Organic Compounds Containing Nitrogen 231

$IBQUFS 0SHBOJD
$PNQPVOET
"' $POUBJOJOH
/JUSPHFO
1. The correct increasing order of basic strength by HNO 2 to give an unstable compound ‘B’.
for the following compounds is ‘B’, on treatment with phenol, forms a beautiful
/) /) /) coloured compound ‘C’ with the molecular
formula C 12H 10 N 2 O. The structure of
compound ‘A’ is
/) /0
(a) (b)
/0 $) $/ $0/)
*
**
***
(c) (d)
(a) III < I < II (b) III < II < I
(c) II < I < III (d) II < III < I
(NEET 2017) (NEET-II 2016)

2. Which of the following reactions is appropriate 5. The correct statement regarding the basicity
for converting acetamide to methanamine? of arylamines is
(a) Hoffmann hypobromamide reaction (a) arylamines are generally more basic than
(b) Stephen’s reaction alkylamines because of aryl group
(c) Gabriel phthalimide synthesis (b) arylamines are generally more basic than
(d) Carbylamine reaction (NEET 2017) alkylamines, because the nitrogen atom in
arylamines is sp-hybridised
3. Which one of the following nitro-compounds (c) arylamines are generally less basic than
does not react with nitrous acid? alkylamines because the nitrogen lone-pair
) electrons are delocalised by interaction
(a) )$ $ $ with the aromatic ring p-electron system
) /0 (d) arylamines are generally more basic than
alkylamines because the nitrogen lone-pair
) electrons are not delocalised by interaction
)$ $ with the aromatic ring p-electron system.
(b) $) /0 (NEET-I 2016)
)$ 6. The product formed by the reaction of an
)$ aldehyde with a primary amine is
(c) )$



$



/0 (a) carboxylic acid (b) aromatic acid
)$ (c) Schiff ’s base (d) ketone.
(NEET-I 2016)
$)
7. The following reaction
(d) )$ $) 0* 0C1*

0 /0 %N *
(NEET-II 2016) 1 0
4. A given nitrogen-containing aromatic
compound ‘A’ reacts with Sn/HCl, followed
1
232

is known by the name 12. Which of the following will be most stable
(a) Perkin’s reaction diazonium salt RN2+X–?
(b) Acetylation reaction (a) CH3N2+X– (b) C6H5N2+X–
(c) Schotten-Baumann reaction (c) CH3CH2N2 X+ –
(d) C6H5CH2N2+X–
(d) Friedel-Craft’s reaction. (2015) (2014)
8. Method by which aniline cannot be prepared 13. Nitrobenzene on reaction with conc.
is HNO3/H 2SO4 at 80–100°C forms which one
(a) degradation of benzamide with bromine in of the following products?
alkaline solution (a) 1, 4-Dinitrobenzene
(b) reduction of nitrobenzene with H2/Pd in (b) 1, 2, 4-Trinitrobenzene
ethanol (c) 1, 2-Dinitrobenzene
(c) potassium salt of phthalimide treated with (d) 1, 3-Dinitrobenzene (NEET 2013)
chlorobenzene followed by hydrolysis with
aqueous NaOH solution
(d) hydrolysis of phenylisocyanide with acidic
solution. (2015) 14. In the reaction
9. The number of structural isomers possible
from the molecular formula C 3H 9N is
(a) 5 (b) 2
(c) 3 (d) 4 (2015) A is
(a) H3PO2 and H2O (b) H+/H2 O
10. The electrolytic reduction of nitrobenzene in (c) HgSO4/H2SO 4 (d) Cu2Cl2
strongly acidic medium produces
(NEET 2013)
(a) azobenzene (b) aniline
(c) p-aminophenol (d) azoxybenzene. 15. On hydrolysis of a “compound”, two
(2015, Cancelled) compounds are obtained. One of which on
treatment with sodium nitrite and hydrochloric
11. In the following reaction, the product (A) is acid gives a product which does not respond
+ –
N NCl NH2 to iodoform test. The second one reduces
Tollens reagent and Fehling’s solution. The
H+ “compound” is
+ (A)
Yellow dye (a) CH3CH2CH2NC
(b) CH3CH2CH2CN
(a) N N NH (c) CH3CH2CH2ON O
(d) CH3CH2CH2CON(CH3)2
(Karnataka NEET 2013)
NH2
16. Some reactions of amines are given. Which
(b) N N one is not correct?

