NITROGEN COMPOUNDS

IIT-JEE Syllabus

1. Amines: Basicity of aniline and aliphatic amine

2. Preparation from nitro compounds, reaction with nitrous acid, formation and reactions of

diazonium salts and its coupling with phenols, carbylamine reaction.

3. This chapter includes : Aliphatic amine, Nitro alkane, Aniline, Nitrobenzene, Diazonium

salt

Total No. of questions in Nitrogen Compounds are :

Solved examples…....…………………………..…14
Exercise # 1 …….……………………………….…35
Exercise # 2 …….……………………………….…24
Exercise # 3 …….……………………………….…32
Exercise # 4 ……………………………………..…12
Exercise # 5 ……………………………………..…20
Total No. of questions………………..137

*** Students are advised to solve the questions of exercises in the same sequence or as directed by
the faculty members.

NITROGEN COMPOUNDS 1
 Index : Preparing your own list of Important/Difficult Questions
Instruction to fill

(A) Write down the Question Number you are unable to solve in column A below, by Pen.
(B) After discussing the Questions written in column A with faculties, strike off them in the
manner so that you can see at the time of Revision also, to solve these questions again.
(C) Write down the Question Number you feel are important or good in the column B.

COLUMN :A COLUMN :B
EXERCISE
NO. Questions i am unable
Good/Important questions
to solve in first attempt

Advantages

1. It is advised to the students that they should prepare a question bank for the revision as it is
very difficult to solve all the questions at the time of revision.

2. Using above index you can prepare and maintain the questions for your revision.

NITROGEN COMPOUNDS 2
 EXERCISE # 1

Questions product (A) is

based on Preparation of amines
(A) COOH (B) NH2
Q.1 N-Ethyl pthalimide on hydrolysis gives–
(A) Methyl alcohol (C) Br (D) None of these
(B) Ethyl amine
(C) Dimethyl amine
(D) Diethyl amine Sol. [B] C – NH2 Br / KOH
2   NH2
Sol. [B] O
O
||
C COOH
N–C2H5+2HOH
C COOH (i) HNO3, H2SO4
|| + Q.5 (P), final product P is
O (ii) SnCl2 / HCl
pthalimide C2H5NH2 (iii) HNO2
ethyl amine (iv) CuBr/
Therefore option (B) is correct. Br N2Cl

Q.2 Which of the following reaction does not give (A) (B)
1° amine as final product
NH2
H 3O 
(A) CH3 – CN 
(B) CH3CN LiAlH
 4  (C) (D) None of these

(C) CH3 – NC H
3O

Br
(D) CH3 – NC LiAlH
 4 
LiAlH Sol.[A]
Sol. [D] CH3 – NC  
4  does not give 1° amine
as final product
Conc. Conc. Questions
Q.3 (i) HNO3, H2SO4 (low temp.) based on Reactions of Amines
X
(ii) SnCl2 / HCl
Q.6 The correct set of the products obtained in the
Incorrect statement about [X] is -
following reactions–
NH2 NO2
(a) RCN reduction
(A) X is (B) X is (i) CH3MgBr
(b) RCN
(ii) H2O
hydrolysis
(C) X undergoes carbylamine test (c) RNC
(D) All of these
(d) RNH2 HNO2
NO2 The answer is–
(A) A B
Sol. [B] X does not 2º Amine Methyl ketone
C D
1º Amine Alcohol
(B) A B
Br2 / KOH
Q.4 C – NH2    A 1º Amine Methyl ketone
O C D
NITROGEN COMPOUNDS 3
 1º Amine Alcohol

(C) A B CH3CH2 C H 2 + Cl– Alkene CH3CH=CH2
2º Amine Methyl ketone   +
C D CH3CH2CH2-OH
 Alcohol
CH3– C H 2 –CH3 or
2º Amine Acid CH3–CH–CH3
(D) A B + |
OH
2º Amine Methyl ketone
C D CH3CH2CH2–Cl
Alkyl halides or
2º Amine Aldehyde
CH3–CH–CH3
Sol.[B] (a) R–CN reduction R–CH2NH2 |
Cl
1º Amine Therefore option (D) is correct
CH3
CH3MgBr |
(b) R–CN R–C= N–MgBr
H 2O Q.9 Which of the following amine does not react
with Hinsberg reagent–
H2O R– C– CH3 + NH3 + Mg Br (A) Neopentyl amine
|| OH
(B) Isopropyl amine
O
Methyl ketone
(C) Triethyl amine
(D) Ethyl methyl amine
hydrolysis Sol.[C] Only 1º and 2º amine react Hinsberg reagent.
(c) R–NC R–NH–CH3
2º Amine 3º amine can not be react with Hinsberg
..
HNO2 reagent. Therefore triethyl amine (C 2 H 5 ) 3 N .
(d) R–NH2 R–OH
Alcohol Which is 3º Amine can't be react with Hinsberg
reagent.
Therefore option (B) is correct.
option (C) is correct

Q.7 Which amine will not react with nitrous acid– Q.10 Methyl amine on reaction with chloroform in
(A) Methyl amine (B) Ethyl amine the presence of NaOH gives–
(C) Dimethyl amine (A) Methyl isocyanide
(D) N, N Dimethyl ethane amine (B) Methyl chloride
Sol.[D] Due to steric hindrance N, N-dimethyl ethane (C) N-Methylchloramine
(D) Chloramine
amine can not be reaet with nitrous acid.
Sol.[C] CH3NH2 + Cl2 NaOH
 CH3–NH–Cl + HCl
Therefore option (D) is correct
N-methyl chloroamine
There fore option (C) is correct.
Q.8 Which of the following compound cannot be
produced if 1-propane amine is treated with Q.11 Which of the following diazonium salt is
NaNO2 and HCl – relatively stable of 0-5ºC–
(A) Propane -1-ol (A) CH3–NN} Cl¯
(B) Propane-2-ol (B) CH3–C(CH3)2–NN} Cl¯
(C) 2-Chloropropane (C) C6H5–NN} Cl¯
(D) 2-Propaneamine (D) (CH3)3C–NN} Cl¯
Sol.[C] Benzene diazonium salt is stable at 0–5ºC due
Sol.[D] CH3CH2CH2–NH2+NaNO2 + 2HCl (
HONO )

H O to the resonance.
2

Therefore option (C) is correct.

[CH3CH2C H 2 –
– NN:Cl ]
diazonium salt + NaCl
(highly unstable) Q.12 Alkylamine dissolve in hydrochloric acid to
form alkylammonium chloride. The nitrogen
–N2 in the latter salt is–
(A) Quadricovalent only
NITROGEN COMPOUNDS 4
 (B) Tricovalent only (B) Trimethyl ammonium bromide
(C) Unielectrovalent only (B) (A) Ethyl ammonium iodide
(D) Quadricovalent, Unielectrovalent (B) Methyl ammonium bromide
 [ RNH 3 ]Cl– or
Sol.[D] R–NH2 + HCl  (C) (A) Ethyl ammonium iodide
H+ (B) Trimethyl ammonium bromide

..
R– N –H Cl– (D) All of these
| Sol.[C] C2H5NH2 + HI  C2H5NH–I
H
Ethyl ammonium iodide
alkylammonium chloride
In this salt nitrogen have Quadricovalent and (CH3)3N + HBr  (CH3)3N – Br
Unielectrovalent bond. trimethyl ammonium bromide
There fore option (D) is correct. Therefore option (C) is correct.

