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UNIT 12

AMINES

Points to Remember

1.  .
Amines are alkyl and/or aryl derivatives of NH 3

2. Functional groups of 1º, 2º and 3º amines are respectively as given below :

3. Gabriel phthalimide synthesis can’t be used for the preparation of 2º and 3º

amines. It gives aliphatic primary amine only.

4. Hoffmann’s bromamide reaction gives 1º amines having one carbon atom less
than parent primary amide.

5. The order of basic strength of aliphatic amines is :

(i)  .
Aliphatic amines are more basic than NH 3

(ii) In aqueous solution medium, the order is 2º > 1º > 3º (for–CH3 group) and
2º > 3º > 1º for – C2H5 group.

(iii) In non-aqueous medium or gaseous phase, the order is 3º > 2º > 1º.

6. Basic strength of aromatic amines :

(i)  .
Aromatic amines are weaker bases than NH 3

(ii) ERGs like – CH3, – OR, – NH2 etc. increase basic strength while EWGs
like – NO2, – CN etc. decrease the basic strength. The effect of
substituents is more at para positions and less at meta position.

7. Basic strength of amines is expressed in terms of Kb or pKb.

8. 1º, 2º and 3º amines can be distinguished by Hinsberg’s test.

9. Hinsberg’s reagent is benzenesulphonyl chloride (C6H5SO2Cl).

10. 3º amines like trimethylamine are used as insect attractants.

11. Diazonium salts are represented by the general formula [Ar N ≡ N]+ X−.
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12. Structure of amines : Pyramidal for trimethyl amine ( CH 3 )3 − N.

 They are
Lewis bases.

13. Carbylamine test only given by 1º amines.

14. Manich reaction involves the reaction of ketones with HCHO and NH3 (or
amine) in acidic medium to form Manich bases.

15. 1º amines give effervescence with HNO2.

16. − NH2 group in aniline is o- and p- directing and is highly activating in nature.

17. Acylation of aniline is done before subjecting it to nitration or halogenation.

18. Aliphatic diazonium salts are very unstable and do not exist while aromatic salts
are relatively stable.

19. These salts are prepared from 1º aryl amines by diazotization reactions.

20. Diazotised salts (diazonium salts) are used to prepare a variety of aromatic com-
pounds.

21. R – C ≡ N have generally pleasant odours but alkyl isocyanides have highly
unpleasant odours.

22. Alkyl isocyanides have lower boiling points than that of isomeric alkyl cyanides
due to lower dipole moments.

23. Arenediazonium salts are highly reactive compounds and reactivity is due to
excellent leaving ability of diazo group as N2 gas.

NAME REACTIONS

1. Gabriel phthalimide synthesis

Gabriel synthesis is used for the preparation of primary amines. Phthalimide on
treatment wi ethanolic potassium hydroxide forms potassium salt of phthalim-
ide which on heating with alkyl halide followed by alkaline hydrolysis produces
the corresponding primary amine. Aromatic primary amines cannot be prepared
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Amines | 211

by this method because aryl halides do not undergo nucleophilic substitution

with the anion formed by phthalimide.

O O O

C KOH C – R–X C
N–H NK+ N–R
C C C

O O O
Phthalimide N–Alkylphthalimide
O
O
C –
NaOH (aq) C ONa+
N–R – + R – NH2
C ONa+
C (1° amine)
O
O
2. Hoffmann bromamide degradation reaction
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 present in the amide.
O

R – C – NH2 + Br2 + 4NaOH R – NH2 + Na2CO3 + 2NaBr + 2H2O

3. Carbylamine reaction
Aliphatic and aromatic primary amines on heating with chloroform and eth-
anolic 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.
Heat
R – NH2 + CHCl 3 + 3KOH R – NC + 3KCl + 3H 2O
4. Hinsberg Test:
Benzenesulphonyl chloride (C6H5SO2CI), which is also known as Hinsberg’s
reagent, reacts with primary and secondary amines to form sulphonamides.
(a) The reaction of benzenesulphonyl chloride with primary amine
yields N-ethylbenzenesulphonyl amide.
O O

