CLASS - XII CHEMISTRY (Amines)

Topic:- Nomenclature
1. Give IUPAC name of

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2. Write structure of following
(i) Aminobut -2- ene
Ans: NH2 CH2 CH = CH CH3
(ii) N- Methyl –N- ethylaniline
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iii) N- Ethyl -2- pentanamine

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(iv) 2,4,6 – Tribromoaniline

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(v) N, N- Dimethyl methanamine

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(vi) N- Phemylaniline
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(vii) 3-Phenyl propanamine
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(viii) Benzylamine
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IUPAC name - 1- Phemylmethamine

Topic:- Reasoning Questions.

Give Reasons
1. It is difficult to prepare pure amines by ammonolysis of alkylhalides. [2]
Ans: The process of ammonolysis yields a mixture of primary, secondary, tertiary
amines and quaternary salts. The separation of this amines is a very complicated process
and difficult. Therefore it is difficult to prepare pure amines by ammonolysis of alkyl
halides.

2. Amines have higher boiling points than hydrocarbons of similar molecular mass.[2]
Ans: Amines have higher boiling points than hydrocarbons of comparable
molecular mass due to the presence of intermolecular hydrogen bond in amines which is
absent in hydrocarbons. Therefore, amines exist as associated molecules and have higher
boiling points. In alcohols and carboxylic acids, the electro- negativity of oxygen is more
than nitrogen of amines. Therefore the hydrogen bonds of alcohols and acids are stronger
than in amines and alcohols & carboxylic acids have higher boiling points.

3. Aniline is weaker base than cyclohexylamine.[2]

Ans: As a result of resonance in aniline; the lone pair on nitrogen delocalized
over the benzene ring and is less available for protonation than in cyclohexyl amine
which does not undergo resonance. Resonating structure of aniline –
4. Methylamine is a stronger base than aniline.[2]
Ans: Due to electron donating nature of CH3, group, electron pair. Availability at
N- atom in methyl amine is much higher than that in aniline; in aniline the benzene ring
decreases the electron density at N- atom in aniline. Thus CH3NH2 is a stronger base
than aniline.

5. Before nitration, aniline is converted to acetanilide.[2]

Ans: Aniline is very much susceptible to nitration and nitric acid is a strong
oxidizing agent. Therefore to avoid oxidation of aniline, -NH2 group is protected by its
acetylation to acetanilide which undergo nitration smoothly without any oxidation.

6. It is easier to brominate aniline as compared to benzene.[2]

Ans: In aniline, due to +R effect of –NH2 group the benzene ring gets activated to a
large extent and it becomes easier to brominates aniline as compared to benzene.

7. Reduction of nitro compound to aniline using iron scrap and HCl is preferred.[2]
Ans: For reduction of nitro compounds to aniline, iron scrap and HCl is preferred
because FeCl2 formed gets hydrolysed to release HCl during the reaction & therefore
only a small amount of HCl is required to initiate the reaction.

8. Aromatic amines cannot be prepared by Gabriel Phthalimide synthesis.[2]

Ans: Aromatic amines cannot be prepared by Gabriel pythalimide synthesis as aryl
halides do not undergo nucleophilic substitution with the anion formed by pythalimide

9. During acylation of amines, pyridine is added.[2]

 Ans: Acylation of amines is carried out in presence of pyridine or another base
stronger than amines as it removes HCl so formed and shifts the equilibrium in forward
direction.

10. Aniline does not undergo Friedel – Craft’s reaction.[2]

Ans: During Fridel Craft’s reaction, aniline forms salt with aluminum chloride, the
catalyst of reaction due to which nitrogen acquires a positive charge and acts as a strong
deactivating group for further reaction.

Topic:- Identification Question.

1.

