26 Amines: Solutions
26 Amines: Solutions
26 Amines: Solutions
Amines
Solutions
SECTION - A
Objective Type Questions
CH3
H
1. CH3 C N is a
H
CH3
(1) Primary amine (2) Secondary amine (3) Tertiary amine (4) Ammonium salt
Sol. Answer (1)
NH2
NH
CH3
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120 Amines Solution of Assignment
4. A secondary amine is
(1) A compound with two –NH2 group
(2) A compound with two carbon atoms and a –NH2 group
(3) A compound with a –NH2 group on the carbon atom in number two position
(4) A compound in which two of the hydrogens of NH3 have been replaced by alkyl or aryl groups
Sol. Answer (4)
CH 3 – N – CH 3 is secondary amine.
H
6. Best method for preparing primary amines from alkyl halides without changing the number of carbon atoms
in the chain is
(1) Hoffmann bromamide reaction (2) Gabriel phthalimide synthesis
(3) Sandmeyer reaction (4) Reaction with NH3
Sol. Answer (2)
1° amine can be prepared by Gabriel phthalimide reaction
8. When acetamide is treated with Br2 and caustic soda, then we get
(1) Bromoacetic acid (2) Acetic acid (3) Methylamine (4) Ethane
Sol. Answer (3)
O
–
Br21OH
CH 3 – C – NH 2 CH 3 – NH 2
Reduction
9. CONH2 CH2NH2
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Solution of Assignment Amines 121
10 Amines are basic in character because they have
(1) A lone pair of electrons on the nitrogen atom (2) A hydroxyl group in the molecule
(3) Replaceable hydrogen atom (4) Saturated C atom
Sol. Answer (1)
:
NH2
12. Aliphatic amines are ______ basic than NH3 but aromatic amines are ______ basic than NH3.
(1) More, less (2) Less, more (3) Both (1) & (2) (4) None of these
Sol. Answer (1)
Because in aromatic amine lone pair is in conjugation with benzene ring.
NH2 NH2
15. The correct increasing order of basic strength for the following compounds is
NH2 NH2 NH2
NO2 CH3
(I) (II) (III)
(1) II < III < I (2) III < I < II (3) III < II < I (4) II < I < III
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122 Amines Solution of Assignment
CH3 NO2
(+H) (–M)
Basic strength
NO2
17. The decreasing order of the basic character of NH3, CH3NH2, C2H5NH2 and C6H5NH2 is
(1) NH3 > CH3NH2 > C2H5NH2 > C6H5NH2 (2) C2H5NH2 > CH3NH2 > NH3 > C6H5NH2
(3) C6H5NH2 > C2H5NH2 > CH3NH2 > NH3 (4) CH3NH2 > C2H5NH2 > C6H5NH2 > NH3
Sol. Answer (2)
N
is least basic
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Solution of Assignment Amines 123
Sol. Answer (3)
NH2 is the strongest base among the other shown bases because of max e– density over N-atom.
O O
+
:
NH2 NH2
NH2
resonance
CH2
(1) CH3CH2CH2NH2 (2) (CH3)3N (3) NH (4) CH3OH
CH 3
CH3
N is most volatile in above choices
CH3 CH3
O O
NH2+ NH–C–CH3
Cl
acetanilide
23. The compound obtained by heating a mixture of a primary amine and chloroform with ethanolic potassium
hydroxide is
(1) An alkyl isocyanide (2) An alkyl halide
(3) An amide (4) An amide and nitro compound
Sol. Answer (1)
OH−
R – NH2 + CHCl3 ⎯⎯⎯ → R − N= C
alkyl isocyanide
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124 Amines Solution of Assignment
24. A compound X has the molecular formula C7H7NO. On treatment with Br2 and KOH, X gives an amine Y.
The latter gives carbylamine test. Y upon diazotisation and coupling with phenol gives an azo dye. Thus X
is
25. An organic compound (A) on reduction gave a compound (B). Upon treatment with HNO2, (B) gave ethyl
alcohol and on warming with CHCl3 and alcoholic KOH, (B) gave an offensive smell. The compound (A) is
CH3–CH2–N =C
26. An amine reacts with C6H5SO2Cl and the product is soluble in alkali, amine is
(1) 1° amine (2) 2° amine (3) 3° amine (4) All of these
Sol. Answer (1)
O O
R–NH2 + Cl–S– R–N–S–
(1°)
O H O
Base
Soluble
27. Which would not react with benzene sulphonyl chloride in aqueous NaOH?
(1) Aniline (2) N, N-dimethylaniline (3) p-toluidine (4) N-ethyl aniline
Sol. Answer (2)
Me O
N + Cl–S Because of lack of H on nitrogen.