S Cl + H —N — C2H5 S N —C2H5 + HCl

O O H
N-Ethylbenzenesulphonamide
(soluble in alkali)
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The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the

presence of strong electron withdrawing sulphonyl group. Hence, it is soluble
in alkali.
(b) In the reaction with secondary amine, N, N-diethylbenzenesuIphonamide
is formed.
O O

S Cl + H —N — C2H5 H3C S N —C2H5 + HCl

O C2H5 O C2H5
N,N-Diethylbenzenesulphonamide

Since N, N-diethylbenzene sulphonamide does not contain any hydrogen atom

attached to nitrogen atom, it is not acidic and hence insoluble in alkali.
(c) Tertiary amines do not react with benzenesulphonyl chloride. This property
of amines reacting with benzenesulphonyl chloride in a different manner
is used for the distinction of primary, secondary and tertiary amines and
also for the separation of a mixture of amines.
5. Sandmeyer Reaction
The C1-, Br- and CN- nucleophiles can easily be introduced in the benzene ring
of diazonium salts in the presence of Cu(I) ion.
CuCI/HCl ArCl + N2

+ – CuBr/HBr
ArN2X ArBr + N2

CuCN/KCN
ArCN + N2

6. Gatterman Reaction
Chlorine or bromine can be introduced in the benzene ring by treating the dia-
zonium salt solution with corresponding halogen acid in the presence of copper
powder.
Cu/HCl
+ – ArCl + N 2 + CuX
ArN2X
Cu/HBr
ArBr + N2 + CuX

7. Coupling reactions
The azo products obtained have an extended conjugate system having both the
aromatic rings joined through the -N=N- bond. These compounds are often co-
loured and are used as dyes. Benzene diazonium chloride reacts with phenol in
which the phenol molecule at its para position is coupled with the diazonium
salt to form p-hydroxyazobenzene. This type of reaction is known as coupling
reaction.
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Similarly the reaction of diazonium salt with aniline yields p-aminoazobenzene.

– –
+ OH
N NCl + H OH N=N OH + HCl

P-Hydroxyazobenzene (orange dye)

– +
+ H
N NCl + H NH2 N=N NH2 + HCl

p-Aminoazobenzene
(yellow dye)

DISTINCTION BETWEEN PAIRS OF COMPOUNDS

Give one chemical test to distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine
(ii) Secondary and tertiary amines
(iii) Ethylamine and aniline

MULTIPLE CHOICE QUESTIONS

1. In the nitration of benzene using a moisture of Conc H2SO4 and conc. HNO3
the species which initiates the reaction is:
(a) NO2 (b) NO+
(c) NO2+ (d) NO2–
2. The correct IUPAC name of Cu2 = CH—CH2NHCH3 is:
(a) Allymethyl amine (b) 2-amino-4-pentene
(c) 4-aminopent-lene (d) N-methylprop-2-en-anine
3. Which is the weakest base:
NH2
(a) (b) N—H
NH2

(c) (d) CH3NH2

4. The correct order of basic strength for the following compounds is:
NH2 NH2 NH2

(i) (ii) (iii)

NO2 CH3
(a) ii < iii < i (b) iii < i < ii
(c) iii < ii < i (d) ii < i < iii
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5. Methylamine reacts with HNO2 to form

(a) CH3—O—N==0 (b) CH3OCH3
(c) CH3OH (d) CH3CHO
6. CH3CH2COOH
The structure of ‘c’ would be
(a) CH3CH2CO NH2 (b) CH3CH2NHCH3
(c) CH3CH2NH2 (d) CH3CH2CH2NH2
NH2 CH3
N
NaNO2 CH3
7. B C
HCl Cold
The structure of ‘c’ would be
CH3 CH3
N N
(a)
CH3
CH3
(b) N N N
CH3
CH3
(c) N N N
CH3

