Chemistry : Nitrogen Containing Compounds

ASSIGNMENTS

SECTION - I
SUBJECTIVE QUESTIONS
LEVEL - I
1. Write the major product in the following reaction :
Ag 2 O, H 2O
CH3 — CH 2 — CH — CH3  heat

|
 N(CH ) I
3 3

2. Aniline does not undergo Friedel-Crafts reaction. Explain in not more than 2, 3, lines.
3. How is 2, 4-dinitrophenylhydrazine prepared from chlorobenzene?
4. Why it is necessary to add excess of mineral acids to diazotisation of amines?
5. Nitrobenzene does not undergo Friedel-Crafts alkylation. Give reason in one or two sentences.
6. Arrange ethylamine, 2-amino ethanol and 3-amino-1-propanol in the order of decreasing basicity and
give your reason.
7. Identify (A) through (E) in the following sequence

– HCl NaOH EtBr H 3O
PhSO 2Cl  EtNH 2  (A)  (B)  (C)  (D)  (E)
8. Suggest a structural formula for a chiral compound (A) C8H11N, that dissolves in dilute HCl and
releases N2 with HNO2.

9. Provide structures for the products of the reaction of PhN 2 with

(a) PhNMe2
(b) 2-naphthol
(c) PhCH3 .
10. Account for the fact that 2-aminoethanoic acid (glycine) exists as a dipolar ion, as does
p-aminobenzenesulfonic acid (sulfanilic acid) but p-aminobenzoic acid does not
 Chemistry : Nitrogen Containing Compounds

LEVEL - II
1. How will you carry out the following conversions?
O

C NH
NH2 CH3 NH2
(a) 
 (b) NH2 


2. A mixture of two aromatic compounds (A) and (B) was separated by dissolving in chloroform followed
by extraction with aqueous KOH solution. The organic layer containing compound (A), when heated
with alcoholic solution of KOH produced a compound (C) (C7H5N) associated with an unpleasant
odour. The alkaline aqueous layer on the other hand, when heated with chloroform and then acidified
give a mixture of two isomeric compounds (D) and (E) of molecular formula C7H6O2. Identify the
compounds (A), (B), (C), (D) and (E).
3. A neutral compound (A) C8H9ON on treatment with sodium hypobromite forms an acid soluble substance
(B), C7H9N. On addition of aqueous sodium nitrite to a solution of (B) in dil. HCl at 0 – 5°C, an ionic
compound (C). C7H7N2Cl is obtained. (C) gives a red dye with alk  -naphthol solution. When treated
with potassium cuprocyanide, (C) yields a neutral substance (D), C8H7N. ON hydrolysis (D) gives (E),
C8H8O2. (E) liberates CO2 from aqueous sodium bircarbonate. (E) on permanganate oxidation furnishes
(F), C8H6O4, (F) on nitration yields two isomeric mononitro derivatives (G) and (H) having molecular
formula, C8H5NO6. Write the reaction involved in different steps.
4. An optically active amine (A) is subjected to exhaustive methylation and Hoffman elimination to yield
on alkene (B). (B) on ozonolysis gives an equimolar mixture of formaldehyde and butanol. Deduce the
structures of (A) and (B). Is three any structural isomer of (A), if yes draw its structure?
5. Compound (A), C14H10N2O when heated with dilute sulphuric acid gives ammonium sulphate, compound
(B), C8H6O4 and compound (C), C6H7N (as its sulphate). Compound (B) on heating gives (D), C8H4O3
and on heating with sodalime gives benzene. Compound (C) with dilute H2SO4/NaNO2 in the cold
followed by heating with water gives (E), C6H6O. Compound (E) on heating with Zn dust again gives
benzene. Identify (A), (B), (C) and (e) giving proper reactions?
6. How would you bring about the following conversion (in 3 steps) ?

