9.

AMINES
Quick Revision Points:
Amines are alkyl / aryl derivatives of ammonia. In amines nitrogen atom is sp3
hybridised and contains one lone pair.
Primary amine (10) Secondary amine (20) Tertiary amine (30)
One- H atom is replaced by Two-H atom is replaced Three-H atom is
R/Ar. by R/Ar. replaced by R/Ar.

IUPAC Name: -
Aliphatic amine:
Alkanamines
Aromatic amine:
Benzenamine/Aniline
CH3-NH2 CH3-NH- CH3 (CH3)3N
Methanamine N-Methylmethanamine N, N-
CH3-CH- CH3 dimethylmethanamine
NH2
Propan-2-amine
CH3-NH- CH2- CH3
N-Methylethanamine
CH3 - CH2-NH- CH2- CH3
N-Ethylethanamine
N, N-
Aniline/benzenamine
Dimethylbenzenamine
Preparation of Amines:
Reduction of Nitro Compounds gives aliphatic
and aromatic primary amines. (Reducing
Agents): -
• Hydrogen and nickel/ palladium or
platinum.
• Iron scrap and hydrochloric acid (Fe + HCl).
• Tin and hydrochloric acid (Sn + HCl).
Ammonolysis of alkyl halides: - NH3 RX RX RX
RX → RNH2 → R 2 NH → R 3 N → R 4 N+ X −
Reagent: Ethanolic solution of ammonia. −HX
Disadvantage: Mixture of amines formed.
Reduction of nitriles Reducing agents: - H2 /Ni or Na(Hg)/C2 H5 OH
R − CN →⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ R − CH2 NH2
LiAlH4/Catalytic hydrogenation.
Reduction of Amides: CH3 CONH2
LiAll4
→ CH3 CH2 NH2
H2 O
Hoffmann bromamide degradation Reaction: An amide is heated with Bromine in
aq. solution of NaOH/KOH gives primary amine.
R − CONH2 + Br2 + 4NaOH → R − NH2 + Na2 CO3 + 2NaBr + 2H2 O
The amine formed contains one carbon less than that present in the amide.

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Gabriel Phthalimide Synthesis: Only aliphatic
primary amines are prepared by this method.
Aromatic primary amines cannot be prepared
because aryl halides do not undergo
nucleophilic substitution with the anion
formed by phthalimide.

Physical properties Chemical reaction and Basic Nature

In Tertiary amines H-Bonding is Amines are Lewis bases due to presence of lone
not possible due to absence of H pair.
atoms. Larger the value of Kb or smaller the value of
Hydrogen bonding 30 <20<10 pKb, stronger is the base.
Solubility in water 30 <20<10 NH3 < 10 < 20 < 30 (gas phase) (due to +I effect)
Boiling Point 30 <20<10 NH3< C2H5NH2< (C2H5 )3N<(C2H5)2NH (aqueous
phase)
Boiling point
NH3 < (CH3 )3N <CH3NH2 < (CH3 )2NH (aqueous
Alkane < Amine < Alcohol phase)

• Aliphatic amines are stronger base than ammonia due to +I effect of alkyl groups.
• Aromatic amines are weaker bases than ammonia due to the electron withdrawing
nature of the aryl group.
Acetylation: (replacement of H-atom of (C2H5)2NH + CH3COCl → CH3CON(C2H5)2 +
–NH2 />N–H group by the acyl group). HCl
Reacting agent: stronger base.
Benzoylation: (replacement of H-atom
of –NH2 />N–H group by the benzoyl CH3NH2 + C6H5COCl →C6H5 CONH-CH3 + HCl
group).
Carbylamine reaction (Isocyanide HEAT
RNH2 + CHCl3 + 3KOH →⎯⎯ RNC + 3KCl + 3H2 O
Test) Secondary and tertiary amines do not show
Primary amines react with chloroform this reaction.
and KOH give isocyanides It is used as a test for primary amines.
(Carbylamine) which has unpleasant
smell (foul smell).
Reaction with nitrous acid (HNO2) NaNO2 +HCl H2 O
RNH2 +HNO2 →⎯⎯⎯⎯⎯⎯⎯ [RN2+ Cl− ] →⎯ ROH + N2 + HCl
Primary aliphatic amines react with
nitrous acid to form aliphatic
diazonium salts (unstable) which 278K
liberate nitrogen gas and alcohols. C 6 H 5 NH 2 + HNO 2 →⎯⎯ C6 H5 N2+ Cl− + NaCl + 2H2 O
Aromatic amines at low temperatures
(273-278 K) forms diazonium salts.