(d) N N CH2 N N

CH3
8. Which of the following statement about primary amine is false:
(a) Aryl amines react with nitrous acid to produce phenol
(b) Alkylamines are stronger base than ammonia
(c) Alkyl amines are stronger base than aryl amines
(d) Alkyl amines react with nitrous acid to produce alcohol
9. Which of the following is most stable diazoniom salt?
(a) CH3N2+ X– (b) C6H5N2+ X–
(c) CH3CH2N2+ X– (d) C6H5CH2N2+ X–
10. Method by which aniline can not be prepared is:
(a) reduction of nitrobenzene with H2/Pd in ethanol.
(b) potassium salt of phthalimide treated with chlorobenzene
(c) hydrolysis of phenyl isocyanide with acidic solution
(d) degradation of benzamide with bromine in alkaline medium solution.
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Amines | 215
11. In the chemical reaction:
CH3CH2NH2 + CHCl3 + 3KOH → A + B + 3H2O
The compound A and B are respectively:
(a) CH3CH2CONH2 and 3KCl (b) CH3CH2NC + K2CO3
(c) CH3CH2NC and 3KCl (d) CH3CH2CNB + 3KCl
12. Considering the basic strength of amines in aqueous solution which one has
the smallest pkb value?
(a) (CH3)2NH (b) C6H5NH2
(c) CH3NH2 (d) (CH3)3N
13. Which of the following compound will give significant amount of meta
product during mono-nitration reaction?
OH OCOH3

(a) (b)

NH2 NHCOCH3

(c) (d)
14. The final product (c) in the following sequence of reaction is:
NH2
−

Br2 / OH
→ A 
NaNO2
HCl
→ B 
(i) HBF4
(ii)
→ C.

NH—Br CH2
F Br
(a) (b)

NO2 F
NH2 F
F F Br Br
(c) (d)

Br Br
O (i) NaOH, Br2
15. In the reaction C O
A
NH2 (ii) C
Cl
The structure of product A is:
O O
(a) CH3 NH (b) H3C C
C O C
O

O O
(c) NH (d) H3C C
C CH3 NH C
O
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16. A positive carbylamine test is given by

(a) N< N-Dimethylaniline (b) 2, 4-Dimethylaniline
(c) N-Methyl-0-methylaniline (d) p-methylbenzylamine
17. Which of the following reactions form benzylamine:

CONH2  →
LiAlH
(a) 4
H + / H 2O (b) C6H5CONH2 →
NaOBr

+ C NH  →
(i) KOH
(c) C6H5CN 
H / H 2O
→ (d) (ii) C H CH Br
C 6 5 2
(iii) aqOH −

O
18. Which reagent among the following can affect the conversion?
CH3—C≡≡N → CH3CH2NH2
(a) H2, Pt (b) Ammonical AgNO3
(c) LiA/H4 (d) NaBH4
19. In which of the following amines,the first has lower pkb value than the second
(a) aniline, m-nitroaniline (b) m-Toluidine, p-toluidine
(c) aniline, p-chloroaniline (d) aniline, p-aminophenol
20. Bromobenzene can be prepared from benzene diazonium chloride. When its
is treated with
(a) Cu/HBr (b) Br2; HBr
(c) CuBr/HBr (d) Br2, CCl4

Assertion Reason Type Questions

The question given below consist of an Assertion and the Reason. Use the following key
to choose the appropriate answer.
(a) Assertion and reason both are CORRECT and reason is the CORRECT
explanation of the assertion.
(b) Assertion and reason both are wrong statements.
(c) Assertion is correct statement but reason is wrong statement.
(d) Assertion is wrong statement but reason is correct statement.
(e) Assertion and reason both are correct statements but reasson is not correct
explanation of assertion.

Assertion and Reasoning

21. Assertion : n-Propylamine has higher boiling point than trimethylamine.

Reason : Among n-propylamine molecules, there is hydrogen bonding but there
is not hydrogen bonding in trimethylamine.
22. Assertion : Aniline does not undergo Friedel Crafts reaction.