(a) (CH3)2N + NaNO2 + HCl ®

NH2
(c) N N (CH3)2N N NCl
(b) CH3CH2NH2 + HNO2 ® CH3CH2OH + N2
(c) CH3NH2 + C6H5SO2Cl ® CH3NHSO2C6H5
(d) N N NH2 (d) (CH3)2NH + NaNO2 + HCl
® (CH3)2N—N O
(2014) (Karnataka NEET 2013)
Organic Compounds Containing Nitrogen 233

17. An organic compound (C 3H 9N) (A), when The structure of ‘Y’ would be
treated with nitrous acid, gave an alcohol and
N 2 gas was evolved. (A) on warming with (a)
CHCl3 and caustic potash gave (C) which on
reduction gave isopropylmethylamine. Predict
the structure of (A).
(a) (b)

(b) CH3CH2 – NH – CH3 (c)

(c)
(d)

(d) CH3CH2CH2 – NH2 (2012) (2010)

18. What is the product obtained in the following 21. Which of the following statements about
reaction? primary amines is false?
 (a) Alkyl amines are stronger bases than aryl
— amines.

• (b) Alkyl amines react with nitrous acid to


produce alcohols.
(c) Aryl amines react with nitrous acid to
(a) produce phenols.
(d) Alkyl amines are stronger bases than
  ammonia. (2010)
(b) 22. Predict the product.
NHCH3
 + NaNO2 + HCl Product
(c)
 
CH3
N – NO2

(a)
(d) (2011)
NHCH3 NHCH3
19. Which of the following compounds is most NO
basic? (b) +
(a)
NO
(b) OH
N – CH3
(c)
(c)
CH3

(d) (Mains 2011) N–N O

(d) (2009)

20. Aniline in a set of the following reactions 23. Nitrobenzene can be prepared from benzene
yielded a coloured product Y. by using a mixture of conc. HNO 3 and
conc. H2SO 4 . In the mixture, nitric acid acts
N ,N -dimethylaniline as a/an
(a) acid (b) base
(c) catalyst (d) reducing agent.
(2009)
234

24. In a reaction of aniline a coloured product C 29. The final product C, obtained in this reaction
was obtained.
CH3 NH2
NH2 N
NaNO2 CH3 Ac2O Br2 H2O
B C
HCl cold A B C
CH3COOH H+
A
CH3
The structure of C would be
CH3 would be
NH NH N
(a) CH3 NH2 COCH3

COCH3 Br
CH3
(b) N N N (a) (b)
CH3
CH 3 CH3
(c) N N CH2 N NH2 NHCOCH3
CH3 Br Br
CH3 CH3 (c) (d)
(d) N N (2008, 2004) CH3 CH3
(2003)
25. Which one of the following on reduction with C N
lithium aluminium hydride yields a secondary H 3O †
amine? 30. + CH3MgBr P
(a) Methyl isocyanide (b) Acetamide OCH3
(c) Methyl cyanide (d) Nitroethane
(2007) Product ‘P’ in the above reaction is
OH O
26. Which of the following is more basic than CH – CH3 C – CH3
aniline?
(a) Benzylamine (b) Diphenylamine (a) (b)
(c) Triphenylamine (d) p-Nitroaniline
OCH3 OCH3
(2006)
CHO COOH
27. Electrolytic reduction of nitrobenzene in weakly
acidic medium gives
(a) N-phenylhydroxylamine (c) (d)
(b) nitrosobenzene OCH3 OCH3
(c) aniline (2002)
(d) p-hydroxyaniline. (2005)
28. Aniline in a set of reactions yielded a product 31. Intermediates formed during reaction of RCNH 2
D. O
NH2 with Br2 and KOH are
NaNO 2 CuCN
A B (a) RCONHBr and RNCO
HCl
HNO2 (b) RNHCOBr and RNCO
H2
C D (c) RNH – Br and RCONHBr
Ni
(d) RCONBr2 (2001)
The structure of the product D would be
(a) C6H5NHOH (b) C6H5NHCH2CH3 reduction CHCl3/KOH reduction
32. A B C
(c) C6H5CH2NH2 (d) C6H5CH2OH
N-methylaniline,
(2005)
then A is
Organic Compounds Containing Nitrogen 235

