Unit: AMINES

I. Multiple choice questions:

1. The correct IUPAC name for CH3 – CH2- CH2- N(CH3) -C2H5 is
a. N, N- diethyl propan-1-amine b. N-Ethyl –N-methyl propan-1-amine
c. N, N-dimethyl propan-1-amine d. N-methyl 1- pentanamine
Ans: b. N-Ethyl –N-methyl propan-1-amine

2. Which of the following statement is not correct?

a. Primary amines show intermolecular hydrogen bonding.
b. Secondary amines show intermolecular hydrogen bonding.
c. Tertiary amines show intermolecular hydrogen bonding.
d. Amines have lower boiling points as compared to those of alcohols and carboxylic
acids of comparable molar masses.
Ans: c. Tertiary amines show intermolecular hydrogen bonding.

3. Which of the following statement is correct?

a. The pKb of ammonia is more than that of methanamine.
b. The Kb of ammonia is more than that of methanamine
c. The pKb of ammonia is more than that of aniline.
d. The pKb of ammonia is less than that of methanamine.
Ans: a. The pKb of ammonia is more than that of methanamine.

4. Ramesh heated a mixture of primary amine and chloroform with ethanolic potassium
hydroxide (KOH) to form isocyanides which has foul smelling. What is the name of the
reaction involved in the statement?
a. Hoffmann bromide degradation reaction b. Hinsberg's Test
c. Gabriel Phthalimide reaction d. Carbylamine reaction
Ans: d. Carbylamine reaction

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5. The correct increasing order of basic strength for the following compounds is:

H2N NH2 NH2

CH3 NO2
(i) (ii) (ii)

a. II < III < I b. III < I < II

c. III < II < I d. II < I < II
Ans: c. III < II < I

6. The reaction C6H5N2Cl C6H5Cl + N2 is named as:

a. Sandmeyer reaction Cu,HCl b. Gattermann reaction
c. Claisen reaction d. Carbylamine reaction
Ans: b. Gattermann reaction

7. The -NH2 group is o-, p- directing and strongly activates the aromatic ring. Therefore,
aromatic amines undergo electrophilic substitution reactions readily and it is difficult
to stop the reaction at the monosubstitution stage. However, sometimes
monosubstitution product is required. How can the activating effect of -NH2 group be
controlled to get monosubstitution product?
a. Protecting -NH2 group by chlorination with chlorine
b. Protecting -NH2 group by nitration with nitric acid
c. Protecting -NH2 group by alkylation with alkyl chloride
d. Protecting -NH2 group by acetylation with acetic anhydride
Ans: d. Protecting -NH2 group by acetylation with acetic anhydride

8. A and B in the folowing reactions are:

NH2
H2/Pd Br2, NaOH
A B
Ethanol

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 a. A = Nitrobenzene, B = Nitrobenzene b. A = Nitrobenzene, B = benzamide
c. A=Nitrobenzene,B = Nitrotoluene d. A = benzamide, B = Nitrobenzene
Ans: b. A = Nitrobenzene, B = benzamide

9. Gabriel phthalimide reaction is used for the preparation of:

a. Primary aromatic amine b. Primary aliphatic amine
c. Secondary amine d. Tertiary amine
Ans: c. Secondary amine

10. Hinsberg's reagent is:

a. Phenylisocyanide b. p- toluenesulphonic acid
c. benzensulphonyl chloride d. o-dichlorobenzene
Ans: c. benzensulphonyl chloride

II. Assertion Reason Type Questions:

In the Following questions a statement of Assertion(A) is followed by a statement of
Reason(R). Select the most appropriate answer from the options given below:
a. Both A and R are true and R is the correct explanation of A
b. Both A and R are true but R is not the correct explanation of A.
c. A is true but R is false.
d. A is false but R is true.
The question given below consist of an assertion and a reason. Use the following key
to choose.
1. Assertion(A): Primary aromatic amines cannot be prepared by Gabriel phthalimide
synthesis.
Reason(R): Aryl halides undergo nucleophilic substitution with anion formed by
phthalimide.
Ans: c. A is true but R is false.