Me
O
No reaction
28. Reaction of nitrous acid with aliphatic primary amine in the cold gives
(1) A diazonium salt (2) An alcohol (3) A nitrite (4) A dye
Sol. Answer (2)
R–NH2 + HONO R–OH
(Alcohol)
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Solution of Assignment Amines 125
29. The gas evolved when methylamine reacts with nitrous acid is
(1) NH3 (2) N2 (3) H2 (4) C2H6
Sol. Answer (2)
CH3NH2 + 2HNO2 C-H3–O–N =O + N2 + H2O
Methyl nitrite
2CH3NH2 + 2HNO2 CH3–O–CH3 + 2N2 + 3 H2O
Methoxy methane
1° Amine reacts with nitrous acid to form alcohol except methyl amine at ordinary temperature.
(1) CH3 – O – NO (2) CH3 – CH2 – NO2 (3) CH3CH2CN (4) CH3 – CH – CH
CH3
Sol. Answer (2)
O OH
CH3 – CH2 – N CH3 – CH = N
O O
Nitro form Aci form
31. A compound ‘A’ when treated with HNO3 (in presence of H2SO4) gives compound B, which is then reduced
with Sn and HCl to aniline. The compound is
(1) Toluene (2) Benzene (3) Ethane (4) Acetamide
Sol. Answer (2)
Nitration Sn/4HCl
NO2 NH2
(Benzene) (Aniline)
32. A mixture of 1°, 2° and 3° amines can be separated by Hinsberg’s reagent which is
(1) Benzoyl chloride (2) Acetyl chloride
(3) Benzene sulphonyl chloride (4) Benzyl chloride
Sol. Answer (3)
Hinsberg's reagent
O
–S–Cl
O
Benzene sulphonyl chloride
NHCOCH3
HNO3 H2O
Intermediate X
H2SO4
O
NH–C–CH3 NH–C–CH3 NH2
O Nitration H2O
NO2
Br
H2O
–NH2 + Br2 Br – NH2
Br
37. Which of the following forms a stable diazonium salt at 273 - 278 K?
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Solution of Assignment Amines 127
38. Which one of the following compounds gives dye test?
(1) Aniline (2) Methylamine (3) Diphenylamine (4) Ethylamine
Sol. Answer (1)
Aniline gives a dye test.
39. The strongest ortho-para and strongest meta directing groups are respectively
(1) –NO2 and –NH2 (2) –CONH2 and –NH2 (3) –NH2 and –NO2 (4) –NH2 and CONH2
Sol. Answer (3)
– NH2 Strongest o/p directing because of + R nature
– NO2 Strongest m directing because of – R nature
N2+Cl– + H2O OH
41. Benzenediazonium chloride on reaction with phenol in weakly basic medium gives
(1) Diphenyl ether (2) p-Hydroxyazobenzene (3) Chlorobenzene (4) Benzene
Sol. Answer (2)
OH
–
+ – OH
N2 Cl + OH
N
N
42. When benzenediazonium chloride is heated with fluoro boric acid, fluorobenzene is formed. This reaction is
called
(1) Balz Schiemann reaction (2) Gattermann reaction
(3) Sandmeyer reaction (4) Hofmann bromamide reaction
Sol. Answer (1)
+ – + –
N2 Cl + H BF4 F
(Benzene)
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128 Amines Solution of Assignment
44. Diazotisation can be carried out by the action of NaNO2 and dilute HCI at ice cold temperature
(1) Aromatic secondary amine (2) Aromatic primary amine
O–5°C
NH2 + HONO NH2+ C–
45. When benzene diazonium chloride is treated with cuprous chloride and HCI the product formed is
(1) Chlorobenzene (2) Benzene
HCl
N2+Cl– + Cu2Cl2 Cl (Sandmeyr's reaction)