NH2 37. An aniline on nitration gives

NH2
(a)

NO2 (a)
NO2
(b)
CH3

(c) CH3NH2
(b) NO2
NC NO2

(d) (2000) NH2

NO2
(c)
33. Amides may be converted into amines by a
reaction named after (d) both (a) and (c). (1996)
(a) Hoffmann (b) Claisen
38. Which product is formed, when acetonitrile
(c) Perkin (d) Kekule
is hydrolysed partially with cold concentrated
HCl?
(1999) (a) Methyl cyanide
34. Phenyl isocyanides are prepared by which (b) Acetic anhydride
of the following reaction? (c) Acetic acid
(a) Reimer-Tieman reaction (d) Acetamide (1995)
(b) Carbylamine reaction 39. When aniline reacts with oil of bitter almonds
(c) Rosenmund’s reaction (C 6H 5 CHO) condensation takes place and
(d) Wurtz reaction benzal derivative is formed. This is known as
(1999) (a) Schiff’s base
35. Aniline is reacted with bromine water and the (b) Benedict’s reagent
resulting product is treated with an aqueous (c) Million’s base
solution of sodium nitrite in presence of dilute (d) Schiff’s reagent. (1995)
hydrochloric acid. The compound so formed 40. The action of nitrous acid on an aliphatic
is converted into a tetrafluoroborate which primary amine gives
is subsequently heated dry. The final product (a) secondary amine (b) nitro alkane
is (c) alcohol (d) alkyl nitrite.
(a) p-bromoaniline (1994)
(b) p-bromofluorobenzene
41. Which one of the following order is wrong,
(c) 1, 3, 5-tribromobenzene
with respect to the property indicated?
(d) 2, 4, 6-tribromofluorobenzene.
(a) Benzoic acid > phenol > cyclohexanol (acid
(1998) strength)
36. The compound obtained by heating a mixture (b) Aniline > cyclohexylamine > benzamide
of ethyl amine and chloroform with ethanolic (basic strength)
potassium hydroxide (KOH) is (c) Formic acid > acetic acid > propanoic acid
(a) an amide (acid strength)
(b) an amide and nitro compound (d) Fluoroacetic acid > chloroacetic acid >
(c) an ethyl isocyanide bromoacetic acid (acid strength)
(d) an alkyl halide.  (1997) (1994)
236

42. For carbylamine reaction, we need hot alcoholic 43. Indicate which nitrogen compound amongst
KOH and the following would undergo Hofmann reaction
(a) any primary amine and chloroform (i.e., reaction with Br2 and strong KOH) to
(b) chloroform and silver powder furnish the primary amine (R–NH2 )?
(c) a primary amine and an alkyl halide (a) RCONHCH3 (b) RCOONH4
(d) a monoalkylamine and trichloromethane. (c) RCONH2 (d) R – CO – NHOH
(1992) (1989)

Answer Key

1. (c) 2. (a) 3. (c) 4. (b) 5. (c) 6. (c) 7. (c) 8. (c) 9. (d) 10. (c)
11. (d) 12. (b) 13. (d) 14. (a) 15. (a) 16. (a) 17. (a) 18. (a) 19. (b) 20. (a)
21. (c) 22. (d) 23. (b) 24. (b) 25. (a) 26. (a) 27. (c) 28. (d) 29. (c) 30. (b)
31. (a) 32. (b) 33. (a) 34. (b) 35. (d) 36. (c) 37. (d) 38. (d) 39. (a) 40. (c)
41. (b) 42. (a) 43. (c)
Organic Compounds Containing Nitrogen 237

1. (c) %*%* %*

2. (a) : 2. 0*
0
Propanamine
$) $ /) 
#S 
,0) )PGGNBOO 3. CH3CH2NHCH3
"DFUBNJEF CSPNBNJEF
N-Methylethanamine
SFBDUJPO

$) /) 
,#S 
,$0 
)0

 
%*
.FUIBOBNJOF
3. (c) : Tertiary nitroalkanes do not react with 4. %* 0 %*
nitrous acid as they do not contain a-hydrogen 00&KOGVJ[NOGVJCPCOKPG
atom. 10. (c) :
4. (b) :
/0 4O)$M
/) )/0