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Reaction with Benzenesulphonyl chloride (Hinsberg's test)(C6H5SO2Cl)
Primary Amine Secondary Amine Tertiary Amine
Primary amines form Secondary amines form Tertiary amines do
N-alkylbenzene sulphonamide N, N- not react with
which is soluble in alkali due dialkylbenzenesulphonamide Hinsberg’s reagent.
to presence of acidic hydrogen which is not soluble in alkali
at N-atom. due to absence of hydrogen
atom at N-atom.

Electrophilic substitution:
–NH2 group is ortho and para directing and a powerful activating group.

In direct Nitration meta product is formed due to formation of anilinium ion which is
meta directing.

Electrophilic substitution:
Aniline is converted into acetanilide by acetylation with acetic anhydride and then the
desired substitution is carried out followed by hydrolysis the lone pair on nitrogen is
less available for donation to benzene ring by resonance. Therefore, activating effect of -
NHCOCH3 group is less than that of amino group.

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Benzene Diazonium Chloride Preparation and Reactions:

MULTIPLE CHOICE QUESTIONS (1 MARKS)

Q: 1 The correct IUPAC name for CH3 – CH2- CH2- N(CH3) -C2H5 is
(a) N, N- diethyl propan-1-amine (c) N, N-dimethyl propan-1-amine
(b) N-Ethyl –N-methyl propan-1-amine (d) N-methyl 1- pentanamine
Q: 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.
Q: 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.
Q: 4 Atharv 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 (c) Gabriel Phthalimide reaction
(b) Hinsberg’s Test (d) Carbylamine reaction
Q: 5 The correct increasing order of basic strength for the following compounds
is:

(a) II < III < I (c) III < II < I

(b) III < I < II (d) II < I < II
𝐂𝐮,𝐇𝐂𝐥
Q: 6 The reaction 𝐂𝟔 𝐇𝟓 𝐍𝟐 𝐂𝐥 →⎯⎯⎯ 𝐂𝟔 𝐇𝟓 𝐂𝐥 + 𝐍𝟐 is named as
(a) Sandmeyer reaction (b) Gattermann reaction
(c) Claisen reaction (d)Carbylamine reaction

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Q: 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
Q: 8 A and B in the folowing reactions are:

(a) A = Nitrobenzene, B = Nitrobenzene (c) A=Nitrobenzene,B = Nitrotoluene

(b) A = Nitrobenzene, B = benzamide (d) A = benzamide, B = Nitrobenzene
Q: 9 Gabriel phthalimide reaction is used for the preparation of:
(a) Primary aromatic amine (c) Secondary amine
(b) Primary aliphatic amine (d)Tertiary amine
Q: 10 Hinsberg's reagent is:
(a) Phenylisocyanide (c) benzensulphonyl chloride
(b) p- toluenesulphonic acid (d) o-dichlorobenzene
Question 1 2 3 4 5 6 7 8 9 10
Answer B C A D C B D B B C
ASSERTION REASON TYPE QUESTIONS(1MARKS)
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.
11. Assertion(A): Primary aromatic amines cannot be prepared by Gabriel
phthalimide synthesis.
Reason(R): Aryl halides undergo nucleophilic substitution with anion formed by
phthalimide.
12. 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.
13. Assertion(A): Aliphatic amines are stronger bases than ammonia.
Reason(R): Aromatic amines are weaker bases than ammonia.
14. 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.
15. 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.