Aniline 
 Benzylamine
7. Complete the following reactions with appropriate reagents.
I
O
? ? ? ?
NH C CH3         NO2

I
8. Write all the inter mediates in the synthesis of m-bromotoluene from p-toluidine.
9. Prepare PhD from PhNH2
10. Optically active sec butyl benzene from an amine intermediate.
Chemistry : Nitrogen Containing Compounds

SECTION - II
SINGLE CHOICE QUESTIONS
1. The increasing order of basicity of RCN, RCH = NR and RHN 2 is

(a) RCN < RCH = NR < RH 2 N (b) RNH 2 < RCN < RCH = NR

(c) RCH = NR < RNH 2 < RCN (d) RH 2 N < RCH = NR < RCN.
2. The bromination of aniline produces
(a) 2-bromoaniline (b) 4-bromoaniline
(c) 2,4,6-tribromoaniline (d) 2, 6-dibromoaniline.
3. In the reaction,
excess CH3Cl Ag 2 O 
CH3 NH 2   (X) 
moist
 (Y)  (Z) the final product (Z) is

(a) (CH3 )3 N (b) (CH 3 ) 4 N  Cl –

(c) (CH 3 ) 4 N  OH – (d) (CH 3 ) 2 NH .

4. Which of the following amine form N-nitroso derivative when treated with NaNO 2 and HCl?

(a) H3C NH2 (b) NH2

(c) N(CH3)2 (d) NH(CH3)

5. Identify compound (A) in the following oxidation reaction.

K Cr O , H SO
(A)  O O
2 2 7 2 4

NH2 OH

(a) (b)

NH2 NH2

OH

(c) (d) All of these.

OH
 Chemistry : Nitrogen Containing Compounds

i) (CH 3CO)2 O
6. PhNH2 
(2) ClSO3 H
 A . Product (A) is

(a) o-ClSO2 C6H4 NH2 H3 (b) o-ClSO2C6H4NHCOCH3

(c) m-ClSO2C6H5NHCOCH­3 (d) C6 H5 NHCOCH 3
7. Acetamide is treated with the following reagents. Which one of these would give methylamine?
(a) PCl5 (b) NaOH + Br2
(c) Soda lime (d) Hot conc. HSO4
8. Treatment of ammonia with excess of ethyl chloride will yield
(a) diethyl amine (b) ethane
(c) tetraethylammonium chloride (d) methyl amine
9. Acetaldoxime reacts with P2O5 to give
(a) Methyl cyanide (b) Methyl cyanate
(c) Ethyl cyanide (d) None of these
10. Nitrosoamines (R2N—N = O) are in-soluble in water. On heating with conc. H2SO4, they give secondary
amines. The reaction is called
(a) Libermann nitroso reaction (b) Etard reaction
(c) Fries reaction (d) Perkin reaction
11. In the given reaction :

NO2

CH3
(i) NaOH
 CH3 CHO 
(ii) 
[X]

[X] will be :

NO2 NO2

CH CHCHO CH3
(a) (b)

NO2 NO2
CH2 CH2 CH2 OH CH2 CH2 CHO
(c) (d)
Chemistry : Nitrogen Containing Compounds

12. In the given reaction :

NH OH / H  Na / C H OH
C6 H 5 —C — CH 3 
2
[X] 
2 5
[Y]
||
O
[Y] will be :

(a) C6 H 5 —CH — NH 2 (b) C6 H 5 —CH — NH — CH 3

| |
CH3 CH3

O O
|| ||
(c) C6 H 5 —C — NH — CH 3 (d) CH3 —C — NH — C6 H5
13. In the given reaction :

CH3 I (excess)
 [X]
N

[X] will be :

(a) (b)
N N
H CH3 H3C CH3

H2 C CH2
CH3 CH2
(c) (d)
N
N H3C CH
CH3 3
H H
14. In the given reaction

OH


C6 H 5 — N  N Cl  OH
 [X]

COOH

[X] will be :
 Chemistry : Nitrogen Containing Compounds

OH

H5 C6 N N

(a) H5 C6 N N OH (b)

COOH

COOH

H5 C6 N N

(c) (d) H C N N COOH

5 6

OH

15. In the given reaction :

NH2

2 moles of

ICI / CH COOH
[X]
3

OH

[X] will be

I
N NH2
I
I I
(a) (b)