Reason : Friedel Crafts reaction is an electrophilic substitution reaction.
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23. Match column 1 and column II

Column-I Column-II
(A) Ammolysis (p) Amine with lesser no. of carbon
atom
(B) Gabriel phthalimide (q) Detection of primary amine
(C) Hoffmann bromide amide degradation(r) Reaction of pthalimide with KOH
and R—X
(D) Carbylamine reaction (s) Reaction of alkyl halides with NH3
(a) A–s, B–r, C–p, D–q (b) A–p, B–q, C–r, D–s
(c) A–r, B–s, C–p, D–q (d) A–s, B–r, C–q, D–p
24. Match column 1 and column II
Column-I Column-II
(A) Benzene sulphonyl chloride (p) zwitter ion
(B) Sulphanilic acid (q) Hinsberg reagent
(C) Alkyl diazonium salts (r) Dyes
(D) Aryl diazonion salts (s) Conversion to alcohols
(a) A–p, B–q, C–s, D–r (b) A–q, B–p, C–s, D–r
(c) A–q, B–p, C–r, D–s (d) A–s, B–r, C–q, D–p
25. The no. of amines having pkb less than C6H5NH2 among the following.
P—CH3—C5H4 NH2, O—CH3—C6H4NH4, m—CH3C6H4—NH2, C6H5N(CH3)2,
C6H5NHCH3, p—NO2C6H4 NH2, p—ClC6H4NH2, C6H5CH2NH2, C6H5CH2CH2NH2
0 1 2 3 4 5 6 7 8 9

ANSWERS
1. (c) 2. (d) 3. (a) 4. (d) 5. (c) 6. (c) 7. (c) 8. (a) 9. (b) 10. (b)
11. (c) 12. (a) 13. (c) 14. (d) 15. (a) 16. (b, d) 17. (a, d)
18. (a, c) 19. (a, c) 20. (a, c) 21. (a) 22. (b)
23. (a) 24. (b) 25. 7

VERY SHORT ANSWER TYPE QUESTIONS (1 Mark)

Q. 1. Write IUPAC name of CH3NC.

Ans. Methane carbylamine.

Q. 2. Convert m-dinitrobenzene to m-nitro aniline.
NO2 NH2
(NH4)2s
Ans.
[H]
NO2 NO2
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Q. 3. Draw structure of TNT, an explosive.

Ans.

Q. 4. Write IUPAC name of

Ans. 3-Methyl-N,N-dimethyl pentanamine

Q. 5. Give one use of quaternary ammonium salts.

Ans. It is used as detergents, e.g., [CH3(CH2)15N(CH3)2]+Cl−.

Q. 6. What is Hinsberg’s reagent ?

Ans. Benzene sulphonyl chloride,

Q. 7. Why aniline dissolves in HCl ?

Ans. C6H5NH2 + HCl → [C6H5NH3]+Cl−.

It dissolves due to its basic nature.

Q. 8. How will you test the presence of primary amine ?

Ans. By carbyl amine test.

RNH2 + CHCl3 + 3KOH → R—NC + 3KCl + 3H2O

Q. 9. What is vapour phase nitration ?

Ans. CH4 + HNO3 CH3NO2
(High temperature and nitration in vapour phase only)

Q. 10. Write one use of dopamine and atropine alkaloid.

Ans. Dopamine : Neurotransmitter

Atropine alkaloid : 0.5-1.0% solution ophthalmic examination.

Q. 11. Direct nitration of aniline is not carried out. Explain.

Ans. (H2SO4 + HNO3) easily oxidized aniline into tarry complex product due to high
e− density on the benzene ring of aniline.
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Q. 12. Among the compounds as following which will react with

to give product containing > C = N − ?
(i) C6H5NH2 (ii) (CH3)3N

(iii) C6H5NHC6H5 (iv) C6H5NHNH2

Ans. C6H5NH2 and C6H5NHNH2.

Q. 13. How will you give expression for Kb to indicate its basic strength ?

 RNH 3+   OH − 
Ans. Kb = 
[ R − NH 2 ]
Q. 14. What happens when aniline is treated with bromine ?

Ans.