"

0) / $M


o

/



/ 0) #FO[FOF
EJB[POJVN
DIMPSJEF
VOTUBCMF

Q)ZESPYZB[PCFO[FOF
SFE
DPMPVS
EZF

+ –
11. (d) : N N Cl + H NH2
5. (c) : In arylamines, lone pair of electrons on +
nitrogen atom is delocalised over the benzene ring, H
thus, not available for donation. So, arylamines are
less basic than alkylamines .
N N NH2 + HCl
6. (c) : $




0

) /3 $



/ 3 p-Aminoazobenzene (yellow dye)
4DIJGGhT
CBTF (A)
7. (c) : Benzoylation of compounds containing 12. (b) : Aromatic diazonium salts are more stable
an active hydrogen atom such as alcohols, phenols due to dispersal of the positive charge in benzene
and amines with benzoyl chloride in the presence ring.
of dilute aq. NaOH solution is called Schotten-
Baumann reaction.
8. (c) : Aniline cannot be prepared by this method
because aryl halides do not undergo nucleophilic
13. (d) :
substitution reaction with potassium phthalimide
under mild conditions.
9. (d) : The possible structural isomers are :
+ −
1. CH3CH2CH2NH2 14. (a) : H3PO2 and H2O reduces the − N 2 Cl to –H.
Propanamine
H+
15. (a) : CH3CH2CH2NC + 2H2O ⎯⎯⎯
→
238

CH3CH2CH2NH2 + HCOOH
I II

II (HCOOH) reduces Tollens’ reagent and Fehling’s

solution.
16. (a) : Aromatic tertiary amines undergo
electrophilic substitution with nitrosonium ion at
p-position of the phenyl ring to form green-coloured
p-nitrosoamines.
NaNO2 + HCl ® HNO2 + NaCl



21. (c) : Aryl amines react with nitrous acid to

   produce diazonium salts.
™ ’›˜   ’–Ž‘¢•
Š—’•’—Ž ›ŽŽ—
17. (a) : As A gives alcohol on treatment with
nitrous acid thus it should be primary amine. C3H9N
has two possible structure with –NH2 group.
22. (d) : 2° aliphatic and aromatic amines react with
nitrous acid to form N-nitrosoamine.
NH – CH3
+ NaNO2 + HCl
As it gives isopropylmethylamine thus it should be
isopropyl amine not n-propyl amine. CH3

N–N O

N -nitroso-N -methylaniline
23. (b) :

24. (b) :
18. (a) :  o
NH2 N NCl
 — 
•


NaNO 2


ŽŠ HCl
(A) (B ) N(CH3)2
Benzene diazonium (Dimethyl aniline)
19. (b) : In benzylamine the electron pair present on chloride
the nitrogen is not delocalised with the benzene ring.
N N N(CH3)2
p-Dimethyl amino azobenzene
20. (a) : (Butter yellow)
(C)
25. (a) : Alkyl isocyanides on reduction with lithium
(X) aluminium hydride forms secondary amines
containing methyl as one of the the alkyl groups.
Organic Compounds Containing Nitrogen 239

LiAlH 4 NHCOCH3 NH2

R –N C + [H] RNHCH3
Alkyl isocyanide Secondary amine
Br Br
H2O
LiAlH4 H+
H3C – N C + 4 [H] H3C – NH – CH3
CH3 CH3
Methyl isocyanide Dimethylamine
(B) (C)
26. (a) : Any group which when present on benzene
30. (b) :
ring has electron withdrawing (– NO2, – CN, – SO3H,
C N H3C – C NMgBr
– COOH, – Cl, – C6H 5, etc.) group decreases basicity
of aniline. e.g. Aniline is more basic than nitroaniline + CH3MgBr
and diphenyl amine. While a group which has OCH3 OCH3
electron repelling effect (– NH2, – OR, – R, etc.)
H3O+
increases basicity of aniline.
Thus, benzylamine is more basic than aniline. H3C – C NH
H3C – C O
27. (c) : Electrolytic reduction of nitrobenzene in H3O+
weakly acidic medium gives aniline but in strongly
acidic medium it gives p-aminophenol through the OCH3 OCH3
acid-catalysed rearrangement of the initially formed (P)
phenylhydroxylamine. 31. (a) : The reaction RCONH2 + Br2 + KOH ® RNH2
Electrolytic is known as Hoffmann-bromamide reaction. The
C6H5NO2 C6H5NH2
reduction mechanism of the reaction is
Nitrobenzene Weakly acidic Aniline
O O
medium