NO2 NO2

NH2 NHI

(c) (d)
I I

NO2 NO2
Chemistry : Nitrogen Containing Compounds

16. In the given reaction :

 CH3 
 | 
 C 6 H5 — CH 2 — CH 2 —N  — CH 2 — CH3  OH  

[X]
 | 
 CH3 
 
as major product will be :
(a) C6 H5 —CH=CH2 (b) CH2=CH2
(c) C6 H5—CH=CH—CH3 (d) CH3 —CH=CH—CH3
17. In the given sequence of reactions :
CH3


(CH 3CO) 2 O Br2 / CH 3COOH H/ HOH
 (A)  (B)   (C)
Major

NH2

(C) will be :

CH3 CH3
Br
(a) (b)

Br
NH2 NH2

CH3 CH3
COCH3

(c) (d)
COCH3
NH2 NH2

18. In the given reaction :

(i) CH 3MgBr (excess)
CH3 — C  N 
(ii) H O / H 
[X]
2

[X] will be
O O
|| ||
(a) CH 3 —C —H (b) CH3 —C — CH3
OH O
| ||
(c) CH3 —C — CH3 (d) CH3 —C — NH 2
|
CH3
 Chemistry : Nitrogen Containing Compounds

19. In the given reaction :

NaNH2 / NH3 (1)
CH3 — CN  CH3CHO 
 [X]
[X] will be :
OH
|
(a) CH3 —CH — CH 2 — CN (b) CH3 —C  NH
|
CH 2 —CHO

(c) CH3—CH=CH—CN (d) CH3 —CH=CH—CHO

20. In the given reaction :
C2 H 5OH
C6 H 5 — C  N 
dry HCl
 [X]

[X] will be :
NH O
|| ||
(a) C6 H 5 —C — OC 2 H5 (b) C6 H 5 —C — OC 2 H5

OC2H5 O
| ||
(c) C6 H 5 —C — OC 2 H5 (d) C6 H 5 —C — NH 2
|
OC2H5
Chemistry : Nitrogen Containing Compounds

SECTION - III
MULTIPLE CHOICE QUESTIONS
1. The conversion of m–dinitrobenzene into m–nitroaniline can be brought about with
(a) (NH4 )2 S (b) sodium polysulphide
(c) Sn + HCl (d) Zn + NH4Cl
2. Benzylamine can be prepared by
LiAlH
(a) C6 H 5CONH 2 
ether
4
 (b) C6 H 5CH 2CONH 2  Br2  KOH 


LiAlH LiAlH
(c) C6 H 5CN 4
 (d) C6 H 5CH 2 NC 4


3. Which of the following statements are correct?

(a) In the case of primary, secondary and tertiary amines, the basic strength depends on the extent of
hydrogen bonding in the protonated amines
(b) The presence of groups like —OCH3 and —CH3 increases the basic strength of amines
(c) The presence of groups like —NO2, —CN and halogens reduces the basic strength of amines
(d) The basic strength of amines depends on their concentration
4. An aliphatic nitro compound turns red with the addition of a concentrated NaOH solution, followed by
the addition of an excess of an NaNO2 solution and then dilute H2SO4. The colour disappears with the
addition of the excess of an acid but reappears if the solution is made alkaline. The aliphatic nitro
compound is
(a) CH 3CH 2NO 2 (b) (CH3 )2 CHNO 2
(c) (CH3) 3CNO 2 (d) CH3 CH 2 CH 2 NO 2
5. Intermolecular hydrogen bonding is possible in the case of
(a) N–methylaniline (b) N, N–dimethylaniline
(c) methylamine (d) nitrobenzene
6. The product obtained in the reaction

CH3 — NO 2  Cl2  NaOH 



is
(a) ClCH2NO2 (b) Cl2CHNO2
(c) Cl3CNO2 (d) CH 3 NH 2
7. Which of the following reactions can be used to prepare ethyl isocyanide?
C H OH / H O alcohol
(a) CH3CH 2 I  AgCN 
2 5 2
(b) CH3CH 2 I  KCN 

alcohol alcohol
(c) CH3CH 2 NH 2  CHCl3  KOH 
(d) CH3CH 2Cl  KCN 
 Chemistry : Nitrogen Containing Compounds