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2. A compound (X) having formula C3H7 NO reacts with Br2 in the presence of NaOH to give
another compound (Y). Compound (Y) reacts with HNO2 to form ethanol and N2 gas . Identify
(X) and (Y) . Write the reaction involved.
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Since Y gives ethanol and N2 gas with HNO2, therefore it is CH3 CH2 NH2.
Ethan amine (Y) is formed on reacting (X) with Br2 and NaOH;
Therefore X is CH3 CH2 CO NH2.
Therefore
X= CH3 CH2 CONH2
Y = CH3 CH2 NH2
The reactions are –

3. An organic compound A (C3H5N) on boiling with alkali gives NH3 and sodium salt of an
acid B
(C3H6O2). The compound A on reduction gives C (C3H9N) which on treatment with nitrous
acid
gives an alcohol D (C3H8O). Identify A to D

Since the compound (A) gives sodium salt and ammonia, (A) is cyanide. The compound (C)
is a primary amine as it reacts with HNO2 and forms an alcohol (D) Therefore
A= CH3 CH2 CN , B= CH3 CH2 COOH,
C= CH3 CH2 CH2 NH2 , D= CH3 CH2 CH2 OH
Equations are-

4.
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5.

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6.

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7.

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8.

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9.

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10.

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Topic:- Conversions
1. Aniline to N- phenylethanamide
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2. Aniline to P- aminoazobenzene
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3. Benzene to Aniline
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4. Nitrobenzene to bromobenzene
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5. Benzene to m- bromoaniline
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6. Aniline to benzoic acid

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7. Aniline to p- nitro aniline

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8. Methylamine to ethylamine
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9. Nitroethane to Nitro methane

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10. Benzene to 1,3,5 – tribromobenzene

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Topic:- Miscellaneous Questions

1. For an amine RNH2, write an expression to indicate its basic strength [1]
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2. Give one use of quaternary ammonium salts. [1]

Ans: Quaternary ammonium salts are widely used for manufacture of synthetic
detergents.
 3. Give one example of Hoffmann – Bromamide reaction [1]
Ans: In Hoffmann – Bromamide reaction an acid amide is reacted with Bromine in
presence of a base to give a primary amine having one carbon less than the starting
amide.

4. Distinguish between ethylamine and aniline. [1]

Ans: Ethylamine and aniline can be distinguished by azodye test. On treating aniline
with benzene diazonium salt, orange or red coloured azodye is formed which is not
formed with ethyl amine.

5. The IUPAC name of secondary amine having lowest molecular mass is _________. [1]
Ans: N- Methylmethanamine.

6. Give an example of diazotization [1]

Ans: During diazotization benzene diazonium chloride is prepared by the reaction of
aniline with nitrous acid at 273 – 278 K

7. Write one use of diazonium salt [1]

Ans: Diazonium salts are used in preparation of substituted aromatic compounds.

8. How can the reactivity of aromatic amines be controlled? [1]

Ans: The reactivity of aromatic amines can be controlled by acylation.

9. Give one use of tertiary amines. [1]

Ans: Tertiary amines like trimethylamine are used as insect attractants.

10. Name a reagent which can distinguish between primary, secondary and tertiary amines[1]
Ans: P- Toluenesulphonyl chloride Hinsberg reagent can be used as a distinguishing
reagent for primary, secondary and tertiary amines.

Previous year questions

1. How will you convert: (i) Ethanamine into methanamine

2. Explain :- (i) Hoffmann bromamide degradation reaction
Ans: Hoffmann developed a method for preparation of primary amines by treating an amide
with bromine in an aqueous or ethanolic solution of sodium hydroxide. The amine so
formed contains one carbon less than that present in the amide.

(ii) Carbylamine reaction

Ans: Aliphatic and aromatic primary amines on heating with chloroform and ethanolic potassium
hydroxide form isocyanides or carbylamines which are foul smelling
substances. Secondary and tertiary amines do not show this reaction. This reaction is known as
carbylamine reaction or isocyanide test and is used as a test for primary amines.

