Amines 291
27 Amines
Trend Analysis with Important Topics & Sub-Topics
2020 2019 2018 2017 2016
Topic Name Sub-Topic QNS. LOD QNS. LOD QNS. LOD QNS. LOD QNS. LOD
carbylamine
1 E
reaction
basic strength of
1 A 1 A 1 A
amines
Aliphatic and aromatic
Hoffmann
amines
bromamide 1 A
reaction
electrophillic
1 A
substitution
LOD - Level of Difficulty E - Easy A - Average D - Difficult Qns - No. of Questions
Topic 1: Aliphatic and Aromatic Amines (b) CH3 — CH — NH — CH — CH3
1. Which of the following amine will give the | |
CH3 CH3
carbylamine test? [2020]
NHCH3 N(CH3)2 CH2CH3
|
(c) CH 3 — CH 2 — N — CH 2CH 3
(a) (b)
NH2
|
NHC2H5 NH3 (d) CH3 — C — CH 2CH 2CH3
|
(c) (d) CH3
3. The correct order of the basic strength of methyl
2. The amine that reacts with Hinsberg’s reagent substituted amines in aqueous solution is :
to give an alkali insoluble product is (a) (CH3)2NH > CH3NH2 > (CH3)3N [2019]
[NEET Odisha 2019]
CH3 (b) (CH3)3N > CH3NH2 > (CH3)2NH
|
(a) CH3 — C — CH — NH 2 (c) (CH3)3N > (CH3)2NH > CH3NH2
| | (d) CH3NH2 > (CH3)2NH>(CH3)3N
CH3 CH3
EBD_83
292 CHEMISTRY
4. Nitration of aniline in strong acidic medium also (d) Arylamines are generally more basic than
gives m-nitroaniline because [2018] alkylamines, because the n itrogen atom
(a) Inspite of substituents nitro group always in arylamines is sp-hybridized.
goes to only m-position. 8. The electrolytic reduction of nitrobenzene in
(b) In electrophilic substitution reactions, strongly acidic medium produces :- [2015]
amino group is meta directive. (a) Azoxybenzene (b) Azobenzene
(c) In acidic (strong) medium aniline is present (c) Aniline (d) p-Aminophenol
as anilinium ion. 9. The number of structural isomers possible from
(d) In absence of substituents, nitro group the molecular formula C3H9N is : [2015 RS]
always goes to m-position. (a) 4 (b) 5
5. The correct increasing order of basic strength (c) 2 (d) 3
for the following compounds is : [2017] 10. Method by which aniline cannot be prepared is:
[2015 RS]
NH2 NH2 NH2
(a) hydrolysis of phenylisocyanide with acidic
solution
(I) (II) (III)
(b) degradation of benzamide with bromine in
CH3 alkaline solution
NO2
(c) reduction of nitrobenzene with H2/Pd in
(a) III < I < II (b) III < II < I ethanol
(c) II < I < III (d) II < III < I (d) potassium salt of phthalimide treated with
chlorobenzene followed by hydrolysis with
6. Which of the following reactions is appropriate
aqueous NaOH solution.
for converting acetamide to methanamine? [2017]
11. Some reactions of amines are given. Which one
(a) Hoffmann hypobromamide reaction is not correct ? [NEET Kar. 2013]
(b) Stephens reaction (a) (CH3)2NH + NaNO2 + HCl ®
(c) Gabriels phthalimide synthesis (CH3)2 N – N = O
(d) Carbylamine reaction (b) (CH3)2N – + NaNO2 + HCl ®
7. The correct statement regarding the basicity of
arylamines is [2016] (CH3)2N – – N = NCl
(a) Arylamines are generally less basic than
alkylamines because the nitrogen lone-pair (c) CH3CH2NH2 + HNO2 ® CH3CH2OH + N2
electrons are delocalized by interaction (d) CH3NH2 + C6H5SO2Cl ®
with the aromatic ring p electron system. CH3NHSO2C6H5.
(b) Arylamines are generally more basic than 12. In a set of reactions m-bromobenzoic acid gave
alkylamines because the nitrogen lone-pair a product D. Identify the product D. [2011]
electrons are not delocalized by interaction COOH
with the aromatic ring p electron system.