Q.13 The presence of primary amines can be Q.17 When propionamide reacts with Br2 in the
confirmed by– presence of alkali the product is–
(A) Reaction with HNO2 (A) CH3CH2CH2NH2 (B) CH3CH2NH2
(B) Reaction with CHCl3 and alc. KOH (C) C3H7CN (D) C2H5CN
(C) Reaction with Grignard reagent
Sol.[B] CH3–CH2–C–NH2 KOH
Br2
(D) Reaction with acetyl chloride ||
Sol.[B] Only primary amine give carbyl amine reaction O CH3CH2–NH2+KBr +KHCO3
 – There fore option (B) is correct.
R–NH2+CHCl3 KOH
 R– N  C +3KCl+3H2O
There fore option (B) is correct. Q.18 A reaction of ethyl amine & acetic
Q.14 In the reaction CH3CH2NH2 + CH3MgBr  anhydride leads to the formation of–
(A) CH3NHCOCH3
X, the product is–
(B) C2H5CONHCH3
(A) CH3CH3
(C) CH3CONHC2H5
(B) CH3CH2CH3
(D) CH3–CH=N–OC2H5
(C) CH3CH2CH2CH3
(D) CH4
Sol.[C] CH3CH2–NH2 + (CH3CO)2O   
CH3–C–NH–CH2–CH3+CH3COOH
Sol.[D] ||
O
Br Therefore option (C) is correct.
CH3–CH2NH2+CH3MgBrCH4 +Mg
Methane NH–CH2CH3
Q.19 Which of the following is not correct–
Therefore option (D) is correct.
(A) Ethyl amine & aniline both have NH2
Q.15 The compound obtained by the reaction group
between primary amine and aldehyde is– (B) Ethyl amine & aniline both dissolve in
(A) An amide (B) imine HCl
(C) Nitrite (D) Nitro (C) Ethyl amine & aniline both react with
CHCl3 & KOH to form unpleasent gas
H
R– CH = O + N–R R – CH = N – R (D) Ethyl amine and aniline both react with
Sol.[B] H aldimine HNO2 to give hydroxy compound
Sol.[D] Ethyl amine react with HNO2 (NaNO2+HCl)
Therefore option (B) is correct
and formed ethyl alcohol
Q.16 Name the products in the acid- base reaction- C2H5NH2 HNO2  C2H5OH
(A) CH3CH2NH2 + HI (B) (CH3)3N + HBr But C6H5–NH2 react with HNO2(NaNO2+HCl)
(A) (A) Trimethyl ammonium iodide to give benzene diazonium salt (BDC)
NITROGEN COMPOUNDS 5
 NaNO  HCl
C6H5NH2  2 C6H5 N 2 Cl –
Br
Q.24 CH3–CH2– CH2 2  A
NaOH
BDC NO2
Therefore option (D) is correct. Here A is–
O
Questions Preparation and chemical Reaction of (A) CH3–CH2– C – OH
based on Alkyl cyanides and nitroalkanes
Br
(B) CH3–CH2–CH –NO2
Q.20 Cyanides exists in–
Br
(A) Tautomeric form
(B) Geometrical form (C) CH3–CH –CH2–NO2
(C) In both form Br
(D) None
(D) CH2 –CH2–CH2–NO2
Sol.[A] Cyanides exists in tautomeric form.
 Br
H – C N CN –H
Sol.[B] CH3–CH2–CH –NO2
Therefore option (A) is correct. Q.25 Which of the following is functional isomer
of nitro methane–
(A) CH3–NO2 (B) CH3–O–NH2
Q.21 Hydrolysis of alkyl isocyanide yields–
(A) Primary amine (B) Tert. amine (C) CH3–O–N=O (D) O – N = O
(C) Alcohol (D) Aldehyde CH3
Sol.[C] CH3–O–N=O is functional isomer of nitro
 HOH O–H
Sol.[A] R– N C R–N = C methane
H
O
|| 
HOH/ H /  True / False type questions
[R–NH–C–H] R–NH2+HCOOH
So the primary amine is formed by hydrolysis Q.26 Tertiary amines react with Grignard reagents
of alkyl isocyanide to evolve alkanes.
Therefore option (A) is correct. Sol. Tertiary amine can't be react with Grignard
reagent.
Therefore statement is False.
Q.22 Dipole moment of which of the following is
highest- Q.27 The boiling point of ethylenediamine is lower
(A) Ether (B) Alcohol than that of ethylamine.
(C) Halo alkane (D) Nitro alkane Sol. Molecule of ethylene diamines
Sol.[D] Factual (NH2–CH2–CH2–NH2) can form strong
hydrogen bonds to each other compare to
NaNO
2 A ; ethylamine thus boiling point of ethylene
Q.23 CH3–CH2–Cl   
diamine is higher than that of ethylamine.
Cl
AgNO 2 Therefore statement is False.
CH3 – CH2     B. A and B are–
Q.28 Catalytic reduction of isocyanides gives
(A) CH3–CH2–NO2, CH3–CH2–O–N=O primary amines.
(B) CH3–CH2–O–N=O, CH3–CH2–NO2 Sol. Isocyanides gives secondary amine by catalytic
(C) Both are CH3–CH2–NO2 reduction.
reduction
NO R – N C R–NH–CH3
sec. amine
(D) Both are CH3 – CH2
Therefore statements is False.
Sol.[B] CH3–CH2–O–N=O, CH3–CH2–NO2
Q.29 Nitrobenzene is more reactive than benzene

NITROGEN COMPOUNDS 6
 towards electrophilic substitution reactions.
Sol. Due to the e– withdrawing nature (–I effect) and
–M effect of –NO2 group
Nitrobenzene is less reactive than benzene
towards electrophilic substitution
Therefore statement is False.

Q.30 Carbylamine reaction is used as a test to

distinguish primary amines from secondary
and tertiary amines.
Sol. Only primary amine gives positive corbylamine
test. Secondary and tertiary amines do not give
carbylamine test
Therefore statement is True.

 Fill in the blanks type questions

Q.31 (CH3)3C–NH2 is classified as a .......... amine
Sol. 1º amine

Q.32 Reduction of cyanides with ........ followed by

hydrolysis gives aldehydes.
Sol. SnCl2/HCl

Q.33 All primary amine react with grignard reagent

to give ……...