3. Give reason:-
(i) It is difficult to prepare pure amines by ammonolysis of alkyl halides.
Ans : It is difficult to prepare pure amines by ammonolysis of alkyl halides, because in this
reaction a mixture of primary, secondary, tertiary amines and quaternary ammonium salts
is produced.

4. Primary and secondary amines have higher boiling point than tertiary amine. Why?
Ans: Primary and secondary amines have intermolecular association due to H-bonding.

5. a) How will you convert 4-nitro toluene to 2-bromo benzoic acid?

b) Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis?
Ans : a)

b) Gabriel phthalimide synthesis is used for the preparation of aliphatic primary amines. It
involves nucleophilic substitution of alkyl halides by the anion formed by the phthalimide. But
aryl halides do not undergo nucleophilic substitution with the anion formed by the phthalimide.

6. Amines are basic substances while amides are neutral. Why?

Ans: Due to presence of lone pair of electrons on nitrogen of amines, they are basic in nature
whereas nitrogen of amides acquires positive charge due to resonance with carbonyl group which
makes it neutral.

7.
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8. Which of the two has higher pkb value and why? CH3CONH2 or CH3CH2NH2
Ans: CH3CONH2 has a higher pkbvalue than CH3CH2NH2. In CH3CONH2 lone pair on N is
in resonance with C=O, thus lowering down availability of lone pair and thus lower basic
strength while in CH3CH2NH2 , ethyl being electron releasing group, increases electron
density on N making it a stronger base.

9. Give IUPAC names of following

(a) C6H5CH3
(b) C6H5NHCH3
Ans: (A) Toluene (b) N- Methyl aniline

10.
Δ
C6 H5 COO NH4 ---------------->C6 H5 CONH2 + H2O

11. (i) Convert benzamide to toluene

(ii) Write the name of reactants, reagents and products involved in conversion of
nitrobenzene to m-bromoaniline
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12. An organic compound A (C3H5N) on boiling with alkali gives ammonia and sodium salt
of an acid B (C3H6O2). Upon reduction, A gives C (C3H9N) which on treatment with
nitrous acid gives D (C3H8O). Identify A, B, C and D. Give all equations involved.
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 13. (a) Identify A and B in the following:

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14. Why do amines react as nucleophiles?

Ans: A nucleophile is an electron-rich species seeking electron-deficient sites. Amines are
nucleophilic due to the presence of unshared or lone pair of electrons.

15. Account for any two of the following

(a) Amines are basic substances while amides are neutral.
(b) Nitro compounds have higher boiling points than the hydrocarbons having almost the same
molecular mass.
(c) Aromatic amines are weaker bases than aliphatic amines.
Ans: (a) Amines are basic because of the presence of unpaired or lone pair of electrons.Amides,
on the other hand, are neutral species because the lone pair of electrons is involved in resonance.
Hence, no electron pair remains for donation.
(b) Nitro compounds are polar compounds whereas hydrocarbons are non-polar. Due to their
polarity, nitro compounds have higher boiling points than the hydrocarbons having almost same
molecular mass.
(c) Aromatic amines are weaker bases than aliphatic amines. This is because in aromatic
amines, owing to resonance, the lone pair of electrons on the nitrogen atom is less
available for protonation. The partial positive charge on the nitrogen atom tends to repel a
proton.

16. Amines are basic substances while amides are neutral. Why?
Ans: Due to presence of lone pair of electrons on nitrogen of amines, they are basic in nature
whereas nitrogen of amides acquires positive charge due to resonance with carbonyl group
which makes it neutral.