+ –
N2 Cl
N2+Cl– CN COOH
+
CuCN H NaOH
H2O Cao,
SECTION - B
Objective Type Questions
1. R–NH 2 + CH 3COCl A.
(excess)
O O
R–NH2+CH3–C–Cl R–NH–C–CH3
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Solution of Assignment Amines 129
2. Arrange the following compound in decreasing order of boiling point
(1) (CH3)3N < CH3NHC2H5 < C3H7NH2 < C3H7OH (2) (CH3)3N < C3H7NH2 < C3H7OH < CH3NHC2H5
(3) C3H7NH2 < CH3NHC2H5 < (CH3)3N < C3H7OH (4) (CH3)3N < CH3NHC2H5 < C3H7OH < CH3H7NH2
Sol. Answer (1)
CH3
+
At PH = 2 : H3N – CH – COOH
CH3
At PH = 10 : NH2 – CH – COO–
4. Which product is formed, when acetonitrile is hydrolysed partially with cold concentrated HCl?
(1) Methyl cyanide (2) Acetic anhydrides (3) Acetic acid (4) Acetamide
Sol. Answer (4)
O
partially
CH3CN + H2O CH3 – C – NH2
5. Which one of the following on reduction with lithium aluminium hydride yields a secondary amine?
(1) Methyl isocyanide (2) Acetamide (3) Methyl cyanide (4) Nitroethane
Sol. Answer (1)
Me
CH3N = C + LiAlH4 NH
Me
(2°) amine
6. Which of the following pair make fastest coupling reaction in acidic medium?
NO2 N2+Cl– +
N
N
NO2
+ –
NH2 + HONO N2 Cl
(Stable)
8. The reaction of the benzyl chloride with sodium cyanide followed by reduction with hydrogen in the presence of
nickel gives
(1) -phenyl ethylamine (2) N-isobutylaniline (3) Benzyl amine (4) Aniline
Sol. Answer (1)
– [H]
+ CN
Cl CN NH2
(-phenyl
ethylamine)
COCH3
is most reactive because the Migration step is RDS step and assisted by (+M) of –OCH3 at p-
OCH3
position.
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Solution of Assignment Amines 131
10. Amine is obtained as major product in
CH3
NH3 NaNH2
(1) Cl (2) CH3 CH2 CH CH3 NH3
Cl
O
LiAlH4
(3) CH 3 C NH CH3 (4) All of these
NO2
+
KCN H2O/H
A B
11. .
Br
NO2 COOH
NO2 COOH
COOH COOH Br Br
NO2
+
KCN H2O/H
A B
COOH
COOH
B is
Br
Mechanism
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132 Amines Solution of Assignment
(1) HNO2 acid (2) CHCl3 /KOH (3) Br2 water (4) Schiff ’s reagent
NH2
NH2
CH3 CH3
N
1
2
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Solution of Assignment Amines 133
NO2
(NH4)2S NaNO2 /
15. (A) (B)
HCl, 0ºC
NO2
H3O+ CuCN/
(D) (C)
HCN
The above reaction sequence (D) is
COOH
NO2
O
The product (C) is
O O
COOH CO C
NH O
(1) (2) NH (3) (4)
COOH CO C NH NH
O O
O O
+ NH2NH2, EtOH
O
NH
R – NH2 +
NH
O
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134 Amines Solution of Assignment
N(CH3)2
HNO2
17. A . The product A will be
N(CH3)2 N(CH3)2
NO2 O=N–NCH3
18. Write the correct order of the following diazonium cations for the coupling with phenol
OCH3
CH3 NO2
I II III IV
(1) III > IV > I > II (2) II > I > IV > III (3) III > I > II > IV (4) II > IV > I > III
Sol. Answer (1)
The order of reactivity for coupling with phenol is
+ + + +
N2 N2 N2 N2
OCH3
NO2 CH3
19. When methyl iodide treated with ammonia, the product obtained is
(1) Methyl amine (2) Dimethyl amine (3) Trimethyl amine (4) All of these
Sol. Answer (4)
+ +
CH3I + NH3 CH3NH2 + NH (CH3)2 + I N (CH3)4 + N (CH3)3
–
20. C7H9N has how many isomeric forms that contain a benzene ring?
(1) 4 (2) 5 (3) 6 (4) 7
Sol. Answer (2)
NH2
NH2 NH2
CH3
CH3 CH3
NH – CH3 CH2 – NH2
SECTION - C
Previous Years Questions
NH2
NaOH
+ Cl
O
H
N
O
The synthesis of amides from amines with acyl halides or anhydrides in the presence of aqueous base is known
as the Schotten-Baumann reaction.