Q. 15. Write a chemical equation to illustrate the ammonolysis.

Ans. For alcohols :

C 2 H 5 OH → 3
Al O /620K2
NH 
C 2 H 5 NH
3
2 
2 5
−H O
→ ( C 2 H 5 )2 NH
C H OH
2
 
2 5
→ ( C 2 H 5 )3 N

C H OH

For alkyl halides :

+
C 2 H 5 I 
3
− HI
 
→ C2 H 5 NH
NH /373 K
2
2 5
− HI
→ ( C2 H 5 )2 NH
C H I  
2 5
− HI
→ ( C 2 H 5 )3 N
C H I  
2 5
− HI
→ ( C2 H 5 )34 N
C H I   I −

Q. 16. Write the structure of p-toluidine.
CH3

Ans.

NH2
Q. 17. Prepare/convert nitrobenzene into aniline.

NO2 NH2
H2/Ni
Ans.
Reduction

Q. 18. Convert C6H5COOH to C6H5NH2.

COOH CONH2 NH2

NH3(aq) Br2/KOH
Ans.
∆ ∆
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Q. 19. Write isomerism exhibited by different amines.

Ans. Chain, position, metamerism, functional.

Q. 20. Arrange the following compounds in increasing order of solubility in water:

C6H5NH2, (C2H5)2NH, C2H5NH2

Ans. C6H5NH2 < (C2H5)2NH< C2H5NH2

SHORT ANSWER TYPE QUESTIONS (2 Marks)

Q. 1. Complete the following acid-base reactions and name the products :

(i) CH3CH2CH2NH2 + HCl →

(ii) (CH3CH2)3N + HCl →

Ans. (i) CH3CH2CH2N+H3Cl− (n-propyl ammonium chloride)

(ii) (CH3CH2)3 – N+HCl− (Triethyl ammonium chloride)

Q. 2. Write chemical reaction of C6H5NH2 + C6H5COCl and name product ob-

tained.

Ans.

Q. 3. How will you convert :

(i) 3-methylaniline → 3-nitrotoluene

(ii) Aniline → 1, 3, 5-tribromobenzene

Ans. (i)

NH2 NH2 N2Cl

Br Br Diazo Br Br H3PO2 + H2O Br Br
Br2/H2O
(ii)
NaNO2/HCl (Cu+ )
Br Br Br
Q. 4. How will you convert :

(i) Propanoic acid → Ethanoic acid

(ii) Nitromethane → Dimethylamine

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Ans. (i) C2 H5COOH 

NH
∆
3
→ C2 H5CONH 2 
Br KOH
2
→ C2 H5 NH 2 
HNO2
→ CH3CH 2 OH → CH3CHO → CH3CHO → CH3COOH
[O] [O] [O]

(ii) CH 3 NO 2 
H /Ni
→ CH 3 NH 2 →
2 CH Cl/KOH
CH 3 N ≡ C 
3 H /Ni
→ CH 3 − NH − CH 3
2

Q. 5. Draw the structures of the following compounds :

(i) N-isopropylaniline (ii) t-butylamine

Ans. (i) (ii)

Q. 6. Why C6H5N+(CH3)3OH− a stronger base than NH4OH ?

Ans. Due to – I effect of phenyl group, it decreases e− density on nitrogen atom but
no such group in NH4OH.

Q. 7. Explain Kb order : Et2NH > Et3N > EtNH2 in aqueous solution.

Ans. Basicity of amines in aqueous solution depends upon :

(i) + I effect of an alkyl group.
(ii) Extent of hydrogen bonding with H2O.
(iii) Steric effects of alkyl groups.

Q. 8. Distinguish between 1º, 2º and 3º amines by HNO2 acid test.

Ans. 1º gives N2 gas. 2º gives yellow oily compound. 3º form water soluble salts.
CH3CH2NH2 + HNO2 → C2H5OH + N2 + H2O
R2NH + HNO2 → R2N – N = O + H2O
⊕
→ [(CH3CH 2 )3 NH] NO 2−
(CH3CH 2 )3 N + HNO 2 
Soluble in water
Q. 9. A compound ‘A’ having molecular formula C3H7ON reacts with Br2 in pres-
ence of NaOH to give compound ‘B’. This compound ‘B’ reacts with HNO2
to form alcohol and N2 gas. Identify compound ‘A’ and ‘B’ and write the
reaction involved.