+
R – C – NH2 + Br2 oR –C–N Br
H
+ HBr
NH2 N2Cl– KOH –H +
R –
NaNO 2/HCl CuCN O
28. (d) : . –KBr ..
O . ..
C–N R –C–N K+
(Benzene diazonium . . – Br
chloride) rearrangement
(A ) 2KOH
[O C N – R] K2CO3 + RNH 2
CN Alkyl isocyanate
CH2 – NH 2
This reaction is used in the descent of series, i.e.
H2 / Ni
for preparing a lower homologue from a higher one.
(B) (C)
(1° – amine) 32. (b) : ‘C’ must be an isocyanide and obtained
HNO2 from a 1° amine by Carbylamine reaction (CHCl3 +
CH2– OH KOH). Further 1° amine must be obtained by
reduction of nitrohydrocarbon. So ‘A’ is
nitrobenzene.
NO2 NH2
(D) CHCl3
Reduction
KOH
Nitrobenzene Aniline
NH2 NHCOCH3
NHCH3
Ac2O Br2 NC
29. (c) :
CH3COOH
Reduction
CH3 CH3
(A) Phenyl isocyanide N-Methylaniline.
240

33. (a) : 37. (d) :

R – C – NH2 + Br2 + 4KOH R – NH2 + K2CO3 .. ⊕ ⊕ ⊕
1° amine
NH2 NH2 NH2 NH2
O
Acid amide + 2KBr + 2H2O – –

This reaction is called Hoffmann bromamide –

reaction.
As, NO2+ electrophile can attack both ortho and
34. (b) : C6H5 – NH2 + CHCl3 + 3KOH ® para positions, therefore both (a) and (c) product
C6H5 – NC + 3KCl + 3H2O will be obtained.
The above reaction is called as carbylamine conc. HCl
38. (d): CH3 – C N CH3 – CO – NH2
reaction, which is a specific reaction of 1°-amine. In H2O
Acetonitrile Acetamide
this reaction aniline is treated with an alkaline 39. (a) : Benzaldehyde reacts with primary aromatic
solution of chloroform to give phenyl isocyanide. amines to form Schiff’s base (Benzylidene aniline).
35. (d) : C6H5HC O + C6H5NH2 → C6H5HC NC6H5 + H2O
Benzaldehyde Aniline Benzylidene aniline
NH2 NH2 N2Cl 40. (c) :
Br Br Br Br
NaNO 2 + HCl
R − NH 2 + HNO 2 ROH + N2 + H2 O
+ Br2
(HNO 2) Primary amine Nitrous acid Alcohol
Br Br 41. (b) : Basic strength decreases as,
2,4,6-tribromoaniline Diazonium salt
cyclohexylamine > aniline > benzamide.
N2BF4 F Lesser basicity in aniline and benzamide is due to
Br Br Br Br participation of lone pair of electron of – NH2 group.
HBF4 '
–HCl
+ N2 + BF3 42. (a) : In carbylamine reaction, primary amines on
heating with chloroform in presence of alcoholic
Br Br KOH form isocyanides (or carbylamines). It is used
Diazonium 2,4,6-tribromofluorobenzene to distinguish 1° amines from 2° and 3° amines.
tetrafluoroborate
R–NH2 + CHCl3 + 3KOH ® RNC + 3KCl + 3H2O
36. (c) : CH3CH2NH2 + CHCl3 + 3KOH ® (alc.)
Ethyl amine Chloroform 43. (c) : The amide (–CONH2) group is converted
CH3CH2NC + 3KCl + 3H2O into primary amino group (–NH2) by Hofmann’s
Ethyl isocyanide bromamide reaction.
Isocyanide can be easily characterised by their '
RCONH2 + Br 2 + 4KOH
offensive odour. The reaction is called carbylamine
R – NH2 + KBr + K2CO3 + 2H2O
test. 1° amine