisation and coupling with phenol gives an azo dye. Thus X is
(1) C6H5CONH2 (2) C6H5CH2NO (3) C6H5COONH4 (4) All of these
Sol. Answer (1)
Br 2 / KOH
C7H 7NO Y Carbylamine test
(X)
NaNO2 /HCl
273 - 278 K
Diazonium salt
Phenol
Azo dye
CONH2
Here Y must be aniline, therefore, X must be .
39. An organic compound (A) on reduction gave a compound (B). Upon treatment with HNO2, (B) gave ethyl
alcohol and on warming with CHCl3 and alcoholic KOH, (B) gave an offensive smell. The compound (A) is
(1) CH3NH2 (2) CH3NC (3) CH3CN (4) C2H5CN
Sol. Answer (3)
Reduction HNO2
A B C2H5OH
CHCl 3/alc . KO H
Offensive smell
B is primary amine (C2H5NH2) which is formed by reduction of CH3CN and offensive smell is of isocyanide
formed.


Amines 1

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Amines 1

Uploaded by

Copyright:

Available Formats

Level-I

Very Short Answer Type Questions :

Aniline Benzenediazonium Phenol

4. Give a chemical test to distinguish between primary and secondary amines.

Short Answer Type Questions :

Br2 NaNO2 / HCl

NH2 NH2 N2Cl

NH2 N2Cl CN COOH

Aniline Benzene Benzonitrile Benzoic acid

19. Give reason :

(i) C 6H 5N (CH 3) 3OH is stronger base than NH4OH.

(ii) Aniline is acetylated to prepare monobromo derivative.

NO2 NH2 N2Cl OH

Sn / HCl NaNO2 / HCl H2O

Nitrobenzene Aniline Phenol

273 - 278 K HCl

26. Suggest a route by which the following conversion can be accomplished :

C NH2 Br2 / KOH NH2 CHCl3 / KOH N C

Cyclohexylamine Cyclohexyl carbylamine

27. How is classification of amines different from that of alcohols?

–NH2 NH N –CH2OH CHOH C OH

30. How will you carry out the following conversion?

NO2 NH2 NHCOCH3

Long Answer Type Questions :

(iii) CH3CONH2 + Br2 + 4KOH CH3NH2 + K2CO3 + 2KBr + 2H2O

C2H5Cl C2H5Cl C2H5Cl + –

NaNO2 + HCl CuCN

CH2Br CH2CN CH2CH2NH2

Bromomethyl (A) (B)

(I) (II) (III) (IV)

NH2 NH2 NH2 NH2 NH2

NaNO2, HCl CuCl

H2SO4 / SO3 Fe / HCl

NO2 NO2 NO2

NaNO2, HCl CuCl

NO2 NO2 NH2

H2SO4 / SO3 Fe / HCl

Nitrobenzene (A) (B)

2. Final product of the following sequence of reactions would be

Sol. Answer (4)

3. Consider the following sequence of reaction.

The product [P] would be

Sol. Answer (2)

[A] H [B] H [C] H

NaCN Ni/H Acetic

Z in the above reaction sequence is

5. Which of the following is most basic?

(1) CH 3O NH2 (2) O 2N NH2 (3) Cl NH2 (4) NH2

Sol. Answer (1)

6. The order of nucleophilicity among Ph—NH2, Et-NH2, Ph—NH—NH2, NH2—C—NH—NH2

basic than other.

NH2 NH2 NH2

Sol. Answer (1)

(1) CH3CH2NHCOCH3 + CH3CH2N ≡ C (2) CH3CH2NO2 + CH3COOH

13. End product of the given reaction sequence is

(i) CHCl3/KOH (ii) H2 / Pd

(1) — NH — CH3 (2) — CH2 — NH2

(3) — NH — CH3 (4) NH2

Sol. Answer (3)

Sol. Answer (2)

What would be the structure of methyl orange?

(1) HO3S — — —N (2) — N N— —N

Sol. Answer (2)