‘A’ is CH3CH2CONH2  → CH3CH2NH2  → C2H5OH + N2 + H2

BrHNO 2
Ans. 2
NaOH

(B)

Q. 10. Write chemical equation for the following conversions :

(i) CH3 − CH2 – Cl → CH2 – CH2 – CH2 – NH2

(ii) C6H5 – CH2 – Cl → C6H5CH2CH2 – NH2

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Ans. (i) With NaCN and reduction.
i.e., C2H5Cl  → C2H5 – C ≡ N  → CH3 – CH2 – CH2 – NH2
Ethanol
red n
NaCN

(ii) C6H5CH2Cl 

Ethanol
NaCN
→ C6H5 – C ≡ N 
H 2 / Ni
→ C6H5CH2CH2 – NH2
Q. 11. Account for :

(i) Amino group in aniline is o- and p- directing in aromatic electrophilic

substitution reactions. Aniline on nitration gives a substantial amount
of m-nitroaniline.

(ii) Aniline does not go Friedel Crafts reaction.

⊕
Ans. (i) It is because aniline is protonated to form anilinium cation, in which N H 3
.
group is meta-directing.
(ii) It is because aniline is basic, can form adduct with AlCl3, electrophile
cannot be generated.

Q. 12. Account for the following :

(i) Electrophilic substitution in aromatic amines takes place more
readily than benzene.

(ii) Nitro compounds have higher boiling points than hydrocarbons

having almost same molecular mass.

Ans. (i) –NH2 is ERG, electrophilic substitution takes place faster.

(ii) Nitro compounds are more polar than hydrocarbons therefore have more
van der Waal’s forces of attraction.
Q. 13. Write short notes on :
(i) Coupling reaction
(ii) Ammonolysis

Ans. (i) alkaline

N º NCl + H NH2 N=N NH2 + HCl
(pH 4-5)

(ii) Ammonolysis : R – X + NH3 → R – NH2 + HX

RNH2 + R – X → (R)2N + HX

(R)2NH + R – X → (R)3N + HX

(R)3N + R – X → [R4N]⊕X−
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Q. 14. Prepare pure sample of 1º amine from 1º alkyl halide.

Ans. By Gabriel Phthalimide Reaction

ANSWER-II TYPE QUESTIONS (3 Marks)

Q. 1. What happens when :
(i) An alkyl halide reacts with AgNO2 and product is reduced.
(ii) An alkyl halide is treated with AgCN and product is hydrolysed.
(iii) Methyl magnesium is treated with cyanogens chloride.

Ans. (i) R – X + AgNO2 

− AgX
→ R – NO2 
Sn/HCl
[H]
→ R – NH2

H O/H +
(ii) R – X + AgCN 
− AgX
→ RNC →
2
RNH2 + HCOOH

(iii) CH3MgBr + CN – Cl → CH3CN + Mg<

Q. 2. How would you prepare :

(i) C6H5NH2 from C6H5NO2

(ii) CH3NH2 from C2H5NH2

(iii) C2H5NH2 from CH3NH2

Ans. (i)

→ C2H5OH →
(O)
(ii) C2H5NH2 
HNO 2
K 2 Cr2 O7 /H 2SO 4
CH3COOH 
NH3
→
∆
CH3COONH4 
− H2O
→ CH3CONH2 
Br2 /KOH
→ CH3NH2

(iii) CH3NH2 

HNO 2
→ CH3OH 
SOCl2
→ CH3Cl 
KCN
→ CH3CN
 [H]
→ CH3CH2NH2
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Q. 3. Write the structure of the products in each case :

(i) CH3CH2NH2 

(CH 3CO)2 O
→
∆

(ii) CH3CONHC6H5 

Br2 /Fe
→
H 2O/ H +
(iii) CH3CH2CN  →

Ans. (i) CH3CH2NHCOCH3, CH3COOH

(ii)