SOCl NH
NaOH
¾¾®
2
B ¾¾®
3
C ¾¾®
Br D
(c) Arylamines are generally more basic than 2
alkylamines because of aryl group. Br
Amines 293
SO2NH2 COOH (4) CH3CH(OH)CH3 (iv) with Lucas
(a) (b) reagent
cloudiness
Br NH2 appears
after 5 minutes
NH2 CONH2 Options :
(c) (d) (1) (2) (3) (4)
(a) (iv) (ii) (iii) (i)
Br Br (b) (ii) (i) (iv) (iii)
(c) (iii) (ii) (i) (iv)
13. Which of the following compounds is most basic? (d) (ii) (iii) (i) (iv)
[2011 M] 16. Predict the product: [2009]
NHCH3+NaNO2+ HCl ¾® Product
(a) O2N NH2 (b) CH2NH2
CH3
(c) N – COCH3 (d) NH2 N NO2
H (a)
14. Which of the following statements about primary
NHCH3 NHCH3
amines is ‘False’ ? [2010]
(a) Alkyl amines are stronger bases than aryl NO
amines (b) +
(b) Alkyl amines react with nitrous acid to
produce alcohols NO
OH
(c) Aryl amines react with nitrous acid to
produce phenols N CH3
(c)
(d) Alkyl amines are stronger bases than ammonia
15. Match the compounds given in List - I with their
characteristic reactions given in List - II. Select CH3
the correct option. [2010] N N=O
(d)
List - I List - II
Compounds Reactions
17. Which of the following is more basic than
(1) CH3CH2CH2CH2NH2 (i) alkaline aniline? [2006]
hydrolysis (a) Triphenylamine (b) p-Nitroaniline
(c) Benzylamine (d) Diphenylamine
(2) CH3C º CH (ii) with KOH
18. The major organic product formed from the
(alcohol) and following reaction : [2005]
CHCl3 produces
O
bad smell (i) CH NH
¾ ¾ ¾ ¾ ¾ ¾ ® ......
3 2
(3) CH3CH2COOCH3 (iii) gives white (ii) LiAlH 4, (iii) H 2O
ppt. with
is
ammonical
AgNO3
EBD_83
294 CHEMISTRY
O – NHCH3 23. The compound obtained by heating a mixture
(a) of a primary amine and chloroform with ethanolic
potassium hydroxide (KOH) is [1997]
(a) an alkyl cyanide (b) a nitro compound
(b)
(c) an alkyl isocyanide (d) an amide
NCH3
24. When aniline reacts with oil of bitter almonds
H
(C6 H5CHO), condensation takes place and benzal
derivative is formed. This is known as [1995]
H
(a) Million's base (b) Schiff's reagent
NCH3
(c) (c) Schiff's base (d) Benedict's reagent
OH 25. What is the decreasing order of basicity of
primary, secondary and tertiary ethylamines and
H NH3 ? [1994]
NCH3 (a) NH 3 > C 2 H 5 NH 2 > (C 2 H 5 ) 2 NH >
(d)
OH (C 2 H 5 )3 N
19. Electrolytic reduction of nitrobenzene in weakly (b) (C2 H 5 )3 N > (C2 H 5 )2 NH >
acidic medium gives [2005]
C2 H5 NH 2 > NH 3
(a) N-Phenylhydroxylamine
(b) Nitrosobenzene (c) (C2 H 5 )2 NH > C2 H 5 NH 2 >
(c) Aniline (C 2 H 5 )3 N > NH 3
(d) p-Hydroxyaniline (d) (C 2 H 5 ) 2 NH > (C 2 H 5 )3 N >
20. The consituent of the powerful explosive RDX
C 2 H 5 NH 2 > NH 3 .
is formed during the nitration of [2000]
(a) Toluene (b) Phenol 26. Mark the correct statement [1988]
(c) Glycerol (d) Urotropine (a) Methylamine is slightly acidic
21. Which of the following is most basic in nature? (b) Methylamine is less basic than ammonia
(a) NH3 (b) CH3NH2 [2000] (c) Methylamine is a stronger base than ammonia
(c) (CH3)2NH (d) C6H5NHCH3 (d) Methylamine forms salts with alkalies.