Q.34 Dipole moment of alkyl cyanides is ....... than

that of isomeric alkyl isocyanides.
Sol. Higher

Q.35 When aniline is heated with chloroform and

alcoholic potassium hydroxide, .......... is
formed.
Sol. phenyl isocyanide

NITROGEN COMPOUNDS 7
 EXERCISE # 2

Part-A (Only single correct answer type NH–CO–CH3

Questions) +
X H2O / H Z, Z is –
HNO3/H2SO4
Q.3
heat
Q.1 Choose the false statement–
(A) –NH2 is strongly activating while NH2 NH2
– NHCOCH3 is activating
(A) (B)
(B) –NO2 is strongly deactivating while –
NO2
CHO is deactivating
NO2
(C) –NH– C–R and –CH = O are m–directing
|| NHCOCH3 NH2
O O2N NO2
(D) –CF3 and – C–R are m–directing (C) (D)
||
O NO2
NO2
Sol.[C] Activating group always o- and p-directing
.. Sol.[B]
– NH – C – R activating group ..
|| NHCOCH3 NH –CO–CH3 NH–C–CH3
O ||
NH2 O
So its o, p- directing not m-directing HNO3/H2SO4
+
Therefore option (C) is correct.

Q.2 Identify X in the reaction NO2

.. NH2
NH2
H2O/H+
CHCl3/KOH
Intermediate HCl X
heat 300K
NO2
Cl
Therefore option (B) is correct.
..
COOH NH2
Q.4 Identify 'Z' in the reaction given below–
(A) (B) NH2

Cl COOH 1.HNO2(280K) NaOH CH3I

X Y Z
.. 1.H2O; Boil
NC NH2
NH–CH3 N2Cl
(C) (D) H 3C CH3 H3C CH3
(A) (B)

Cl Cl
NH2 CH3 CH3
NH–CHCl2 NH2
OCH3 OCH3
CHCl3/KOH HCl
Sol.[C] heat OH OH
(C) (D)
Cl Cl Cl
Therefore option (C) is correct. OH

NITROGEN COMPOUNDS 8
 NH2 OH .. ..
N2Cl OH
(i) HNO2(280K) CH2OH CH2NCl
Sol.[C] NaOH (A) (B)
(ii) H2O Boil
–H2O
(X) ..
ONa OCH3 OH
CH3NCl
CH3I (C)

(Y) ..
(Z) N2Cl
Therefore option (C) is correct. CH2NCl
(D)

Q.5 Of the following statements– NH2

N 2 Cl –
(P) C6H5N=CH–C6H5 is a Schiff's base CH2–NH2
CH2–OH
(Q) A dye is obtained by the reaction of Sol.[A] NaNO2+HCl
or
aniline and C6H5N=NCl HNO2
(R) C6H5CH2NH2 on treatment with Therefore option (A) is correct.
[NaNO2 + HCl] gives diazonium salt
(S) p–Toluidine on treatment with
[HNO2 + HCl] gives diazonium salt Q.7 Compound A when reacted with PCl5 and
(A) Only (P) and (Q) are correct then with ammonia gave B. B when treated
(B) Only (P) and (R) are correct with bromine and caustic potash produced C.
(C) Only (R) and (S) are correct C on treatment with HCl and NaNO2 at
(D) (P), (Q) and (S) are correct 0ºC and then boiling produced ortho-
Sol.[D] (A) C6H5N=CH–C6H5 is a Schiff's base cresol.Compound A is–
(B) (A) o-Toluic acid (B) o-Chlorotoluene
C6H5N2 Cl+H NH2   (C) o- Bromotoluene (D) m-Toluic acid
Sol.[A]

N=N NH2 CH3 CH3

COOH
Peraamino azobenzene(dye) C–NH2
(i)PCl5 || Br2
NaNO2+HCl
(C) C6H5CH2NH2 C6H5CH2–OH O
(ii) NH3 KOH
Benzyl alcohol (A) (B)
not a diazonium salt
CH3 CH3
CH3 CH3 HCl+
NH2 N 2 Cl –
NaNO2
Boil
(D) HNO2 0ºC H2O
HCl
Cresol
CH3
NH2 N=N–Cl
OH
p-Toluidine diazonium salt
Therefore option (D) is correct.
Therefore option (A) is correct.
..
NH2
CH2NH2 Q.8 A colourless liquid A (b.p. 184ºC) is
NaNO2 sparingly soluble in warm water to which it
Q.6 ?
HCl gives feebly alkaline reaction on treating with
NaNO2 and dil HCl in the cold solution, it
NITROGEN COMPOUNDS 9
 yields a solution which reacts with an alkaline CH3 O
solution of -naphthol to give an orange N – C – CH3
yellow precipitate. Compound A is–
(A) C6H5N2Cl (B) C6H5NH NH2 Sol.[C] B is
(C) n-C4H9NH2 (D) C6H5NH2 CH3
Sol.[D]
NH2 N 2 Cl – 3  A AlCl
2  B. Br
Q.11 + NH2– OH  
 
water
NaNO2+HCl Here B is–
Br
Benzenediazonium N NH2
A Br
chloride (A) (B)
C6H5–N Br
|| NH2 NH2
N 2 Cl – N Br Br
OH OH (C) (D)
+
Br Br
-Naphthol yellow precipitate NH2
Therefore option (D) is correct. Br Br
Sol.[C]

Q.9 Nitration of aniline is done in– Br

(A) Acidic medium
(B) Alkaline medium H
N 
(C) Neutral medium H C H 3 M gBr
Q.12     A. Here A is–
(D) Acidic medium by first converting it into
acetanilide before nitration NH – CH3 NH – Br
Sol.[D] Direct nitration of aniline is not possible
because NH2 group highly activating group. So (A) (B)
nitration can be carried out after protecting the
NH2 group by acetylating. There fore nitration – +
NH – MgBr NH2
of aniline is done acidic medium by first
CH3
converting it into acetanilide before nitration.
(C) (D)
So option (D) is correct.
– +
NH – MgBr
NH–CH3
O O
|| || Sol.[C]
CH 3 CO CCH 3
Q.10      A AlCl
3  B.
CH3COOH CH 3 Cl

Here B is–
NH–CH3 NH2 Part-B (One or more than one correct
CH3 answer type Questions)
(A) (B)
Q.13 Which of the following statements is/are
CH3 O O
correct?
N – C – CH3 CH3–N–C–CH3 (A) The basic strength of amines depends
upon their concentration
(C) (D)
(B) In the case of primary, secondary and
CH3 tertiary amines, most basic is tertiary
always
(C) The presence of groups like –OCH3 and
NITROGEN COMPOUNDS 10
 –CH3 increase the basic strength of (B) C6H5 N  Cl – + KOH Cu
C6H5CN
2
amines Benzonitrile
(D) The presence of groups like –NO2 and (sandmeyer reaction)