(2) Potassium salt of phthalimide treated with chlorobenzene followed by hydrolysis with aqueous NaOH
solution
Cl
NH2
(p-Aminophenol)
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136 Amines Solution of Assignment
+
NNCl
–
NH2
+
H (A) is [AIPMT-2014]
+
yellow dye
NH 2
(1) N=N–NH (2) N=N
NH2
(3) N=N (4) N=N NH2
–
5. Which of the following will be most stable diazonium salt RN2 X ? [AIPMT-2014]
–
(1) CH3N2 X (2) C6H5N2 X– (3) CH3 CH2 N2 X– (4) C H CH N2 X–
6 5 2
6. An organic compound (C3H9N) (A), when treated with nitrous acid, gave an alcohol and N2 gas was evolved.
(A) on warming with CHCl3 and caustic potash gave (C) which on reduction gave isopropylmethylamine. Predict
the structure of (A) [AIPMT (Mains)-2012]
CH 3
(1) CH–NH2 (2) CH3CH2–NH–CH3 (3) CH 3–N–CH 3 (4) CH3CH2CH2–NH2
CH3
CH3
Sol. Answer (1)
CH3
CH – NH2
CH3
7. Nitrobenzene on reaction with conc. HNO3/H2SO4 at 80–100°C forms which one of the following products?
[NEET-2013]
(1) 1,3-Dinitrobenzene (2) 1,4-Dinitrobenzene (3) 1,2,4-Trinitrobenzene (4) 1,2-Dinitrobenzene
Sol. Answer (1)
NO2
NO 2
A
8. In the reaction Br
+ Br
N2Cl
A is [NEET-2013]
(1) Cu2Cl2 (2) H3PO2 and H2O (3) H+/H2O (4) HgSO4/H2SO4
Sol. Answer (2)
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Solution of Assignment Amines 137
NO2
Zn
9. What is the product obtained in the following reaction:
NH Cl
...........?
4
[AIPMT (Prelims)-2011]
NH2 NHOH
(1) (2)
–
N O
Zn
NO2 NH4Cl
NH OH
N-phenylhydroxylamine
11. Acetamide is treated with the following reagents separately. Which one of these would yield methylamine?
[AIPMT (Prelims)-2010]
(1) NaOH – Br2 (2) Sodalime (3) Hot conc. H2SO4 (4) PCl5
Sol. Answer (1)
O
Br2/OH
CH3 NH2 CH3 – NH2
12. Which of the following statements about primary amines is 'False'? [AIPMT (Prelims) -2010]
(1) Alkyl amines are stronger bases than aryl amines
(2) Alkyl amines react with nitrous acid to produce alcohols
(3) Aryl amines react with nitrous acid to produce phenols
(4) Alkyl amines are stronger bases than ammonia
Sol. Answer (3)
Aryl amines react with nitrous acid to form diazonium salt.