17. In the following cases rearrange the compounds as directed:

(i) In an increasing order of basic strength: C6H5NH2,C6H5 N (CH3)2, (C2H5)2 NH and
CH3NH2
(ii) In a decreasing order of basic strength: Aniline, p-nitroaniline and p-toluidine
(iii) In an increasing order of pKb values: C2H5NH2, C6H5 NHCH3, (C2H5)2 NH and
C6H5NH2
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(i) Basic strength:

Aliphatic amines are stronger bases than aromatic amines due to the presence of lone pair
of electrons on nitrogen atom. In case of aromatic amines the lone pair gets delocalised by
resonance. Diethyl amine has greater + I effect. Hence, electron density over the nitrogen
atom is more in this case. Similarly N, N − dimethyl aniline has greater + I effect than
aniline.
(ii)

Methyl (−CH3) is an electron donating group. It increases the electron density on the
ring. Therefore, the lone pair of nitrogen is available for donation. Hence, it is most
basic. On the other hand nitro (−NO2) is an electron withdrawing group. It decreases
the electron density of the ring. Therefore, the lone pair is more delocalized in this case
and is less available for donation. Thus, it will be least basic among the three.
(iii)

Stronger the base is lesser is the pKb value. (C2H5)2NH is the strongest base due to two
electron releasing group followed by C2H5NH2 which has only one electron releasing
group. C6H5NHCH3 is the next stronger base because of the presence of one electron
releasing alkyl group and electron delocalising phenyl group. C6H5NH2 is the least
basic wherein the electrons get delocalised by resonance.

18. Give a chemical test to distinguish between aniline and N-methyl aniline.
Ans: Aniline and N-methyl aniline can be distinguished by Hinsberg’s method (i.e., reaction
with benzene sulphonyl chloride).Aniline (primary amine) will form N-phenyl benzene
sulphonamide, which dissolves in KOH because of the presence of an acidic hydrogen on the N-
atom. On the other hand, N-methyl aniline (secondary amine) will form N-methyl-N-phenyl
benzene sulphonamide, which does not dissolve in KOH due to the absence of acidic hydrogen
on N-atom.

19. Account for the following:

(a) Electrophilic substitution in case of aromatic amines takes place more readily than
benzene.
(b) CH3CONH2 is a weaker base than CH3CH2NH2.
(c) Nitro compounds have higher boiling points than hydrocarbons having almost same
molecular mass.
Ans: (a) The benzene ring in aniline is highly activated. This is because of the presence of a
lone pair of electrons on the nitrogen atom. The displacement of the lone pair on nitrogen
towards the benzene ring facilitates the electrophilic attack on the ring. Thus, due to the presence
of −NH2 group, electrophilic substitution takes place more readily in aromatic amines than
benzene.
(b) In CH3CONH2, the electron pair on nitrogen is withdrawn towards carboxyl group, as
shown by the following resonance structures.

Thus, the lone pair of electrons is not available for donation. On the other hand, because of the +I
effect of the C2H5 group, the lone pair of electrons can be easily donated in CH3CH2NH2. This
is why CH3CONH2 is a weaker base than CH3CH2NH2.
(c) Nitro group are highly polar in nature, and therefore, there is a strong attraction between the
nitrogen and oxygen of nitro groups. As a result, a large amount of energy is required to separate
them. Hence, compounds containing nitro groups have high boiling points in comparison with
hydrocarbons of the same molecular mass.

20. Why are primary amines higher boiling than tertiary amines?
Ans: Primary amines undergo intermolecular H bonding, and hence, intermolecular association.
However, intermolecular H bonding is absent from tertiary amines. So, they do not undergo
intermolecular association. Hence, primary amines are higher boiling than tertiary amines.

21. What is carbylamine reaction?

22. Give reason for the following:

i) Primary amines are higher boiling point than tertiary amines.
ii) Aliphatic amines are stronger bases than aromatic amines.
iii) Amines are basic substances while amides are neutral.

23. The basic character of amines in the vapour phase decreases in the order
(CH3)3N ›(CH3)2NH › (CH3)NH2 › NH3
while in the aqueous solution the order is CH3)2NH ›(CH3)NH2 › (CH3)3N › NH3.
Explain.

24. Write one chemical equation to exemplify the following reactions:

a) Carbylamine reaction
b) Hofmann bromamide reaction.