22. Aniline is reacted with bromine water and the
Topic 2: Amides, Cyanides and Isocyanides
resulting product is treated with an aqueous
solution of sodium nitrite in presence of dilute 27. The following reaction
hydrochloric acid. The compound so formed is NH2
converted into a tetrafluoroborate which is + Cl
subsequently heated dry. The final product is
O
(a) 1,3, 5-Tribromobenzene [1998]
H
(b) p-Bromofluorobenzene N
NaOH
(c) p-Bromoaniline ¾¾¾®
O
(d) 2,4, 6-Tribromofluorobenzene
O
is known by the name : [2015 RS]
Amines 295
(a) Friedel-Craft's reaction 32. The final product C, obtained in this reaction
(b) Perkin's reaction NH2
(c) Acetylation reaction Ac O Br H O
¾¾®
2
¾¾¾®
A CH 2
B ¾¾®
2
C
(d) Schotten-Baumen reaction COOH
3
+
H
28. On hydrolysis of a “compound”, two compounds
CH3
are obtained. One of which on treatment with sodium
would be [2003]
nitrite and hydrochloric acid gives a product which
does not respond to iodoform test. The second one NHCOCH3 NH2
reduces Tollen’s reagent and Fehling’s solution. The Br COCH3
“compound” is [NEET Kar. 2013] (a) (b)
(a) CH3 CH2 CH2 CON(CH3)2
CH3 CH3
(b) CH3 CH2 CH2 NC
COCH3 NH2
(c) CH3 CH2 CH2 CN Br Br
(d) CH3 CH2 CH2 ON = O (c) (d)
29. An organic compound (C3H9N) (A), when treated
with nitrous acid, gave an alcohol and N2 gas was CH3 CH3
evolved. (A) on warming with CHCl3 and caustic C N
potash gave (C) which on reduction gave
isopropylmethylamine. Predict the structure of (A). H OÅ
33. + CH3MgBr ¾¾¾¾
3 ®P
CH3
(a) CH NH2 [2012 M] OCH3
CH3
Product 'P' in the above reaction is [2002]
(b) CH3CH2 NH CH3 OH O
(c) CH3 N CH3
CH – CH3 C – CH3
CH3
(a) (b)
(d) CH3CH2 CH2 NH2
OCH3 OCH3
30. Acetamide is treated with the following reagents
separately. Which one of these would yield CHO COOH
methylamine? [2010]
(a) NaOH – Br2
(b) Sodalime (c) (d)
(c) Hot conc. H2SO4 OCH3 OCH3
(d) PCl5 34. Intermediates formed during reaction of
31. Which one of the following on reduction with R C NH 2 with Br2 and KOH are [2001]
lithium aluminium hydride yields a secondary ||
O
amine? [2007]
(a) Methyl isocyanide (a) RNHBr and RCONHBr
(b) Acetamide (b) RNHCOBr and RNCO
(c) Methyl cyanide (c) RCONHBr and RNCO
(d) Nitroethane. (d) RCONBr2
EBD_83
296 CHEMISTRY
35. An isocyanide is prepared by [1999] 39. Acetamide and ethylamine can be distinguished
(a) Friedel-Crafts reaction by reacting with [1994]
(b) Perkin reaction (a) Aqueous HCl and heat
(c) Carbylamine reaction (b) Aqueous NaOH and heat
(d) Wurtz reaction (c) Acidified KMnO4
36. Consider the following sequence of reactions :
(d) Bromine water.
Reduction HNO
® [B] ¾¾¾¾
Compound[A] ¾¾¾¾¾ 2®
40. For carbylamine reaction, we need hot alcoholic
CH3CH 2OH KOH and [1992]
The compound [A] is [1996] (a) Any primary amine and chloroform
(a) CH3CH2CN (b) CH3NO2 (b) Chloroform and silver powder
(c) CH3NC (d) CH3CN (c) A primary amine and an alkyl halide
37. Aniline is an activated system for electrophilic
(d) A monoalkylamine and trichloromethane.
substitution. The compound formed on heating
aniline with acetic anhydride is [1996] 41. Indicate which nitrogen compound amongst the
following would undergo Hoffmann reaction
NH2 (i.e., reaction with Br2 and strong KOH) to
furnish the primary amine (R – NH2) [1989]
(a) (a) RCONHCH3 (b) RCOONH4
COCH3
(c) RCONH2 (d) R – CO – NHOH.
NH2
Topic 3: Nitrocompounds, Alkyl Nitrites and
Diazonium Salts
(b)
42. In the following reaction, the product (A) [2014]
COCH3 +
NºNCl
–
NH2
NH2
+ H +
is :
(c) ¾¾® (A)
Yellow dye
COCH3
NHCOCH3
(d) (a) N=N–NH
NH2
38. Which is formed, when acetonitrile is hydrolysed
partially with cold concentrated HCl? [1995] (b) N=N
(a) Acetic acid NH2
(b) Acetamide
(c) N=N
(c) Methyl cyanide
(d) Acetic anhydrides
(d) N=N NH2
Amines 297
43. Which of the following will be most stable 47. Aniline in a set of the following reactions yielded
diazonium salt RN2+X– ? [2014] a coloured product ‘Y’ [2002, 2010]
(a) CH3 N2+X– (b) C6H5N2+X– NH2
(c) CH3CH2N2+X– (d) C6H5CH2N2+X– NaNO /HC1
¾¾¾¾¾¾
2 ®X
(273-278K)
44. In the reaction
NO2 NO2 N, N-dimethylaniline
¾¾¾¾¾¾¾¾® Y
A
The structure of ‘Y’ would be ;
¾®
Br Br
CH3
(a) N=N N
ÅN2C I –
CH3
A is : [NEET 2013]
