MAHARASHTRA BOARD

12th CHEMISTRY TEXTBOOK SOLUTIONS

1. Choose the most correct answer.

i) c vi) a
ii) c vii) c
iii) a viii) a
iv) d ix) c
v) a x) b

2. Answer in one sentence.

i)

ii) Two moles of methylbromide are required to convert ethanamine to N, N-

dimethyl ethanamine.
iii) Propanamide (C2H5CONH2) produces ethanamine by Hofmann
bromamide degradation reaction.
iv) Order of basicity of aliphatic alkylamine in gaseous phase: 3° amine > 2°
amine > 1° amine
v) This is due to the presence of an alkyl group that exerts electron releasing
inductive effect (+I effect). This stabilizes the positive charge on the atom
bonded to it.
The conjugate acid of ammonia is (NH4+) and that of 1° amine is (RNH3+).
The presence of the alkyl group results in increased stability of RNH 3+ as
compared to NH4+. Thus, primary aliphatic amines are stronger bases
than ammonia.
vi)

vii) IUPAC name of benzylamine is ‘phenylmethanamine’.

viii) Trimethylamine (3°) < ethylmethyl amine (2°) < n-propylamine (1°)

ix) The action of dilute sulphuric acid on diethylamine gives

diethylammonium sulphate.
2(C2 H5 )2 NH + H2 SO4 ⇌ [(C2 H5 )2 NH2+ ]2 SO2−
4
(Diethylamine) (Sulphuric acid) (Diethylammonium sulphate)
x) Cyclohexylamine < Aniline < 4-Nitroaniline

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12th CHEMISTRY TEXTBOOK SOLUTIONS

3. Answer the following.

i) C H − CH − Br Alcoholic KCN Na/ethanol
6 5 2 → C6 H5 − CH2 − C ≡ N →
(Benzyl bromide) (Phenylacetonitrile)
A
C6 H5 − CH2 − CH2 − NH2
(2-phenylethylamine)
B
ii) Amines act as Lewis bases due to the presence of lone pair of electrons on
the N-atom.
Example:– Trimethylamine shares its lone pair of electrons with the
electron-deficient boron trifluoride.
Me3N: + BF3 → Me3N+ – B–F3
(Trimethylamine) (Boron trifluoride)

Basic character of amines can be better expressed in terms of Kb and pKb

values.
∖ ∖
−N : + H2O ⇌ −N+ − H + O− H
∕ ∕
(Amine) (Conjugated acid)
In this equilibrium, amine accepts H+, hence it is a Lowry – Bronsted base.
For a stronger base, this equilibrium shifts towards the right, thereby, for
strong bases, the Kb value is larger or the pKb value is smaller.
iii) Aliphatic / aromatic primary amines react with nitrous acid to form
corresponding diazonium salts. This is called as diazotisation.

iv)

v)  Arene diazonium salts when treated with certain reactive aromatic

compounds such as phenols or aromatic amines, give azo compounds.
 These have extended conjugated system of double bonds in which two
aromatic rings are joined through azo group –N=N–. This reaction is
called azo coupling.
 Azo compounds are brightly coloured and used as dyes.
 This is an example of electrophilic aromatic substitution reaction.
Here the electrophiles are positively charged diazonium ions.
 Substitution usually occurs para to the ring activating group.

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 For example: Benzenediazonium chloride reacts with phenol in mild
alkaline medium to give p-Hydroxy-azobenzene (orange dye).

 Azo coupling with 𝛽-naphthol in NaOH is used as a confirmatory test

for primary aromatic amines.
 Benzenediazonium chloride reacts with aniline in mild alkaline
medium to give p-aminoazo-benzene (yellow dye.)

vi) This method is used for the synthesis of primary amine. It involves the
following three stages:
1) Formation of potassium salt of phthalimide from phthalimide on
reaction with alcoholic potassium hydroxide.

2) Formation of N-alkyl phthalimide from the potassium salt by reaction

with alkyl halide.

3) Alkaline hydrolysis of N-alkyl phthalimide to form the corresponding

primary amine.

vii)  Aliphatic or aromatic primary amines on heating with chloroform give

foul (offensive) smelling products called alkyl/aryl isocyanides or
carbylamines.