(iii) CH3CH2COOH + NH4+

Q. 4. Write the structures of A, B and C in following

C6 H 5CONH 2 
→ A  → B → C
2 Br NaOH
2 NaNO +HCl KI
(i) O-5°C

CH 3Cl 
→ A  → B 
→C
KCN 4 LiAlH
3 CHCl +AlCKOH
(ii)

Ans. (i) C6 H5 NH 2 ,C6 H5 N 2+ Cl− ,C6 H5 I

(ii) CH3CN, CH3CH2NH2, CH3CH2NC

Q. 5. Write the structure of reagents/organic compounds ‘A’ to ‘F’ :

A  → B  → C 
→ E →F
Ans. NaOH Br
2 2 NaNO HCl
2 D Cl Fe
H O 2 O'C

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Amines | 225

LONG ANSWER TYPE QUESTIONS (5 Marks)

Q. 1. Arrange the following :

(i) In decreasing order of pKb values :

C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2

(ii) In increasing order of basic strength :

(a) Aniline, p-nitroaniline and p-toluidine

(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2

(iii) In decreasing order of basic strength :

C6H5NH2, C6H5N(CH3)2, (C2H5)2NH, CH3NH2

(iv) Decreasing order of basic strength in gas phase :

C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3

(v) Increasing order of boiling point :

C2H5OH, (CH3)2NH, C2H5NH2

Ans. (i) C6H5NH2 > C6H5NHCH3 > C2H5NH2 > (C2H5)2NH

(ii) (a) p-nitroaniline < aniline < p-toluidine

(b) C6H5NH2 < C6H5NHCH3 < C6H5CH2NH2
(iii) (C2H5)2NH > CH3NH2 > C6H5N(CH3)2 > C6H5NH2

(iv) (C2H5)3N > (C2H5)2NH > C2H5NH2 > NH3

(v) (CH3)2NH < C2H5NH2 < C2H5OH

Q. 2. How will you convert :

(i) Ethanoic acid into methanamine

(ii) Hexane nitrile into 1-aminopentane

(iii) Methanol into ethanoic acid

(iv) Ethanamine into methanamine

CH 3COOH + HN 3  → CH 3 NH 2 + N 2 + CO 2
Conc. H SO
Ans. (i) 2
heat
4

Ethanoic acid Hydrazoic Methylamine

acid
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(ii) CH 3 ( CH 2 )4 CN  → CH 3 ( CH 2 )4 CONH 2  → CH 3 ( CH 2 )4 NH 2

Conc. HCl Br /KOH
2
partial hydrolysis
Hexane nitrile Hexanamide 1-Aminopentane

+
(iii) CH 3OH 
SOCl2
→ CH 3Cl 
KCN (alc)
→ CH 3CN 
H /H 2 O
→ CH 3COOH
Methanol Ethanoic acid

KMnO /H +
CH 3 CH 2 NH 2 
( NaNO + HCl ) → CH 3 CH 2 OH → CH 3 COOH → CH 3 COONH 4
HNO
3 4 4 NH OH
(iv) 2
Ethanamine

 
heat
→ CH 3 CONH 2 
Br2 /KOH
→ CH 3 NH 2
Methanamine

Q. 3. Write short note on the following :

(i) Carbylamine reaction

(ii) Diazotization

(iii) Hoffmann’s bromide reaction

(iv) Coupling reaction

(v) Ammonolysis

Ans. (i) Carbylamine reaction : When primary amine (aromatic or aliphatic)

warmed with chloroform and alc. KOH, isocyanides are formed which
can be identified by their offensive smell. This test is used to identify the
presence of primary amine or chloroform.