–CN, and halogens decrease the basic NaSO4 CN

strength of amines.
Sol. [A, B, D] (C) +NaCN  Na2SO4 +
The basic strength of primary secondary and
tertiary amine depends upon their concentration. Benzonitrile
Electro donating group's increase the basic (D)
strength of amines and electron withdrawing C6H5 (CH3CO)2
group's decrease the basic strength of amine C=N–OH C6H5CN+2CH3COOH
There fore option B, C and D are correct. H
Benzonitrile
Therefore option B, C and D are correct.
Q.14 p-Chloroaniline and anilinium hydrochloride
can be distinguished by–
(A) Sandmeyer reaction Q.17 Depending upon the nature of the reducing
(B) NaHCO3 agent, the reduction of nitrobenzene under
(C) AgNO3 basic condition may give–
(D) Carbylamine test (A) Aniline
Sol. [A, B, C] (B) Azobenzene
p-chloroaniline and anilinium hydrochloride (C) Azoxybenzene
distinguised by sandmeyer reaction NaHCO3 (D) Hydrazobenzene.
and AgNO3 Sol. [B, C, D]
Therefore option A, B and C are correct. The reduction of nitrobenzene yields different
product depending upon reducing agent

Q.15 The products of reaction of alcoholic silver CH3ONa/CH3OH/ 
nitrite with ethyl bromide are– or C6H5–N=N–C6H5
Azoxy benzene
(A) Ethane (B) Ethene glucose/NaOH/
(C) Nitroethane (D) Ethyl nitrite
Sol. [C, D] C6H5NO2 Zn/NaOH/CH3OH/HOH C6H5–N=N–C6H5
Alcoholic O or
C2H5Br C2H5–N +C2H5–ON=O Azobenzene
AgNO3 Alkaline sodium stannite
O Ethyl nitrite
Nitro ethane
(main product) Zn dust / NaOH/
C6H5–NH–NH–C6H5
Therefore option (C) and (D) are correct.
Hydrazobenzene
Q.16 Benzonitrile is obtained when– Therefore option (B) ,(C) and (D) are correct.
(A) Bromobenzene is heated with alcoholic
KCN Q.18 Addition of CH3MgBr to HCN followed by
(B) Benzenediazonium chloride is heated acid hydrolysis gives a compound which can
with KCN in presence of Cu powder also be prepared by–
(C) Sodium benzenesulphonate is fused with (A) Stepen’s reduction of acetonitrile
NaCN (B) Bubbling the gas produced by the action of
(D) Benzaldoxime is heated with acetic water on CaC2 through dil. H2SO4
anhydride. containing HgSO4
Sol. [B, C, D] (C) dry distillation of calcium acetate
(D) addition of CH3MgBr to dry ice followed
by acid hydrolysis.
Sol. [A,B]
NITROGEN COMPOUNDS 11
 CH3 Sol.[D] In strongly acidic solution, aniline convert in to
 |
– anilinium ion. Which is less reactive towards
H–CN+ C H 3 MgBr  H–C=N–Mg–Br
electrophilic reagent.
H+/H2O

Br NH2 NH 3
H–C=O+Mg +NH3
| OH
CH3 H+
Acetaldehyde
Anilinium ion
(A)
SnCl2/HCl In Anilinium ion lone pair of electrons on the
CH3–CN CH3–CH=NH–HCl H2O
imine hydrochloride nitrogen is no longer available for resonance.
CH3CHO+ NH4Cl Therefore Assertion is false but reason is true so
Acetaldehyde option (D) is correct.
(B) CaC2+ 2H2OHCC–H+Ca(OH)2
Hg+2/H3O+ Q.20 Assertion : Benzonitrile is prepared by the
Hg +2
reaction of chlorobenzene with potassium
CH3–CH–O H CH2=CH–OH
| H3O+ cyanide.
–H2O O H
Reason : Cyanide ion is a strong nucleophile.
CH3CHO Sol.[D] The C–Cl bond in chlorobenzene has some
Acetaldehyde double bond character due to resonance so it is
Therefore option (A) and (B) are correct. difficult to replace chlorine from chlorobenzene.
Thus benzonitrile can't be prepared by the
reaction of chlorobenzene with KCN.
Part-C (Assertion & Reasoning type
CN– ion is a strong nucleophile
Questions)
Therefore assertion is false but reason is ture
The following questions 19 to 22 consists of option (D) is correct.
two statements each, printed as Assertion
and Reason. While answering these
Q.21 Assertion : Sulphanilic acid exists as a
questions you are to choose any one of the
dipolar ion whereas p-aminobenzoic acid
following five responses.
does not.
(A) If both Assertion and Reason are true
Reason : Carbonxyl group being more acidic
and the Reason is correct explanation
of the Assertion. than –SO3H group can easily transfer a H+ to
(B) If both Assertion and Reason are true the amino group.
but Reason is not correct explanation NH2 NH 3
of the Assertion.
(C) If Assertion is true but the Reason is Sol.[C]
false.
(D) If Assertion is false but Reason is true. SO3H SO 3–
(E) If Assertion & Reason are false. Sulphanilic acid dipolar ion
Q.19 Assertion : In strongly acidic solution, Whereas p-aminobenzoic acid does not because
aniline becomes more reactive towards SO3H group is more acidic than –COOH group
electrophilic reagents. can easily transfer a H+ to amino group.
Reason : The amino group being completely Therefore Assertion is true but the reason is
protonated in strongly acidic solution, the false option (C) is correct.
lone pair of electrons on the nitrogen is no
longer available for resonance.
Q.22 Assertion : Oxidation of 1-nitronaphthalene
NITROGEN COMPOUNDS 12
 on oxidation gives phthalic acid.
Reason : An amino group attached to the
benzene ring makes it resistant to oxidation
whereas nitro group makes the benzene ring
susceptible to oxidation.
Sol.[E] Assertion and reason both are false
Therefore option (E) is correct.

Part-D Column Matching

Match the items of column A to those of column B :

Q.23 Column A Column B
Reactions Products
O

(a) 2CH3NH2+ O (i) N=CH

O
O
(b) (CH3)2NH+C6H5COCl (ii) (CH3)2N–S
O
O
(c) CHO + NH2(iii) (CH3)2N–C

O O
(d) CH3NH2+ C6H5–SO2Cl (iv) CH3NH–C–(CH2)2–C–O

Sol. (a)-iv, (b)-iii, (c)-i, (d)-ii,

Q.24 Column A Column B

NaNO  HCl
(a) R'NH2  2  (i) RR'N–N = O
NaNO  HCl
(b) PhNH2  2  (ii) Ph–N+NCl–

(c) PhN(CH3)2 NaNO2+HCl (iii) (CH3)2N–Ph–N=O

NaNO  HCl
(d) RR'NH  2  (iv) R'OH + N2
Sol. (a)-iv, (b)-ii, (c)-iii, (d)-i
Factual

NITROGEN COMPOUNDS 13
 EXERCISE # 3

Part-A Subjective Type Questions

NH2 NH2
Q.1 is reacted with HNO2.
Q.6 gives meta product with HNO3 but
OH
Sol. is obtained
O
||
NH–C–CH3

N2Cl OH
gives para product. Why ?

Q.2 reacted with . Sol.

 
NH2 NH3 NH3
Sol. N=N is obtained Nitration
+HNO3
OH NO2
Meta directing due
to inductive effect.
N2Cl O
||
NH–C–CH3
Q.3 is hydrolysed.