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12th CHEMISTRY TEXTBOOK SOLUTIONS
 This reaction is a test for primary amines. Secondary and tertiary
amines do not give this test.
∆
R – NH2 + CHCl3 + 3KOH → R – NC + 3KCl + 3H2O
(1° amine) (Alkyl isocyanide)
viii) a)

b)

ix) a)

b)

x)  When alkyl halide is heated with alcoholic solution of excess ammonia

it undergoes nucleophilic substitution reaction in which the halogen
atom is replaced by an amino (–NH2) group to form primary amine.
 This process of breaking of C–X bond by ammonia is known as
ammonolysis. The reaction is also known as alkylation of ammonia.
 The reaction is carried out in a sealed tube at 373 K.
 The primary amine obtained in the 1st step is stronger nucleophile
than ammonia. Hence, it further reacts with alkyl halide to form
secondary and tertiary amines and finally quaternary ammonium salt
if NH3 is not used in large excess.

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12th CHEMISTRY TEXTBOOK SOLUTIONS
∆
R–X + NH3 (alc.) → R – NH2
(excess) (1°amine)

 The order of reactivity of alkyl halides with ammonia is R–I > R–Br >
R–Cl.
xi)

4. Answer the following.

i) a) N–ethyl–N–methylpropan–1–amine

b) 3, 3–dimethylbutan–1–amine

c) N–ethylpropan–2–amine

ii)  Amines are nitrogen containing organic compounds having basic

character.
 Amines are classified as primary (1°), secondary (2°) and tertiary (3°)
amines.
 Their structures are obtained in simple way by replacing one, two or
three hydrogen atoms of NH3 molecule by alkyl/aryl groups.
 Secondary and tertiary amines are further classified as simple or
symmetrical amines and mixed or unsymmetrical amines.
 When all the alkyl or aryl groups on nitrogen are same, it is a simple
amine. If these groups are different, then the amine is a mixed amine.
 Amines are also divided into two major classes, namely, aliphatic and
aromatic amines on the basis of nature of the groups attached to the
nitrogen atom.
iii) a) Hexane–1,6–diamine

b) 2, 4–dimethylaniline

c) Benzene–1, 4–diamine

iv) a) Acetonitrile on Mendius reduction yields ethanamine.

Na/ethanol
CH3 – C ≡ N + 4[H] → CH3 – CH2 – NH2
(Acetonitrile) (Ethanamine)
b) Nitroethane on reduction in presence of Sn / HCl or LiAlH4 in ether
yields ethanamine.

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12th CHEMISTRY TEXTBOOKSOLUTIONS
LiAlH4 /ether
CH3 – CH2 – NO2 → CH3 – CH2 – NH2
(Nitroethane) (Ethanamine)
c) Propionamide on Hofmann bromamide degradation yields ethanamine.

v)  Ethylamine reacts with acetic anhydride to give N–ethylethanamide.

 Diethylamine reacts with acetic anhydride to give N, N–

diethylacetamide.

 Triethylamine is a 3° amine. It will not undergo acetylation as it does

not contain any hydrogen attached to the nitrogen of the amino group.

vi)  Ethylamine (1° amine) reacts with benzenesulphonyl chloride to form

N–ethylbenzenesulphonamide.

The hydrogen attached to nitrogen in N–ethylbenzenesulphonamide

is strongly acidic. Hence, it is soluble in alkali.
 Diethylamine reacts with benzenesulphonyl chloride to give N, N–
diethylbenzenesulphonamide.

N, N–diethylbenzenesulphonamide does not contain any H-atom

attached to the nitrogen atom. Hence, it is not acidic and does not
dissolve in alkali.
 Triethylamine does not react with benzenesulphonyl chloride as it
does not contain any H–atom attached to the nitrogen atom.

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vii) a) Direct nitration of aniline yeilds (p–nitroaniline) a mixture of ortho,

meta and para nitroanilines. In acidic medium –NH2 group is protonated
to –N⊕ H3 group which is meta-directing and deactivating. Hence
considerable amount of m–nitroaniline is obtained.

However, to get p–nitroaniline as major product, –NH2 group is first

protected by acetylation, nitration is carried out and then amide is
hydrolysed.

b) Aniline reacts with concerntrated sulfuric acid to form anilinium

hydrogen sulfate which on heating with sulphuric acid at 453–473K
produces p–aminobenzene sulfonic acid (sulfanilic acid) as major
product.

Sulfanilic acid exists as a salt; called dipolar ion or zwitter ion. It is

produced by the reaction between an acidic group and a basic group
present in the same molecule.

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