∆
RCH2NH2 + CHCl3 + 3KOH (alc.)  → RCH2NC + 3KCl + 3H2O

(b) Diazotization : When primary aromatic amine is treated with NaNO2 and
HCl at 273-278 K, diazonium salt is obtained. This reaction is known as
diazotization.
+ –
N = NCl
NH2 273 – 278 K
+ NaNO2 + HCl + 2H2O
Aniline Benzenediazonium
chloride

Benzenediazonium chloride is a very important synthetic compound, which can

be changed into heloarenes, phenol, cyanobenzene, benzene etc.
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Amines | 227
(c) Hoffmann’s bromide reaction : When any primary amide (aliphatic or
aromatic) is treated with bromine and alkali, it gives the amine with one
less carbon atom.

This reaction is used to reduce one carbon atom from a compound.

(d) Coupling reaction : When benzenediazonium chloride is treated with

phenols or aromatic amines, azo dyes are produced in which diazo
(− N = N −) group is retained. Coupling reactions generally take place at
p-position of phenol or aromatic amines.
+ – NaOH
N = NCl + OH N=N OH

Benzenediazonium Phenol p-Hydroxyazobenzene

chloride (Azo dye)

(e) Ammonolysis : Reaction of alkyl halides with ammonia is known as

ammonolysis. Ammonolysis generally gives the mixture of 1º, 2º, 3º
amines and quaternary ammonium salt.

Q. 4. Complete the following reactions :

(i) C6H5NH2 + H2SO4 (conc.) →

(ii) C6H5N2Cl + C2H5OH →

(iii) C6H5NH2 + (CH3CO)2O →

(iv) C6H5N2Cl + H3PO2 + H2O →

(v) C6H5NH2 + CHCl3 + 3KOH (alc.) →

Ans. (i) .

(ii) C6H6 + N2 + HCl + CH3CHO

(iii) C6H5NHCOCH3 + CH3COOH

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228 | Chemistry-XII
(iv) C6H6 + H3PO3 + HCl + N2

(v) C6H5NC + 3KCl + 3H2O

Q. 5. Write A, B and C in the given reactions :

H O/ H +
C6 H 5 N 2Cl  → A 
→ B  →C
CuCN NH
(i) 2 3

CH 3 CH 2 Br  → A → B  →C

KCN LiAlH HNO
(ii) 4
0º C
2

H O/ H +
(iii) C6 H 5 NO 2 → A  → B  →C
Fe/ HCl HNO2 2
273 K 2∆

(iv) CH 3 COOH 

NH 3
∆
→ A 
NaOBr
→ B 
NaNO 2 / HCl
→C
−
CH 3 CH 2 I  → A  → B  →C
NaCN OH NaOH/Br
(v) partial hydrolysis
2

Ans. (i) C6H5CN, C6H5COOH, C6H5CONH2

(ii) CH3CH2CN, CH3CH2NH2, CH3CH2OH

(iii) C6H5NH2, C6H5N2Cl, C6H5OH

(iv) CH3CONH2, CH3NH2, CH3OH

(v) CH3CH2CN, CH3CH2CONH2, CH3CH2NH2

Q. 6. Accomplish the following conversions :

(i) C6H5NO2 → C6H5 – COOH

(ii) Benzene → m-bromophenol

(iii) C6H5COOH → C6H5NH2

(iv) Aniline → 2, 4, 6 tribromoaniline

(v) Benzylchloride → 2-phenyl ethanamine

Ans. (i)
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Amines | 229
NO2 NO2 NO2
Conc. HNO3 Br2 Sn + HCl
(ii)
Conc. H2SO3 Fe
Br Br

+
N=N OH
NaNO2+HCl +
H /H2O
0-5°C
Br Br

(iii)

(iv)

(v)

Q. 7. Given reasons : (i) Acetylation of aniline reduces its activation effect.

(ii) CH3NH2 is more basic than C6H5NH2
(iii) Although –NH2 group is o/p directing , yet aniline on nitration gives a
significant amount of m-nitroaniline
Ans. (i) Due to the resonance, the electron pair of nitrogen atom gets delocalised
towards carbonyl group/resonating structures.
(ii) Because of +I effect in methylamine electron density at nitrogen increases
whereas in aniline resonance takes place and electron density on nitrogen
decreases / resonating structures.
(iii) Due to protonation of aniline / formation of anilinium ion

Source: EDUDEL