OH
Sol. is obtained
Para directing due to + M effect.

  Q.7 R–NH–R doesnot give carbilamine test. Why?

Q.4 CH3–CH2– N  C + H2O H ? + ?
Sol. Only 1º amine give carbyl amine test R– NH –
O R is 2º amine so it does not give carbyl amine
||
Sol. CH3CH2 – NH2 + HO – C – H test.

is obtained
OH N2Cl Q.8  ‘H’ of CH3 – CH2 – NO2 is reactive but that
of CH3 – CH2 – NH2 is not. Why ?
Q.5 ? CH3–CH–NO CH3–CH–NO2 + H+
Sol.
|
H Stable due to
CH3 –I effect
O–H  H + H
CH3–CH–NH CH3–CH– N 2
Sol. N=N is obtained | unstable
H
So –H of CH3CH2NO2 is reactive.
CH3

NH2 O O
|| || 
Q.9 + CH–CH  ?
NH2

NITROGEN COMPOUNDS 14
 N CH CH3
 C 4 H 9O  K 
Sol. Q.13     ?
N CH NH–C–H  /  H 2O
||
O
CH
Q.10–11Suggest the mechanism of the following Sol. C–H
reactions- NH

Q.10 + CH3–CH2–CH2–CH2 Li   Q.14 Complete the reaction

N Acidic reagent
R – C – R'    
 ...........
||
NOH
  CH2–CH2–CH2–CH3 Sol. R–NH–C–R
N ||
O
Sol. Organolithiums give addition reaction across
C = N bond
s –s
Q.15 An aromatic organic compound on reduction
 
+ Li – C H 2 –CH2–CH2–CH3  gives (B) C7H9N. Diazotization of (B) and
N subsequent treatment with CuCN/KCN gives
H (C) C8H7N. Hydrolysis of (C) followed by

N CH2–CH2–CH2–CH3 oxidation forms (D) which has equivalent
|
Li weight 83. (D) forms only one mono
substitution product. What are (A), (B), (C)
and (D) ?
CH3 CH3

N CH2–CH2–CH2–CH3 Sol. (A) (B)

NO2 NH2

Q.11 + H–CCl3 NaOH

 CH3 COOH
N
| (C) (D)
H
O CN COOH
||
C–H Cl
+
N N Q.16 An organic compound (A) on treatment with
|
H acetic acid in presence of sulphuric acid
O
produces an ester (B). (A) on mild oxidation
O || gives (C). (C) with 50% KOH followed by
|| CH3–O–C
Q.12 NH2–C –NH2 + CH2 ? acidification with dilute HCl generates (A)
CH3–O–C and (D). (D) with PCl5 followed by reaction
||
O with ammonia gives (E). (E) on dehydration
produces hydrocyanic acid. Identify (A)
O
to(E).
N
Sol.
O N O
NITROGEN COMPOUNDS 15
 O O O O
|| || ||
Sol. (A) CH3 – OH (B) CH3 – C – O – CH3 C–CH3 C–CH3
(A) (B)
O O
|| ||
(C) H – C –H (D) H – C – O – H

O N O N O
|| || ||
(E) H – C – NH2 C–CH3 C–CH3
(C) (D)

Sol.[B]
Q.17 Compound (A) with empirical formula .. .. 

C7H9N on diazotization gives a product which O N N  N

OH OH2
undergoes Sand meyer’s reaction with Cu2Cl2 + +
H
H H –H2O
and HCl to give a compound (B). (B) on +H–N
oxidation gives a compound (C) which when
Tautomerism
heated with soda lime gives chlorobenzene.
Give the structure formula of (A), (B) and (C) O 
N ..
and explain the reactions involved. O N
C–CH3
CH3 + || HOH/H+ C–CH3
N O 
| CH3–C–Cl
Sol. (A) H
||
O
(Z) (X)
Therefore option (B) is correct
NH2
CH3

N
(B) ..
CH3–CH2–Br H2O
Q.19 P.

Cl
P will be–
COOH

(C) N NH2

CH2–CH3 CH2–CH3
Cl (A) (B)

Part-B Passage based Question O

CH2–CH3
Passage - I (Question 18 to 22) (C) (D) none of these
Stork enamine reaction
Secondary amines react with carbonyl compounds

to form enamines. Carbonyl compounds should N

N
have at least one--hydrogen atoms. Enamines

are good nucleophiles. The nucleophilicity of the CH2–CH3
Sol.[C] +CH3–CH2–Br 
carbon of enamine makes them particularly useful
reagents in organic synthesis–
O
O
O HOH/H+ CH2–CH3
|| + ..
H+ CH3–C–Cl H2O/
Q.18 +H–N X Y Z. N
[P] |
H
Z will be–
NITROGEN COMPOUNDS 16
 Therefore option (B) is correct.

Q.21 Choose the correct statement–

(A) Enamine acts a, b both nucleophile as
well as electrophile
N (B) Enamine has two nucleophilic centre
(C) Enamine has single nucleophilic centre
Q.20  A H
+ CH2=CH–CN  2O
 (D) Enamine can’t be acylated.
Sol.[B] Enamines are ambident nucleophile in which
B 
 C. B will be– nitrogen and carbon both are nuclephilic
O
centers.
CH2–CH=CNH
(A)
.. 
O N N
C
CH2–CH2–CN
(B)
nitrogen nucleophile carbon nucleophile

 Therefore option (B) is correct.

N
..
(C) CH2–CH=C=N
O



Q.22 + CH3–NH–CH3 H A
N
CH  CH – NO
2  2  B. B will be–
(D) CH2–CH2–CN O

(A) CH2–CH2–NO2
Sol.[A]
 CH3
CH3 N

.. (B) CH2–CH2–NO2

N N
 CH3
CH3 N
CH2–CH=C=N –..
+CH2=CH–CN O
(C) CH2–CH=N O–..
HOH
O
–..
O
O CH2–CH=N O–..
(D)
CH2–CH=C=NH
Sol.[C]
+
..
(B) N
H

CH2–CH2–C N

(C)

Therefore option (A) is correct.

NITROGEN COMPOUNDS 17
 CH3 .. CH3
O N Q.24 A mixture of m-deuterobenzamide and
Benzamide 15N is taken in Hofmann
H+
+ CH3–NH–CH3 degreadation–
[A] O
||
CH3 .. CH3 CH3 CH3 CONH2 C–15NH2

N N NaOBr
– O– + ?
O CH2–CH=N O– D
+CH2= CH–N
O What will be the product in this reaction.
[B] NH2 15
NH2
Therefore option (C) is correct
(A) &
D
Passage - II (Question 23 to 27) NH2 15
NH2
Hofmann degradation of amides has the special
feature to yielding a product containing one less (B) &
carbon than the starting material. This reaction is an D
example of intramolecular rearrangement. This (C) mix of
15 15
reaction is believed to proceed by the following NH2 NH2 NH2 NH2
steps–
O O , , &
|| .. .. || .. D D
–
(i) R–C– NH2 + OBr  R–C– N –Br + H2O
| (D) none of these
H O
O O || . . ..
(ii) || .. Br .. || .. CONH2 C– N
.. N =C=O
R–C– N + OH –  R–C– N .. –Br + H2O
Br
O O Sol.[A] +NaOBr
|| .. || .. ..– D D D
(iii) R–C–N–Br
.. R–C– N .. + Br +2OH
O NH2
|| .. ..
(iv) R–C– N..  R– N =C=O
+ CO 3–2
.. .. D
(v) R– N = C=O + 2OH R– NH2 + CO 3–2
–

Step III & IV occur simultaneously.

