AMINES & DIAZZONIUM SALTS

CASE-BASED/PASSAGE-BASED INTEGRATED QUESTIONS

JI
I. Read the given passage and answer the questions that follow.
Amines are classified as primary, secondary and tertiary amines. Primary amines cannot be obtained by am-

monolysis of alkyl halide because we will get mixture of 1°, 2° and 3° amines. Cyanides, on reduction give
primary amines where as isocyanides on reduction give secondary amines. Nitro compounds, on reduction also
give primary amines. Primary amines react with CHCl3 and KOH to form foul smelling isocyanide. They react
with HNO2 and liberate N2 gas. They react with Hinsberg’s reagent to form salt soluble in KOH. Secondary
amine form yellow oily compounds with HNO2 and salt formed with C6H5SO2Cl, is insoluble in KOH. 3° amines
form salt soluble in water with HNO2 but does not react with C6H5SO2Cl.
LA
Diazonium salts are prepared by reaction of Aniline with NaNO2 and conc. HCl at 0 – 5 °C. Aromatic diazonium

salts are more stable because phenyl diazonium ion is stabilized by resonance. Benzene diazonium chloride can
be used to prepare halo benzene, phenol, nitro benzene, benzene, p-hydroxy azo benzene (azo dye) and large
number of useful compounds.
(a) Write the isomer of C3H9N which does not react with Hinsberg reagent.

Ans. (CH3)3N, N, N–dimethyl methanamine

CH2NH2

(b) , on heating with CHCl3 and KOH gives ‘X’. Identify ‘X’.
A

CH2N C

Ans. , a foul smelling compound.

(c) Convert Aniline to phenol.
B

NH2 N 2+ Cl – OH
Conc.
NaNO2 + HCl HO
Ans. → →
2
O – 5 °C Warm

Aniline Phenol

(d) Distinguish between Aniline and ethyl amine.

Ans. Add NaNO2 and conc. HCl. Cool it to 0 to 5° C. Then add alkaline solution of phenol. Aniline gives orange dye

where as ethyl amino does not.
(e) Complete the following reaction.

Fe/HCl 2 NaNO + HCl
C6H5NO2 → A →
0 – 5 °C
B. Identify ‘A’ and ‘B’

Ans. ‘A’ is C6H5NH2 ‘B’ is C6H5 N +2 Cl-–

  
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 CuCN H O/H+
(f) C6H5 N 2+ Cl– → A →
2
B, Identify ‘A’ and ‘B’.

Ans. ‘A’ is C6H5CN, ‘B’ is C6H5COOH

(g) What is use of quarternary ammonium salts of long chain tertiary amines?

Ans. It is used as cationic detergents used in hair conditioners and shampoo.

II. Read the given passage and answer the questions that follow.
Organic compounds containing amine as functional group are present in wide variety of compounds namely

amino acids, hormones, neurotransmitters, DNA, alkaloids, dyes etc. Drugs including nicotine, morphine, codein,
heroin etc. which have physiological effects on human also contain —NH2 group in one form or another. Amines

JI
are basic in nature due to presence of lone pair of electron on nitrogen. Adrenaline hormone and ephedrine
drug, both contain second amino group are used for increasing blood pressure. Novacain, a synthetic compound
contains both primary and tertiary amino group, is used as anaesthetic in dentistry. Benadryl, a widely used
antihistamine drug contains tertiary amino group, Quarternary ammonium salts of long chain, tertiary amines
are used as cationic detergents. Diazonium salts are used for synthesis of azodyes and useful aromatic compounds.
(a) Write the formula of tertiary amine with molecular formula C3H9N, which does not react with Hinsberg

reagent?
LA
Ans. (CH3)3N does not react with Hinsberg reagent.

(b) Convert Aniline to p-hydroxy azo benzene.

NH2 N 2+ Cl – OH

NaNO + HCl 0 – 5° C
Ans. →
2
+ → N N— OH
0 – 5 °C

Aniline p-hydroxy benzene

(c) Give one example of cationic detergent.

+
CH3
A
Ans. CH3—(CH2)15—N—CH3 Br–, cetyltrimethyl ammonium bromide.