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138 Amines Solution of Assignment
13. Aniline in a set of the following reactions yielded a coloured product 'Y'
NH2
NaNO2/HCl N, N-dimethylaniline
X Y
(273 – 278K)
CH3 CH3
CH3
(1) N=N N (2) HN NH NH
CH3
CH3 CH3
Ml
Y is a pot of coupling reaction i.e., N=N N
Ml
14. Match the compounds given in Column-I with their characteristic reactions given in Column-II. Select the correct
option
Column-I Column-II
(Compounds) (Reactions)
a. CH3CH2CH2CH2NH2 (i) Alkaline hydrolysis
b. CH3C CH (ii) With KOH (alcohol) and CHCl3 produces bad smell
c. CH3CH2COOCH3 (iii) Gives white ppt. with ammoniacal AgNO3
d. CH3CH(OH)CH3 (iv) With Lucas reagent cloudiness appears after 5 minutes
[AIPMT (Mains)-2010]
(1) a(ii), b(i), c(iv), d(iii) (2) a(iii), b(ii), c(i), d(iv) (3) a(ii), b(iii), c(i), d(iv) (4) a(iv), b(ii), c(iii), d(i)
Sol. Answer (3)
a (ii)
KOH CHCl
H3C CH2 CH2 CH2 NH2
3
H3C CH2 CH2 CH2 NC
It reacts with KOH (alcohol) and CHCl3 produces (1° R – NH2) bad smell (isocyanide)
b (iii)
AgNO
H3C C C H 3
H3C C C Ag HNO3
White ppt.
acidic‘H’
c (i)
NaOH(aq.)
H3C CH2 C OCH3 H3C CH2 C OH + H3COH
d (iv)
H3C CH CH3 gives test with Lucas reagent cloudiness appears after 5 minutes.
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Solution of Assignment Amines 139
15. Predict the product
OH CH3
N– CH3 N– N = O
(3) (4)
H CH 3
N + HONO N
CH3 N=O
CH3
NH2 N
NaNO2 CH3
B C
HCl Cold
A
CH3 CH3
CH3
N=N NH=NH N
(3) (4) CH3
CH3 N
N
CH3
HONO +
NH2 N2
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140 Amines Solution of Assignment
17. Which one of the following on reduction with lithium aluminium hydride yields a secondary amine ?
[AIPMT (Prelims)-2007]
18. Which of the following is more basic than aniline ? [AIPMT (Prelims)-2006]
Br
NH2 HONO
N2+ CuCN CN H2 CH2N2 HONO
OH
(A) (B) (C) (D)
20. The major organic product formed from the following reaction
O
(i) CH3NH2
(ii) LiAIH (iii) H O
......... is [AIPMT (Prelims)-2005]
4 2
21. Electrolytic reduction of Nitrobenzene in weakly acidic medium gives [AIPMT (Prelims)-2005]
SN/HCl
NO2 NH2
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Solution of Assignment Amines 141
22. Which of the following is most basic in a solution of carbon tetrachloride?
23. What will be the final product in the following reaction sequence?
NH
H /H2O
A B
3 NaOBr
CH3CH2CN C
(1) Secondary amine (2) Nitroalkane (3) Alcohol (4) Alkyl nitrite
25. The compound obtained by heating a mixture of ethyl amine and chloroform with ethanolic potassium hydroxide
(KOH) is
HCl Boiling H O
X 2 Y;
CH3CN + 2H Ether
the term Y is
O
[H] Boiling
CH3CN CH3CH = NH CH3 H
H2O
X Y
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142 Amines Solution of Assignment
O –
Br2,OH
R – C – NH2 Hoffman
R–NH2
(amide) reaction amines
30. Aniline is reacted with bromine water and the resulting product is treated with an aqueous solution of sodium nitrite
in presence of dilute hydrochloric acid. The compound so formed is converted into a tetrafluoroborate which is
subsequently heated dry. The final product is
(1) p-bromoaniline (2) p-bromofluorobenzene
(3) 1, 3, 5-tribromobenzene (4) 2, 4, 6-tribromofluorobenzene
Sol. Answer (4)
Br Br Br
+ –
NH2 Br2 HONO + – H BF4
Br NH2 Br N2 Cl Br F
H2O
Br Br Br
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Solution of Assignment Amines 143
Sol. Answer (2)
32. A
Reduction
B
CHCl3 /KOH
C
Reduction
N– methyl aniline.