O 15
Q.23 What is the intermediate in the following
15 || . . 15
..
CONH2 C– N
.. N =C=O
reaction
O +NaOBr
||
CH3–C–NH2 NaOBr
  CH3–NH2
+2OH–
O O
|| ..  || .. 15
NH2
(A) CH3–C– N
.. – BrNa (B)CH3–C– N H –Br
O
|| .. + CO 3–2
(C) CH3–C– N.. (D) All
Sol.[D] All the given species are intermediate of the
Hofmann degradation of amides reaction Therefore option (A) is correct.
therefore option (D) is correct.

NITROGEN COMPOUNDS 18
Q.25 Hofmann degradation of optically active 
-phenyl propanamide gives– Q.27 The product obtained in 26 on heating give
(A) -phenylethylamine of same configuration lactam. The structure of lactam is–

(B) -phenyl ethylamine of inverted

confrguration (A)
(C) Racemic mix of -phenylethylamine
NH
(D) can’t be predicted O
CONH2 NH2 NH
| |
Sol.[A] C6H5 – C*– H NaOBr
C6H5 – C – H (B) CH3 CH3
| |
CH3 CH3 O
-phenyl -phenyl O
ethylamine CH3 H
propanamide
(C)
Hofmann rearrangement occurs with retention NH
of configuration when chiral carbon is directly (D) none of these
attached to the amide group. There fore product COOH NH2
NH
is formed same configuration. Sol.[B]
CH3  CH3
* CH3
Option (A) is correct.
H CH3 H O

COOH CONH2
Passage - III (Question 28 to 32)
..– Compounds capable of forming enol react with a
Q.26 CH3 OBr Product. C is–
mixture of aldehyde and a primary or secondary
H H amine in presence of an acid followed by
CH3
basification to give an aminoalkyl derivative,
COOH NH2
reaction takes place as follow.
Step I
(A) CH3

:O: O– H OH
H H || || ||
CH3 H–C–H+H+ H–C–H  H–C–H

COOH H
OH . .
|| NH 2– R 
(B) CH3 H–C–H R–NH–CH2–OH

|
H
H CH3 NH2 ..
R– NH – CH2– OH
(C) mix of A & B
(D) none of these .. .. H+ .. 
R– NH –CH2– O..H R– NH –CH2– O H 2
Sol.[A] 
R–NH–CH2
Step II
COOH CONH2 COOH NH2 O OH
|| |
–
OBr R–C–CH3 R–C=CH2
CH3 CH3 *
* enol
H CH3 H H CH3 H
Retention in configuration
Therefore option (A) is correct.
NITROGEN COMPOUNDS 19
 O–H
| 
.. .. 
R–C=CH2+CH2–NH–R 
 H+
.. H
CH3–CH2– NH –CH2– O CH3CH2NH–CH2–OH2

O .. 
|| CH3CH2– NH –CH2
R–C–CH2–CH2–NH–R
Step-II
Carbonyl compounds which undergo enolisation
give this reaction. A part from these compounds, H+
some other compounds like 2-methylpyridine also ..
N CH3 N CH2
give this reaction becouse these compounds |
undergo nitrogen-analogue of an enol in presence H
of acid. Step-III


H
CH2–H H 
N
.. N CH2
| + CH2–NH–CH2–CH3 
..
H N CH2 N N
|
Phenol, Furan, pyrrole, indole etc also give this H
reaction.
Q.28 What will be the product of following
reaction

(i ) H  Q.29 What is X in the following reaction

+CH2O+CH3–CH2–NH2  ..– P
CH3 ( ii ) OH
N
CH2O+(CH3)2NH
X
N
(A) |
N CH2–CH2–NH–CH2–CH3 H

(B) (A) CH
CH2–N CH3
N CH3 N 3
|
CH2–NH–CH2–CH3 CH
CH2–N CH3
(B) 3

(C) N
N N
(C)
(D) N
CH3 |
N CH2–N CH
CH3 CH2–N CH3
3
Sol.[C] Step –I (D) none of these
Sol.[D]

O O– H OH ..
|| H+ || || CH3CH2 NH2 H(active hydrogen)
H–C–H H–C–H  H–C–H

OH–
 + CH2O+(CH3)2NH
CH3–CH2–NH–CH2–OH N
 CH
CH2–N CH3
 3

N
[X]
..
CH3–CH2– N H –CH2–OH Therefore option (D) is correct.

NITROGEN COMPOUNDS 20
Q.30 What will be the product in the following O O
reaction || || (i) H+
O C–CH3+H–C–H + N
Q.31 ..– Z
| (ii) OH
H
+ CH2=O + (CH3–CH2)2NH What will be Z ?
O
(
i ) HCl
 P ||
(ii ) NaOH C–CH3–N
(A)
O

N–CH2–CH3 O
(A) ||
| C–CH2–CH2–N
CH2–CH3 (B)
O
CH2–CH3 C=N–
CH2–CH2–N (C) |
(B) CH2–CH3
CH3
O C=N–CH2–CH2–
CH2–CH3 (D) |
CH2–N CH3
(C) CH2–CH3
O
|| O
C–CH3 || (i) H+
CH2–CH3 Sol.[B] +H–C–H+ ..–
CH–N N (ii) OH
(D) CH2–CH3 |
H
Sol.[C] Step-I O

||
C–CH2–CH2–N
O OH OH
|| || |
H–C–H+H+ H–C–H  H–C–H
| CH2–CH3
.. CH2–CH3 N Therefore option (B) is correct.
NH  CH2–CH3
CH2–CH3
Q.32 Give the product of following reaction
–H+
O O O
|| || ||
OH CH3–C–CH2–C–CH3+CH3–C–H
| .. CH2–CH3
H–C– N 

| CH2–CH3 + H2N–CH3 (

i)H

( ii ) OH –
H
O O
H || ||
(A) CH3–C–CH2–C–CH2–CH2–NH–CH3

OH2 O O
| .. CH2–CH3 || ||
 CH2–CH3
CH2=N H–C– N (B) CH3–C–CH–C–CH3
CH2–CH3 CH2–CH3 |
| CH2–NH–CH3
H
Step-II O O
|| ||
(C) CH3–C–CH–C–CH3
O :OH |
N
H+  CH2–CH3 –H CH3 CH3
+ CH2=N CH –CH
2 3 O O
|| ||
O (D) CH3–C–CH–C–CH3
|
CH2–CH3 CH3–CH–NH–CH3
CH2–N
CH2–CH3 Sol.[D] Step-I

Therefore option (C) is correct.