8. In the reaction
NaNO3 / dil. HCl
CH3CH 2CH 2 NH 2 
0 5 C
 CH3CH  CH 2

the possible intermediates are

H
|

(a) CH 3 CH 2 CH 2 —N — NO (b) CH3CH­2CH2 —N=N—OH
|
H

 
(c) CH CH CH — N  N (d) CH CH C H
3 2 2 3 2 2

9. Which of the following statements are correct?

(a) Pyridine is a stronger base than ethylamine
(b) The basis strength of trimethylamine is less than that of dimethylamine
(c) Ethyl amine is a stronger base than ammonia
(d) Aniline is a weaker base than ammonia
10. Which of the following reagents can be used to distinguished between p–H 2 NC 6 H4 NH 2 and
C6 H5 COOH?
(a) KMnO4 (b) Br2/CCl4
(c) NaOH (d) HCl
Chemistry : Nitrogen Containing Compounds

MISCELLANEOUS QUESTIONS
SECTION - IV
COMPREHENSION TYPE QUESTIONS
Write up - I

An amine is a Lewis base and their aqueous solutions are basic. The basic character of amines are
depends on following factors.
Substitution by alkyl groups : As an example consider the relative basicities of ammonia pK b 4.74 and
methylamine pKb 3.36. Alkyl groups are electron donating towards cations, and methylamine has a
methyl group to help stabilize the positive charge on nitrogen. This stabilization lowers the potential
energy of the methyl ammonium cation, making methylamine a stronger base than ammonia. We might
expect secondary amines to be stronger base than primary amines and tertiary amines to be the strongest
bases of all. The actual situation is more complicated because of solution effects.
Resonance effects : Aromatic amines are weaker bases than simple aliphatic amines. The reduced
basicity is due to resonance delocalisation of the non-bonding electrons in the free amine.
Hybridization : It is fact that electrons are held more tightly by orbitals with more ‘s’ character. This
principle helps to explain why unsaturated amines tend to be weaker bases than simple aliphatic amines.

1. Which one is correct order for basic character of following compounds ?

NH2 NH2 NH2 NH2

NO2

OCH3 F
I II III IV

(a) I > II > III > IV (b) IV > III > II > I
(c) II > I > III > IV (d) II > I > IV > III
2. Which of the following statement is true ?
(a) Trimethyle amine is more basic than dimethyl amine in aqueous solution.
(b) Pyridine is less basic than pyrrole.
(c) More the ‘s’ character in hybridisation of nitrogen less the basic strength.
(d) More the pKb value of amines more basic strength
3. Which of the following compound is least basic ?
..
(a) CH3C  N : (b) CH3CH  N H
.. ..
(c) CH3  CH 2  N H 2 (d) CH3CH 2 N HCH3
 Chemistry : Nitrogen Containing Compounds

Write up - II
Nitrous acid reacts with all classes of amines. The products obtained from these reactions depend on
whether the amine is primary, secondary or tertiary and whether the amine is aliphatic or aromatic.
Aliphatic primary amines react with nitrous acid (NaNO2 + HCl) to form alcohol as major product. In
addition to alcohol, alkene and alkyl halides are also formed as minor product.
Certain cyclic primary amines can undergo either ring expansion or ring contraction reactions on
treatment with nitrous acid. This reaction is called Demjanov ring expansion or contraction.
HNO 2
OH
CH2 NH2 CH2OH +

4. What will be the major product when 2-amino propane is treated with nitrous acid ?
(a) 1-propanol (b) 2-propanol
(c) propene (d) cyclopropane
5. Which of the following product(s) will be obtained when n-propyl amine is treated with sodium nitrite
and hydrochloric acid ?