Then A is
NH2 NO2 NC
NO2 NH2 N C
NH – CH3
reduction CHCl3 [H]
OH–
(N - methyl
aniline)
NH2
CH3
would be
O O
NH2 NH–C–CH3 NH–C–CH3 NH2
Br Br
Br2, AlOH H2O
+ Al2O
H+
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144 Amines Solution of Assignment
34. Nitrobenzene can be prepared from benzene by using a mixture of conc. HNO3 and conc. H2SO4. In the mixture,
nitric acid acts as a/an
(1) Catalyst (2) Reducing agent (3) Acid (4) Base
Sol. Answer (4)
+ +
HNO3 + H2SO4 H – O – NO2 NO2
(Nitronium
H
ion)
35. How many isomers of molecular formula C3H9N will liberate N2 gas on treatment with HNO2?
NH2 HONO
N2
(10)
NH2
HONO
N2
(1°)
NO2
(NH4)2S Br2
36. (A) (B) .
CH3COOH
NO2
NO2 AlOH
NO2 NO2
(1) CH3CH2 – NO2 (2) CH3 – C – NH2 (3) CH3 – C – CH3 (4) All of these
O O
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Solution of Assignment Amines 145
Sol. Answer (4)
O OH
CH3 – CH – N CH3 – CH = N
O O
CH3 – C – NH2 CH2 = C – NH2
O OH
O OH
N2Cl
NaNO2/HCl H3PO4
(A) (B) – (C)
OH
NH2
OH
(1) (2)
NH OH
N=N N=N
(3) (4)
OH HO NH2
Sol. Answer (3)
N2+
HONO H2O
+ Boiling
N=N OH
NH2 NH2 OH
SECTION - D
Assertion-Reason Type Questions
1. A : Arene diazonium salts are more stable than alkane diazonium salts.
In NH2 NH2 is highly ring activating group. (Powerful ortho and para director).
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146 Amines Solution of Assignment
KMnO H O /H
R CH 2 NH 2 H4
R CH NH 2 R CHO
2
R R R
+
KMnO4 H2O/H
CH NH2 CH NH CH O
–H2
R H R
2° amine to Tetraalkylhydrazine
R R R
KMnO4
2 NH N N
–H2
R R R
H ----- OH R R
+ N – H ----- OH
R– R – N – H ----- OH2 R – N – H ----- OH2
2
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Solution of Assignment Amines 147
8. A : Primary aliphatic amines react with CS2 and HgCl2, give precipitate of HgS.
R : Secondary amine does not give precipitate of HgS in this reaction.
Sol. Answer (2)
– + – S
HgCl2
R NH H + C S R NH C SH R N C S + HgS + 2HCl
R S R S
NH + C S N C SH
R R
2° amine N2N dialkyldithiocarbamic acid
9. A : In Hofmann's bromamide degradation amines formed containing one carbon atom less than carbon atoms
present in amide.
10. A : Reaction of carboxylic acid with hydrazoic acid in the presence of conc. H2SO4 to form primary amine is
called Schmidt reaction.
R : In this reaction isocyanate intermediate is formed.
OH OH N2Cl
OH
12. A : is less reactive than in coupling reaction with .
OH
OH
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148 Amines Solution of Assignment
O
R : Formula of urethane is NH2 C NH OCH2CH3 .
A : It is correct as
O O
NH2 C OC2H5 + NH3 NH2 C NH2 + C2H5OH
(Urethane) (Urea)
It is nucleophilic substitution.
O
R : It is wrong as Urethane is NH2 – C – O – C2H5 .
N2Cl
R : It is Sandmeyer's reaction.
CuX/HCl
N2Cl (Sandmeyer's reaction)
X Cl, for CN
N
In pyridine , lone pair is available as the does not undergo in resonance.
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Solution of Assignment Amines 149
NH2
16. A : on reaction with HNO2 gives CH2 OH as major product.
+ +
R: CH2 carbocation is more stable than carbocation.
+
In CH2 s-character is 17% and is highly stable due to sigma resonance.
Filtrate Residue
+ R
[R N Ph SO2]K
N SO2 Ph
R
70% H2SO4
70% H2SO4
R NH2
R2 NH
1° amine
2° amine
Zn dust/NaOH/
A. Ph NO2
Ph NH NH Ph
Hydrazobenzene
NO2 NH2
Sn/HCI/
R. (Reduction)
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150 Amines Solution of Assignment
19. A : Coupling reaction is used for the identification of aliphatic primary amine.
R : It is called dye test.
Sol. Answer (4)
1° aime can be identified by treating then with CS2 (Hoffman mustard oil reaction)
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