NITROGEN COMPOUNDS 21
 O H O–
|| .. H | |
CH3–C–H + CH3– NH 2  N–C–CH3 
CH3 |
H
OH
H .. |
N –C–CH3
CH3 |
H
H


OH2
H  –H2O H .. |
N=CH–CH3 N –C–CH3
CH3 CH3 |
Imminium ion H

Step-II
O O
|| ||
OH + C C 
CH3 CH CH3
|
H O O
|| ||
CH3–C–CH–C–CH3+H2O

Step-III
O O
|| ||  H
CH3–C–CH–C–CH3 + CH3–CH=N
CH3

O O
|| ||
CH3–C–CH–C–CH3
|
CH3–CH–NH–CH3

Therefore option (D) is correct.

NITROGEN COMPOUNDS 22
 EXERCISE # 4
 IIT JEE objective questions Sol.[A] The reagent used in Hofmann bromamide
reaction is alkaline halogen (NaOH + X2)
Q.1 CH3NH2 + CHCl3 KOH
 Product, Product Therefore option (A) is correct.
is: [IIT - 2006]
Q.3 Rate determining step of reaction is :
 
(A) CH3– N C : (A) formation of (II)
..  (B) formation of (III)
(B) CH3– N
.. C: (C) formation of (IV)
(C) CH3 – NH – CH3 (D) formation of (VI)
(D) CH3 – C  N Sol.[C] Conversion of (III) to (IV) involing
 – rearrangement is the slowest step. Species (III)
Sol.[A] CH3–NH2 +CHCl3 3 KOH
 CH3– N  C + is electron deficient hence it has a tendency to
2KCl +3H2O get its octet completed by migration of alkyl
this reaction is also known as carbyl amine test. group.
Therefore option (A) is correct. Therefore option (C) is correct.

Passage (Q. 2 to 4) O O
15
The reaction sequence given below represents Q.4 –C–NH2 –C–NH2
Hoffmann bromamide reaction in which D
(A) (B)
RCONH2 is converted into R - NH2 : Products formed when mixture (A) and (B)
[IIT - 2006] undergo Hoffmann bromamide degradation ?
O O O –NH2
 (A) –NH2 +
C – NH2 C – NH–Br C – N–Br
D
15
–NH2 –NH2
Cl + +
–D
Cl Cl (III) 15
(I) (II) –NH2 –NH2
(B) +

H O D
NH2 N – C–O– N=C=O 15
–NH2 –NH2
(C) +

D
Cl Cl Cl 15
–NH2 –NH – D
(VI) (V) (IV) (D) +
Electron donating groups attached to phenyl
D
activates the reaction. The above reaction
Sol.[B] Since the reaction is intermolecular, no cross
sequence is interamolecular reaction.
product will be formed.
Q.2 The reagent used to convert (I) to (II) is :
(A) Br2/NaOH
(B) KBr/NaOH
(C) NBS
(D) KBr
NITROGEN COMPOUNDS 23
 CONH2 NH2 So the electrophile (NO2) attack only this

Br2
benzene ring at p-Position
(i) KOH
D D Therefore option (B) is correct.

15 15
CONH2 NH2
Q.6 Statement-1
Br2 Aniline on reaction with NaNO2/HCl at 0ºC
(ii) KOH
followed by coupling with -naphthol gives a
Therefore option (B) is correct. dark blue coloured precipitate.
and
Statement-2
Q.5. In the following reaction, The colour of the compound formed in the
reaction of aniline with NaNO2/HCl at 0ºC
[IIT - 2007]
followed by coupling with -naphthnol is due
O to the extended conjugation. [IIT-2008]
conc. HNO
cone
 3  X (A) Statement-1 is true, Statement-2 is true ;
N . H SO
H
2 4
Statement-2 is a correct explanation for
Statement-1
the structure of the major product ‘X’ is -
(B) Statement-1 is true, Statement-2 is true ;
O Statement-2 is not a correct explanation
(A)
NO2 for Statement-1
N
H (C) Statement-1 is true, Statement-2 is false
(D) Statement-1 is false, Statement-2 is true
NO2 O Sol.[D] Statement-1 is false, Statement-2 is true
(B)
N
H

O Q.7 Match each of the compounds in Column I

(C) with its characteristic reaction(s) inColumn II.
N
H
[IIT-2009]
NO2 Column I Column II
O (A) CH3CH2CH2CN (p) Reduction with
(D) H2/Pd-C
NO2 N
(B) CH3CH2OCOCH3 (q) Reduction with
H
SnCl2/HCl
Sol.[B] (C) CH3–CH=CH–CH2OH (r) Development of
foul smell on
treatment with
O
chloroform and
..
N CConc
  . HNO3

one. H SO alcoholic KOH
2 4
| (D) CH3CH2CH2CH2NH2 (s) Reduction with
H
Benzene ring disobutylaluminium
NO2
activated due hydride (DIBAL-H)
O
..
to N H - group .. (t) Alkaline hydrolysis
N
| Sol. A p, q, s, t ; B  p, s, t ; C  p ; D  r
H
Q.8 In the reaction [IIT-2010]
NITROGEN COMPOUNDS 24
 O (1) NaOH/Br2 O
H3C C T (C) C (r) Substitution reaction
O
NH2 (2) CH3
C
OH
Cl
1
.LiAlH 4
  CH
the structure of the product T is 
2.H 3O
CH3
O
(A) H3C C O (D) HS Cl (s) Coupling reaction
O– C
Base
 S

(t) Carbocation
NH Ntermediate
(B)
C CH3 Sol. A  r,s ; B  t; C  p,q; D  r
O

(C) H3C NH NaNO / HCl

Q.10 2 
C5H13N     Tertiary alcohol
C  N2
O
O + other products [IIT - 2005]
(D) H3C C O X is optically active. Find X and Y. Is
NH–C Y optically active ? write all intermediate steps.
C2H5
CH CH3
|
Sol. X= CH3 CH2 or CH3–C–NH2
Sol. [C] H3C NH |
NH2 CH
C
O H3C CH3
OH
|
Y = C2H5–C–CH3 (Y is optically inactive)
|
CH3
Q.9 Match the reactions in Column I with
appropriate options in Column II. [IIT-2010] Q.11 The major product of the following reaction
Column I Column II is - [IIT - 2011]
(A) (p) Racemic mixture O
N Cl+ 2 OH
C (i) KOH
NaOH / H 2 O NH
   C
0C
(ii) Br CH2Cl
O
N=N OH
O
C
OH OH (A) N–CH2 Br
C
H3C – C – C – CH3
(B) (q) Addition reaction O
CH3 CH3 O
O
C
C CH3 (B) N CH2Cl
C C
4  H3C
H2SO
 CH3
CH3 O

NITROGEN COMPOUNDS 25
 O treatment with NaNO2 in dill. HCl followed
C by addition to an alkaline solution of
(C) N -naphthol is [IIT - 2011]
N(CH3)2
O–CH2 Br