(a) Cu2Cl2 (b) H3PO2 and H2O CH3 CH3
(c) H+/H2O (d) HgSO4/H2SO4 (b) HN NH NH
45. Nitrobenzene on reaction with conc.
HNO3/H2SO4 at 80 - 100°C forms which one of
(c) H C N=N NH2
the following products ? [NEET 2013] 3
(a) 1, 3 - Dinitrobenzene
CH3 CH3
(b) 1, 4 - Dinitrobenzene
(c) 1, 2, 4 - Trinitrobenzene (d) HN N=N NH
(d) 1, 2 - Dinitrobenzene
48. Nitrobenzene can be prepared from benzene by
46. What is the product obtained in the following using a mixture of conc. HNO3 and conc. H2SO4;
reaction : [2011] in the mixture, nitric acid acts as a/an: [2009]
NO2 (a) acid (b) base
Zn ........... ?
¾¾® (c) catalyst (d) reducing agent
NH4Cl
49. Aniline in a set of reactions yielded a product D.
NHOH NH2
NaNO CuCN
(a) ¾¾¾®
HCl
2
A ¾¾¾® B
N H HNO
¾¾¾®
2
C ¾¾¾®
2
D
(b) N Ni
The structure of the product D would be: [2005]
O
– (a) C6H5NHOH (b) C6H5NHCH2CH3
N=N (c) C6H5CH2NH2 (d) C6H5CH2OH
(c) + 50. Aniline when diazotized in cold and when
treated with dimethyl aniline gives a coloured
NH 2 product. Its structure would be [2004]
(d)
(a) CH3NH N=N NHCH3
E
298 CHEMISTRY
(a) Formaldehyde
(b) CH3 N=N NH2 (b) Trichloromethane
(c) Nitrobenzene
(d) Toluene
(c) (CH3)2N N=N 52. Which of the following reagents will convert
p-methylbenzenediazonium chloride into
p-cresol?
(d) (CH3)2N NH (a) Cu powder (b) H2O [1999]
(c) H3PO2 (d) C6H5OH
51. reduction
[A] ¾¾¾¾® [B] ¾¾¾¾¾¾
3 ®
CHCl +KOH [2000] 53. Diazo coupling is useful to prepare some [1994]
reduction (a) Pesticides (b) dyes
[C] ¾¾¾¾® N-Methylaniline, A is
(c) proteins (d) vitamins
ANSW E R KE Y
1 (d) 7 (a) 13 (b ) 19 (c) 25 (d ) 31 (a) 37 (d ) 43 (b ) 49 (d )
2 (b) 8 (d ) 14 (c) 20 (d ) 26 (c) 32 (d ) 38 (b ) 44 (b ) 50 (c)
3 (a) 9 (a) 15 (d ) 21 (c) 27 (d ) 33 (b ) 39 (b ) 45 (a) 51 (c)
4 (c) 10 (d ) 16 (d ) 22 (d ) 28 (b ) 34 (c) 40 (a) 46 (a) 52 (b )
5 (c) 11 (b ) 17 (c) 23 (c) 29 (a) 35 (c) 41 (c) 47 (a) 53 (b )
6 (a) 12 (c) 18 (b ) 24 (c) 30 (a) 36 (d ) 42 (d ) 48 (b )
Hints & Solutions
1. (d) Aliphatic and aromatic primary amines give In acidic medium aniline is protonated to form
carbylamine reaction. Since aniline is primary anilinium ion which is meta-directing.
aromatic amine, it gives carbylamine test. 5. (c) – NO2 group has strong – R effect and –
2. (b) Hinsberg’s reagent is used to distinguish CH3 shows +R effect.
1°, 2° and 3° amine. Primary amines react with \ Order of basic strength is
Hinsberg’s reagent to give precipitate. which is
soluble in alkali while secondary amines give a NH2 NH2 NH2
product which is insoluble in alkali. Tertiary
amines do not react with Hinsberg’s reagent. < <
3. (a) Account for the inductive effect, solvation
effect (H-bonding.) and steric hinderance for NO2 CH3
basic character in aqueous solutions O
(CH3)2 NH > CH3 NH2 > (CH3)3 N 6. D
(a) CH3 - C - NH 2 + Br2 + 4NaOH ¾¾ ®
4. (c) acetamide
+ + CH3 – NH2 + 2NaBr + Na2CO3 + 3H2O
NH2 NH3 NH3
methanamine
+
H
¾¾¾¾®
+ NO2
¾¾¾®
It is called Hoffmann Bromamide reaction.
nitrating
mixture NO2