Question 1 2 3 4 5
Answer c a b d a

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VERY SHORT ANSWER TYPE QUESTIONS (2 MARKS)
Q: 16 Give the IUPAC name of (i) H2N – CH2 – CH2 – CH = CH2
(ii) CH3—NH—CH2CH3.
Answer: (i) But-3-en-1-amine (ii) N-methylethanamine
Q: 17 Which of the following are tertiary amines

Answer: (iii) and (iv) are tertiary amines

Q: 18 Name the IUPAC names of following.
(i) The amine produced by the Hoffmann bromamide degradation of propanamide.
(ii) The product produced after acylation of aniline.
Answer: (i) Ethanamine (CH3 – CH2 – NH2)
(ii) N-Phenyl ethanamide (CH3CONH- C6H5)
Q: 19 Write the main products of the following reactions:
PH=9−10
(𝑖) C6 H5 N2+ Cl− + C6 H5 OH →⎯⎯⎯⎯⎯⎯⎯
(ii) C6 H5 N2+ Cl− + H3 PO2 + H2 O →
Answer: (i) C6H5N=NC6H4OH
(ii) C6 H6 + N2 + H3 PO3 + HCl
Q: 20 Write the chemical equations involved when aniline is treated with the
following reagents:
(i) Br2 water (ii) CHCl3 + KOH
Answer:

Q:21 How will you convert the following:

(i) Ethanoic acid to methanamine (ii) Benzene diazonium chloride to phenol
Answer:
(i) Ethanoic acid to methanamine
NH Br2 /KOH
CH3 COOH ∆ 3 CH3 CONH2 Hoffmann bromide CH3 NH2
degradation
(ii) Benzene diazonium chloride to phenol
C6 H5 N2+ Cl− + H2 O → C6 H5 OH + N2 + HCl
Q: 22 Give the chemical tests to distinguish between the following pairs of
compounds:
(i)Ethylamine and Aniline (ii)Aniline and Benzylamine
Answer:
Ethylamine and aniline: Azo-dye test
(i)Aniline reacts with C6 H5 N2+ Cl− , forms a yellow dye. Ethylamine does not form dye.
(ii) Aniline reacts with C6 H5 N2+ Cl− , forms a yellow dye. Benzylamine does not form
dye.
Q: 23 Write the reactions involved in the following:
(i) Gabriel phthalimide synthesis (ii) Sandmeyer reaction
Answer: (i)

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(ii) C6 H5 N2+ X − + CuCl/HCl → C6 H5 Cl + N2
Q: 24 How will you bring about the following conversions?
(a) Ethanamine into methanamine (b) Aniline into 4-bromoaniline
Answer:
HNO2 CrO3 ,H2 SO4 NH3,∆ Br2, KOH
(i) CH3 CH2 NH2 →⎯⎯ CH3 CH2 OH →⎯⎯⎯⎯⎯⎯⎯ CH3 COOH →⎯⎯ CH3 CONH2 →⎯⎯⎯⎯ CH3 NH2
(ii)

Q: 25 (i) Arrange the following in increasing order of pKb values:

C6H5CH2NH2, C6H5NHCH3, C6H5NH2
(ii) Arrange the following in decreasing order of solubility in water:
(C2H5)2NH, C2H5NH2, C6H5NH2
Answer: (i) C6H5CH2NH2 < C6H5NHCH3 < C6H5NH2
(ii) C2H5NH2 > (C2H5)2NH > C6H5NH2
SHORT ANSWER TYPE QUESTIONS (3 MARKS)
Q:26 How will you convert the following?
(i) Aniline to chlorobenzene
(ii) Methyl chloride to ethylamine
(iii) Nitrobenzene to benzoic acid
Answer:
NaNO2 +HCl Cu2 Cl2 /HCl
(i) C6 H5 − NH2 →⎯⎯⎯⎯⎯⎯⎯ C6 H5 N2+ Cl− →⎯⎯⎯⎯⎯⎯⎯ C6 H5 Cl
alc.KCN LiAlH4
(ii) CH3 Cl →⎯⎯⎯⎯ CH3 CN →⎯⎯⎯ CH3 CH2 NH2
(iii)

Q: 27 Mr. Krishna, 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 Ranu wrote the reaction as follows.