O
(A)
C NHCH3
(D) N

O CH2Cl (B)
O NH2

C KOH
Sol.. [A] NH
C (C) H3C
O CH2NH2
O O (D)
C  Cl–CH2– – Br C
NK N – CH2– –Br
C C
O O

Q.12 Amongst the compounds given, the one that

would form a brilliant colored dye on
NaNO2 + HCl (dil.)
Sol. [C] CH3 NH2 CH3 N2 Cl
0–5°C

OH
Alkaline solution

HO

CH3 N=N

Coloured dye

NITROGEN COMPOUNDS 26
 EXERCISE # 5
–
OH
 IIT JEE Subjective type questions +
(ii) CH3 = N
O–
Q.1 Carbyl amine test is performed in alc.KOH by
heating a mixture of- [IIT -1984]
(A) chloroform and silver powder Q.5 Complete the following with appropriate
(B) trihalogenated methane and a primary structures : [IIT - 1986]
amine NH2+ COCl base ?
(C) an alkyl halide and a primary amine
(D) an alkyl cyanide and a primary amine Sol. NH2 + COCl 

base

Sol. [B] trihalogenated methane and a primary amine  HCl

NH — CO
Q.2 State the conditions under which the
following preparation is carried out. Give the Q.6 Give a chemical test and the reagents used to
necessary equations which need not to be distinguish between the following :
balanced. “Ethylamine and diethylamine”. [IIT - 1988]
“Aniline from benzene” [IIT - 1983] Sol. Test with benzene sulphonyl chloride
Sol. Aniline from benzene : (C6H5SO2CI)

C6H6 Conc
 . HNO3
 C6H5NO2 Sn
/ 
HCl
 C6H5—NH2 Ethylamine (primary amine) forms N-ethyl
Conc. H 2SO 4
benzene sulphonamide which because of the
benzene nitrobenzene aniline presence of an acidic hydrogen on the N-
atom dissolves in KOH.
Q.3 How would you convert ? [IIT - 1985] On the otherhand, diethyl amine (secondary
“Aniline to chlorobenzene.” amine) forms N, N diethyl benzene
Sol. Aniline to chlorobenzene : sulphonamide which due to the absence of
N2Cl acidic hydrogen on N-atom does not dissolve
NH2
in KOH.
NaNO / HCl
 2
0 –5 ºC
benzene
aniline diazonium chloride Q.7 Arrange the following in increasing order of
Cl base strength : [IIT - 1988]
Cu 2 / Cl 2
methylamine, dimethylamine, aniline,
 
Sandmeyer N-methyl aniline.
reaction
Sol. Increasing order of base-strength :
Chlorobenzene
aniline < N-methylaniline < methyl aniline <
dimethyl aniline.
Q.4 For nitromethane molecule, write structure(s)
(i) showing significant resonance stabilisation
PCl NH
(ii) indicating tautomerism [IIT - 1986] Q.8 5  [C]  
C6H5COOH   3  [D]
O O P2O5 H / Hi
Sol. (i) CH3 – N CH3 – N   C6H5CN 2 [E] [IIT-91]

O O Sol. (C) CH3 – COCl
–
+ O + O O
or CH3 – N CH3 – N ||
O– O (D) CH3 – C – NH2
NITROGEN COMPOUNDS 27
 (E) CH3 – CH2 – NH2 (CH CO) O, heat
Q.14 CH3CH2NH2  3  2   (A) + (B)
[IIT - 98]
O O
Q.9 Compound ‘X’ containing chlorine, on || ||
Sol. CH3 – CH2 – NH – C –CH3 + CH3 –C – OH
treatment with NH3 gives a solid ‘Y’ which is
free from chlorine.(Y) analysed as C =
Br , Fe
49.31%, H = 9.59% and N = 19.17% and Q.15 CH3CONHC6H5 2 (A)+(B) [IIT-98]
reacts with Br2 and caustic soda to give a O
||
basic compound (Z), (Z) reacts with HNO2 to O NH–C–CH3
||
give ethanol. Suggest structures for (X), (Y) NH–C–CH3
and (Z). [IIT-92] Br
Sol. (A) (B)
O
|| Br
Sol. (X) CH3 – CH2 – C – Cl
O
||
(Y) CH3 – CH2 – C – NH2 Q.16 Dimethylamine is a stronger base than
(Z) CH3 – CH2 – NH2 trimethylamine. Why ? [IIT - 98]
Sol. Basicity  stability of cation
 degree of salvation.
Q.10 Complete the following [IIT-92] Degree of salvation of 1º amine and 2º amine is
P2O5 H almost same but degree of salvation of 3º amine
CONH2   A 
  (A)
 is very-very less i.e. almost zero.
CN COOH According to this 3º amine is lest basic therefor
dimethylamine is more basic then rimethyl
Sol. A, B, amine.

O
||
Q.11 N(CH3)2 + HNO2 ? [IIT - 92] Q.17 1. 2. 3.
N–C–CH3   
|
N(CH3)2 H
I
Sol. 4.
 NO2 [IIT - 99]
NO I
Sol. (1) HNO3 + H2SO4
Q.12 2, 4 Dinitroaniline NaNO and HCl at 5 º C
 2     (C) (2) H2O
anisole
(3) ICl + CH3 – COOH
[IIT - 95]
(4)NaNO2 + HCl and H3PO2
Sol. N=N O–CH3

NO2 NO2 Q.18 Compound A (C8H8O) on treatment with

NH2OH.HCl gives (B) and (C). (B) and (C)
Q.13 Write the structure of the foul-smelling rearrange to give (D) and (E), respectively, on
compound obtained when aniline is treated treatment with acid. (B), (C), (D) and (E) are
with chloroform in the presence of KOH. all isomers of mlecular formula (C8H9NO).
[IIT - 96] When (D) is boiled with alcoholic KOH an
NC oil (F) (C66H7N) separates out. (F) reacts
rapidly with CH3COCl to give back (D). On
Sol.
the other hand, (E) on boiling with alkali
followed by acidification gives a white solid
NITROGEN COMPOUNDS 28
 (G) (C7H6O2). Identify (A) to (G). [IIT - 99] Q.19 Write the structure of alanine at pH = 2 and
O pH = 10. [IIT - 2000]
||
C–CH3 Sol. (i) at pH = 2
Sol. (A) +
NH3
|
CH3–CH–COOH
(B) C6H5–C–CH3 (ii) at pH = 10
||
N–OH NH2
|
–
C6H5 CH3 CH3–CH– COO
C
(C) ||
N
HO Q.20 How would you bring about the following
(D) CH3–C–NH conversion (in 3 steps) ? [IIT - 2000]
||
O Aniline 
 Benzylamine
–
NH2 N 2 Cl CN
(E) C–NH–CH3 NaNO2 CuCN
|| Sol. HCl
O
(F) NH2 CH2–NH2
COOH
Sn+HCl

(G)
Benzylamine

NITROGEN COMPOUNDS 29