2. Assertion(A): Among isomeric amines, 30 amines have lowest boiling point.

Reason(R): Tertiary amines do not have intermolecular association due to absence of
H- atoms linked to nitrogen.
Ans: a. Both A and R are true and R is the correct explanation of A

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3. Assertion(A): Aliphatic amines are stronger bases than ammonia.
Reason(R): Aromatic amines are weaker bases than ammonia.
Ans: b. Both A and R are true but R is not the correct explanation of A.
4. Assertion(A): Very high amount of HCl is required in reduction of nitro compounds
with iron scrap
Reason(R): FeCl2 formed gets hydrolysed to release HCl during the reaction.
Ans: d. A is false but R is true.
5. Assertion(A): Aniline reacts with bromine water to give 2,4,6-tribromoaniline.
Reason(R): The -Nh2 group is o-, p- directing and strongly activates the aromatic ring.
Ans: a. Both A and R are true and R is the correct explanation of A

III. Theory Type Questions:

1. Give the IUPAC name of the following:
i.

Ans: N, N–dimethylaniline

ii. m- NC C6H4NH2

Ans:

3-aminobenzonitrile

iii. CH3 CH- CH2CH2NH-CH3

NO2
Ans: N- methyl -3 – nitro -1- butanamine

CH3
iv. CH3 CH2 CH2 N
CH3

Ans: N, N – dimethylpropanamine

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v. CH3 NH C -CH3
CH3
Ans: N- methyl -2- aminopropanamine

CH3
vi.
CH3 C NH2

CH3

Ans: 2- Methyl propane

vii. C6 H5 CH2 CH CH3

NH2
Ans:

1-phenyl-2-propanamine

viii. O -(NH2)2 C6 H4
Ans:

1, 2-benzenediamine

ix. CH3 CH2 CH2 -CH CH3

NH_ CH2 CH3
Ans: N – Ethyl pentan-2-amine

x. N (CH3)2

NO2

Ans: N, N – Dimethyl-4-nitro aniline

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2. Write reactions to prepare ethylamine from
a. Acetonitrile
Ans: CH -C ≡ N +4[H] Na/C→H OH CH -CH -NH
2 5

3 3 2 2

b. Nitroethane
Ans:
Sn/conc. HCl
∆
CH3-CH2-NO2 + 6[H] CH3-CH2-NH2 + 2H2O

c. Propionamide
Ans:
CH3-CH2-CO2-NH2 + Br2 + 4KOH → CH3-CH2-NH2 + K2CO3 + 2KBr + 2H2O

3. Give Reasons:
i. It is difficult to prepare pure amines by ammonolysis of alkylhalides.
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.

ii. Amines have higher boiling points than hydrocarbons of similar molecular mass.
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.

iii. Aniline is weaker base than cyclohexylamine.

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.

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4. Find the compounds A, B, C, D and E in the following conversions:

Ans.

5. 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.
Ans. 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 –

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6. Carry out the following convesions:
i. Aniline to N- phenylethanamide
Ans.

ii. Aniline to P- aminoazobenzene

Ans.

iii. Benzene to Aniline

Ans.

iv. Nitrobenzene to bromobenzene

Ans.

v. Ethanoic acid to methanamine

Ans. NH3 Br2/KOH
CH3COOH CH3 CONH2 CH3NH2
∆ Hoffmann bromide degradation

vi. Benzene diazonium chloride to phenol

Ans. C6H5N2+Cl- +H2O → C6H5OH + N2 + Hcl

vii. Aniline to chlorobenzene

NaNO2+ Hcl Cu2Cl2 /HCl
Ans. C H -NH
6 5 2 C6H5N2 + Cl– C6H5Cl

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viii. Methyl chloride to ethylamine
Ans. CH3Cl alc.KCN LiAlH4
CH3Cl CH3CH2NH2

ix. Nitrobenzene to benzoic acid

Ans.

7. Write the main products of the following reactions:

i.

Ans. C6H5N=NC6H4OH

ii.
Ans. C6H6 + N2 + H3PO3 + HCl

8. Give the chemical tests to distinguish between the following pairs of compounds:
i. Ethylamine and Aniline
+ −
Ans. Aniline reacts with C6H5N2 Cl , forms a yellow dye. Ethylamine does not form dye.

ii. Aniline and Benzylamine

+ −
Ans. Aniline reacts with C6H5N2 Cl , forms a yellow dye. Benzylamine does not form dye.