(a) H3C CH CH3 (b) H3C CH CH2

OH

Cl

(c) H3C CH CH3 (d) all of these

6. Two compounds (A) and (B) are treated with nitrous acid,

NH 2
|
CH3 — CH — CH 3 ; CH3 — CH 2 — CH 2 — NH 2
(A) (B)

The corresponding stable carbocation intermediates are :

(From A) (From B)
 
(a) CH  CH  CH CH3  CH 2  CH 2
3 2 2

 
(b) CH  C H  CH CH3  CH 2  CH 2
3 3

 
(c) CH3  C H  CH 3 CH3  C H  CH 3
(b) none of these
Chemistry : Nitrogen Containing Compounds

MULTIPLE MATCHING TYPE QUESTIONS

Match the following

7. Column – I Column – II

(a) NH2 (p) 0.4

(b) NH 3 (q) 4.63

(c) NH (r) 11.27

(d) NH (s) 9.26

8. Column – I Column – II

COOH NH2

conc. H 2SO 4
 HN 3  
(a) (p) pH 5 – 7
Cl Cl


(b) NH2  C6 H 5 N 2  Azo dye. (q) Curtius reaction


(c) OH  C 6 H 5 N 2  Azo dye. (r) Sulphanilic acid

(d) Methyl orange (s) pH 9 – 10

 Chemistry : Nitrogen Containing Compounds

ASSERTION-REASON TYPE QUESTIONS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
9. Assertion : Aniline is a weaker base than ethyl amine
Reason : Lower the value of pKb , stronger is the base.
10.Assertion : Aniline is a weaker base than cyclohexyl amine.
Reason : Aniline undergoes halogenation even in the absence of a catalyst.
11. Assertion : The reaction between a diazo salt and an aromatic amine or a phenol, giving an aminoazo or
hydroxyazo compounds is called coupling reaction.
Reason : Condensation of diazonium salt with phenol is carried out in weakly acidic medium.
12.Assertion : Nitration of aniline can be done conveniently by protecting the amino group by acetylation.
Reason : Acetylation increases the electron density in the benzene ring.
13.Assertion : p-Anisidine is stronger base than aniline.
Reason : –OCH3 group in anisidine exerts –R effect.
14.Assertion : Pyrrole is less basic than pyridine.
Reason : In pyrrole, nitrogen in sp3 hybridized.
15.Assertion : Aniline does not undergo Friedel Crafts reaction.
Reason : –NH2 group of aniline reacts with AlCl3­ (lewis acid) to give acid­base reaction.
Chemistry : Nitrogen Containing Compounds

SECTION - V

A. Only one option is correct (Objective Questions)

1. In the following reaction,

O conc. HNO3

conc. H 2SO 4
X

N
H

the structure of the major product ‘X’ is

O2 N
O O

(a) NO2 (b)

N N

H H

O
O
N
(c) (d) O N N
2
H
NO2 H
2. Among the following, the least stable resonance structure is
O O
(a) N (b) N
O O

O O
(c) N (d) N
O O

(i) NaNO 2 / HCl

(CH ) NH 0  5C
3. F NO2 
3 2
DMF, 

(A) 
(ii)H / Ni
(B) is :
2

CH3
CH3 O2 N N
(a) H2 N N (b)
CH3
H2 N

(c) H2 N NH2 (d) O2 N NH2

 Chemistry : Nitrogen Containing Compounds

4. The correct order of the basicities of the following compounds is :

NH O
(a) H3 C C , H3 C CH2 NH2 , (CH3 )2 NH , H3C C NH2
NH2
2 3 4
1

(a) 2 > 1 > 3 > 4 (b) 1 > 3 > 2 > 4

(c) 3 > 1 > 2 > 4 (d) 1 > 2 > 3 > 4
5. Assertion : In strongly acidic solutions, aniline becomes more reactive towards electrophilic reagents.
Reason : The amino group being completely protonated in strongly acidic solution, the lone pair of
electrons on the nitrogen is no longer available for resonance.
(a) both assertion and reason are correct and reason is the correct explanation of the assertion
(b) both assertion and reason are correct, but reason is not the correct explanation of the assertion
(c) assertion is correct, but reason is incorrect
(d) assertion is incorrect, but reason is correct
6. Among the following the strongest base is :
(a) C6 H 5 NH 2 (b) p-NO2 C6 H4 NH 2
(c) m-NO 2.C 6 H4 NH 2 (d) C6 H 5 CH 2 NH 2
7. The most unlikely representation of resonance structures of p-nitrophenooxide ion is :