CH3

(d) What is formula of paracetamol, (crosin), a well known antipyretic?

OH
B

Ans.

O

NH—C—CH3
Paracetamol

(e) How will you distinguish between Aniline and Benzyl amine?

Ans. Add NaNO2 and conc. HCl. Cool it to 0 – 5 °C. Then add alkaline solution of phenol. Aniline will give orange,

azo dye, whereas Benzyl amine does not.

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 III. Observe the histogram showing boiling points of pentane, iso pentane, 1°, 2° and 3 ° amines. Answer the questions
that follow based on table and related concepts.

350.8

329.3 K

310.5
309.0

300.8 K

JI
C2H5CH(CH3)2 CH3(CH2)3CH3 C2H5N(CH3)2 (C2H5)2NH C4H9NH2

(a)
LA
Why does CH3CH2CH2CH2NH2 (1° amine) has higher boiling point than (C2H5)2NH and C2H5N(CH3)2?

Ans. It is because extent of H-bonding is more in CH3CH2CH2CH2NH2 than 2° and 3° amines.

(b) Why does ethanol have higher boiling point than ethanamine?

Ans. It is because H-bonds are stronger in alcohols than amines because ‘O’ is more electronegative than ‘N’.

(c) Why amines are more basic than alcohol?

⊕ ⊕
Ans. It is because RNH3 is more stable than ROH2 ,  +ve charge on oxygen is not stable.

(d) Why are Primary amines more soluble in water than 2° and 3° amines?

Ans. It is because primary amines can form H-bonds with water to more extent.

(e) Arrange the compounds shown in graph, increasing order of boiling points. Give reason.

Ans. C2H5CH(CH3)2 < CH3(CH2)3CH3 < C2H5N(CH3)2 < (C2H5)2NH < C4H9NH2
A

Isopentane has lower boiling point that n-Pentane due to branching less surface area, less van der Waals’ forces
of attraction. 3° < 2° < 1° is order of boiling point in amines because extent of H-bonding increases.

IV. Table relates various amines with pKb values. Study this table and answer the questions related to table and
studied concepts.
B

Compounds pKb

1. Ammonia 4.75

2. CH3NH2 3.38

3. (CH3)2NH 3.27

4. (CH3)3N 4.22

5. CH3CH2NH2 3.29

6. (C2H5)2NH 3.00

7. (C2H5)3N 3.25

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 8. C6H5NH2 9.38

9. C6H5NHCH3 9.30

10. C6H5N(CH3)2 8.92

11. C6H5CH2NH2 4.70

12. p-nitro aniline 13.0

13. p-Toluidine 9.21

14. p-Anisidine 8.71

JI
(a) Arrange CH3NH2, (CH3)NH, (CH3)3N in decreasing order of basic character in aqueous solution. Give

reason.
Ans. (CH3)2NH > CH3NH2 > (CH3)3N,  in tertiary amines, there is more steric hindrances.

(b) Arrange C2H5NH2, (C2H5)2NH, (C2H5)3N in decreasing order of basic character in aq. solution. Give reason.

Ans. (C2H5)2NH > (C2H5)3N > C2H5NH2.

It is because in 3° amine, +I effect dominates over steric hindrances.

NO2 NH2
LA
(c) Arrange C6H5CH2NH2, C6H5NH2, C6H5N(CH3)2, , in increasing order of basic character.

NH2 CH3
NH2 NH2 NH2 N(CH3)2 CH2NH2

Ans. < < < <

NO2 CH3
A
(d) Arrange CH3NH2, (CH3)2NH, (CH3)3N in increasing order of basic character in gaseous state. Give reason.

Ans. (CH3)3N > (CH3)2NH > CH3NH2 (in gaseous state)

It is because electron density is maximum on ‘N’ in 3° amine > 2° > 1°, Stearic hindrance does not play any role.

(e) Why is Aniline less basic than benzyl amine?

Ans. It is because C6H5— electron withdrawing is directly attached to —NH2 in aniline but not in C6H5CH2NH2.
B

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