9. i. Arrange the following in increasing order of pKb values:

C6H5CH2NH2, C6H5NHCH3, C6H5NH2
Ans. C6H5CH2NH2 < C6H5NHCH3 < C6H5NH2

ii. Arrange the following in decreasing order of solubility in water:

(C2H5)2NH, C2H5NH2, C6H5NH2
Ans. C2H5NH2 > (C2H5)2NH > C6H5NH2

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10. Mr. Ramana, a chemistry teacher gave his class students a sample of an amine “P”
having molecular formula C4H11N to test, identify and write the reaction. The students
observed that it reacts with Hinsberg's reagent to form an alkali soluble product. A
student ramya wrote the reaction as follows.

O O
S Cl + H N C2H6 S N C2H6 + Hcl
Cl C2H6 O C2H6

Identify the mistakes committed by Ramya. Write the type of amine in sample “P” and
correct chemical equation.
O O
S Cl +CH3 CH2 CH2 CH2 NH2 S N CH2 CH2 CH2 CH3
O O
Ans. The formula of Hinsberg's reagent and sample of P were written by Ramya are
incorrect. The Sample “P” belongs to primary amine. Therefore, sample “P” is
Butanamine. The correct chemical equation is as follows:

11. Account for the following:

i. Aniline does not undergo Friedel-Crafts reaction.
Ans. Aniline being a Lewis base, reacts with Lewis acid AlCl3 to form a salt. Due to this N
atom of aniline acquires positive charge and hence acts as a strong deactivating group
for further reaction.

ii. Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
Ans. The diazonium salts of aromatic amines are more stable than those of aliphatic amines
due to dispersal of the positive charge on the benzene ring.

iii. pKb of methylamine is less than that of aniline.

Ans. In aniline due to resonance the lone pair of electrons on the nitrogen atom are
delocalized over the benzene ring. As a result, the electron density on the nitrogen
decreases. On the other hand, in methyl amine +I effect of CH3 increases the electron
density on the nitrogen atom. Therefore, aniline is a weaker base than methyl amine
and hence its pKb value is higher than that of methyl amine

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12. Arrange the following:
i. CH3NH2, (CH3)2NH, NH3, (CH3)3N [basic strength in gaseous phase]
Ans. (CH3)3N > (CH3)2NH >CH3NH2 > NH3

ii. C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH [basic strength]

Ans. C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH

iii. C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2 [basic strength]

Ans. C6H5NH2 < C6H5N(CH3)2 < CH3NH2 < (C2H5)2NH

13. Complete the following reactions:

i. CH3CONH2 + Br2 + NaOH→.......... + Na2CO3 + H2O
Ans. CH3CONH2 + Br2 + 4NaOH → CH3NH2. + Na2CO3+ 2H2O + 2NaBr

ii. ........ +H2 Pd CH3-CH2-NH2

Ans. CH3-CH2-NO2 + H2 Pd CH3-CH2-NH2

(i)LiAlH4(ii)H2O
iii. CH3CONH2
(i)LiAlH4(ii)H2O
Ans. CH3CONH2 CH3CH2NH2

14. In the following reaction chart identify A, B, C, D and E. Write their IUPAC name and
rewrite the following reaction.
NH2

Br2 H2, Pd
A B C D
KOH KOH LiAlH4/Ether

E
HCL

Ans. A = cyclohexane carboxamide B= Chloroform C = cyclohexylcarbylamine

D= N- methylcyclohexylamine E = Chloromethane

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15. Arrange the following:
i. An amine “X” with formula C3H9N reacts with benzenesulphonyl chloride to give a
precipitate which is insoluble in alkali. Give the structure and IUPAC name of amine
“X”. Write the chemical reaction
Ans. N methyl ethanamine (C2H5 NH CH3)

ii. How will bring out the following conversions:

A. Aniline to Phenol
Ans.

B. Aniline to Iodobenzene.
Ans.

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