Identify the mistakes committed by Ranu. Write the type of amine in sample “P” and
correct chemical equation.
Answer: The formula of Hinsberg’s reagent and sample of P were written by Ranu are
incorrect. The Sample “P” belongs to primary amine. Therefore, sample “P” is
Butanamine. The correct chemical equation is as follows:

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Q: 28 Account for the following:
(i) Aniline does not undergo Friedel-Crafts reaction.
(ii) Diazonium salts of aromatic amines are more stable than those of aliphatic
amines
(iii) pKb of methylamine is less than that of aniline.

Answer: (i) 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) 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) 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
Q: 29 Arrange the following:
(i) CH3NH2, (CH3)2NH, NH3, (CH3)3N [in decreasing order of basic strength in gaseous phase]
(ii) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH [in increasing order of
basic strength]
(iii) C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2 [in increasing order of basic
strength]
Answer: (i) (CH3)3N > (CH3)2NH >CH3NH2 > NH3
(ii) C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH
(iii) C6H5NH2 < C6H5N(CH3)2 < CH3NH2 < (C2H5)2NH
Q: 30 Complete the following reactions:
(i) CH3CONH2 + Br2 + NaOH→………. + Na2CO3 + H2O
𝑃𝑑
(ii) ………. + H2 →⎯⎯ CH3-CH2-NH2
(i)LiAlH4 (ii)H2 O
(iii) CH3CONH2 →⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯
Answer:
(i) CH3CONH2 + Br2 + 4NaOH → CH3NH2. + Na2CO3 + 2H2O + 2NaBr
𝑃𝑑
(ii) CH3-CH2-NO2 + H2 →⎯⎯ CH3-CH2-NH2
(i)LiAlH4 (ii)H2 O
(iii) CH3CONH2 →⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ CH3CH2NH2
LONG ANSWER TYPE QUESTIONS (5 MARKS
Q: 31 in the following reaction chart identify A, B, C, D and E. Write their IUPAC
name and rewrite the following reaction

Answer: A = cyclohexane carboxamide B= Chloroform

C = cyclohexylcarbylamine D= N- methylcyclohexylamine E = Chloromethane

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Q: 32 (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
(ii) How will bring out the following conversions: (A) Aniline to Phenol (B) Aniline to
Iodobenzene.
Answer: (i) N methyl ethanamine (C2H5 NH CH3)

273−278K
(ii) (a) C6 H5 − NH2 + HNO2 →⎯⎯⎯⎯⎯⎯ C6 H5 − N2+ Cl− + NaCl + 2H2 O
∆
C6 H5 N2+ Cl− + H2 O → C6 H5 OH + N2 + HCl
273−278K
(b) C6 H5 − NH2 + HNO2 →⎯⎯⎯⎯⎯⎯ C6 H5 − N2+ Cl− + NaCl + 2H2 O
C6 H5 N2+ Cl− + KI → C6 H5 I + N2 + KCl
CASE BASED QUESTIONS
Q 33.Amines are organic bases having the general formula RR’2N, where R is a
hydrocarbon group, ‘R’ may be H or a hydrocarbon group. As with ammonia, the
reaction of amines with water is
RNH2 + H2O →RNH3+ +OH- .
Like all bases, amines form salts when allowed to react with acids.
CH3NH2 + HCl → CH3N+H3Cl
These salts are usually colourless, odourless solids.
Aromatic amines are used mainly in the manufacture of dyes.
Aniline, the simplest aromatic amine itself is a toxic compound; a number of other
aromatic amines such as 2-naphthylamine and benzidine are potent carcinogens.

Aniline 2- naphthylamine Benzidine

Q(i) Arrange the following in the increasing order of Pkb value

C6H5NH2, C2H5NH2, CH3NH2, NH3 .
(ii) Draw the structure of sulphanilic acid
(iii)In cold conditions, aniline is diazotised to form a compound, which is treated with
phenol to form a coloured product. Write the necessary equations.
OR
Give reasons
(a) Aniline on nitration gives considerable amount of meta product along with ortho
and para.
(b) Aniline is less basic than ammonia.
Answers (i) C2H5NH2, CH3NH2, NH3, C6H5NH2.

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(ii)

(iii)

OR

(a)Aniline being basic, reacts with acid to form anilinium ion, which is meta
directing.
(b) The lone pair of electrons on N in aniline are not readily available due to
delocalization with the benzene ring.

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