- - -
O O O O
N N

(a) (b)

-
O O

-
O O O O
N N

(c) (d)

-
O O

8. Examine the following two structures for the anilinium ion and choose the correct statement from the
ones given below :
Chemistry : Nitrogen Containing Compounds

NH3 NH3

I II

(a) II is not an acceptable canonical structure because carbonium ions are less stable than ammonium
ions
(b) II is not an acceptable canonical structure because it is non-aromatic
(c) II is not an acceptable canonical structure because the nitrogen has 10 valence electrons
(d) II is an acceptable canonical structure
9. Carbyl amine test is performed in alc. KOH by heating a mixture of :
(a) chloroform and silver powder (b) trihalogenated methane and a primary amine
(c) an alkyl halide and a primary amine (d) an alkyl cyanide and a primary amine

SUBJECTIVE QUESTIONS
NaNO2 / HCl
1. C5H13 N  N2
(tertiary alcohol)  other products
optically active

Find X and Y. Is Y optically active? Write the intermediate steps.

NO2 NO 2

2. Convert to in not more than four steps. Also mention the temperature and
OH
reaction condition.
3. Which of the following is more acidic and why?

NH3 NH3

4. There is a solution of p-hydroxybenzoic acid and p-amino benzoic acid. Discuss one method by which
we can separate them and also write down the conformatory test of the functional groups present.

5. How would you bring about the following conversion (in 3 steps). Aniline  Benzylamine.
 Chemistry : Nitrogen Containing Compounds

6. Following reaction gives two products. Write the structures of the products.
(CH3CO)2 O, heat
CH3CH 2 NH 2  
7. Give reasons for the following in one or two sentences :
“Dimethyl amine is a stronger base than trimethyl amine”
8. Write the structure of the foul smelling compound obtained when aniline is treated with chloroform in
the presence of KOH.
9. Complete the following with appropriate structure :
1. NaNO 2 and HCl at 5 C
2,3  dinitro aniline 2. anisole
A

10. Give the structures of A, (explanations are not required.) “A (C3H9N) reacts with benzene-sulphonyl
chloride to give a solid, insoluble in alkali”.
Chemistry : Nitrogen Containing Compounds

ANSWERS
SECTION - I
(Subjective Questions)
Answers are given in separate booklet.

SECTION - II
(Single Choice Questions)
1. (a) 2. (c)
3. (c) 4. (d)
5. (d) 6. (b)
7. (b) 8. (c)
9. (a) 10. (a)
11. (a) 12. (a)
13. (b) 14. (a)
15. (b) 16. (b)
17. (b) 18. (c)
19. (c) 20. (a)

SECTION - III
(Multiple Choice Questions)
1. (a, b) 2. (a, c)
3. (a, b, c) 4. (a, d)
5. (a, c) 6. (a, b, c)
7. (a, c) 8. (a, b, c, d)
9. (b, c, d) 10. (c, d)

SECTION - IV
(Comprehension Type Questions)
1. (a) 2. (c)
3. (a) 4. (b)
5. (d) 6. (b)
 Chemistry : Nitrogen Containing Compounds

(Multiple Matching Type Questions)

7. (a) (q) (b) (s)
(c) (r) (d) (p)
8. (a) (q) (b) (p)
(c) (s) (d) (r)

(Assertion Reason Type Questions)

9. (b) 10. (b)
11. (c) 12. (c)
13. (c) 14. (c)
15. (a)

SECTION - V

A. Only one option is correct (Objective Questions)

1. (b) 2. (a)
3. (a) 4. (b)
5. (d) 6. (d)
7. (c) 8. (c)
9. (b)
SUBJECTIVE
Answers are given in separate booklet.