UNIT

14
0
NITROCOMPOUNDS
NEB Syllabus:

14.1 Aliphatic Nitrocompounds ( Nitroalkane):

 Introduction and nomenclature
 Preparation of nitroalkane from haloalkane and alkane
 Physical properties of nitroalkane
 Reduction of nitroalkane
 Uses
14.2 Aromatic Nitrocompounds:
 Laboratory preparation of nitrobenzene
 Physical properties
 Chemical properties
 Reduction in different media
 Electrophilic substitution reactions
 Uses of nitrobenzene

Nitrocompounds:
Organic compounds containing nitro (-NO2) group as the functional group are called nitro compounds. These
are formed by replacing the hydrogen atom of the hydrocarbon by nitro group
+ NO2
R-H R - NO2
-H
Alkane Nitrocompound

There are two isomeric forms of -NO2 group. These are

and –O–N=O
(I) (II)
The first (I) is nitro group which is linked with carbon of alkyl group through nitrogen. But the structure (II),
which is linked with carbon of alkyl group through oxygen atom, is called the nitrite group.
Classification of nitro compounds
Depending upon the hydrocarbon part to which a nitro group is attached, nitro compounds are classified into
two groups-
i) Aliphatic nitro compounds:
In these compounds nitro group is attached to alkyl (R-) group. Examples are

CH3 - NO2 CH3 - CH2 - NO2 etc.

Nitromethane Nitroethane

1 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075
 These are called nitroalkanes and are represented by R - NO2. Nitroalkanes are further classified as primary
(1°), secondary (2°) and tertiary (3°) nitro alkanes depending upon the degree of carbon atom to which nitro
group is attached.
R
R - CH2 - NO2 R - CH - NO2 R - C - NO2
R R
Primary nitroalkane Secondary nitroalkane Tertiary nitroalkane
ii) Aromatic nitro compounds.
Nitro compounds containing one or more aromatic rings are aromatic nitro compounds. If aromatic group is
directly attached to -NO2 group, these compounds are called nitroarenes (Ar-NO2)

NO2 NO2 NO2

NO2
CH3
Nitrobenzene 1, 3-dinitrobenzene
P-nitrotoluene

The compounds in which nitro group is attached to the side chain are phenyl derivatives of nitroalkanes.

Nomenclature
Nitro compounds are named by adding the prefix nitro before the name of corresponding hydrocarbon. The
position of nitro group is indicated by the serial number of carbon atom to which -NO2 group is attached.
CH3-NO2 CH3-CH2-NO2 CH3-CH2-CH2-NO2 CH3- CH-CH3
Nitromethane Nitroethane 1-nitropropane |
NO2
2-nirtropropane

NO2 NO2 CH3 CH3

NO2 O2N NO2

NO2

1, 3-dinitrobenzene 2-nitrotoluene NO2

Nitrobenzene (m-dinitrobenzene) (O-nitrotoluene) 2, 4, 6 - trinitrotoluene (TNT)

General methods of preparation of aliphatic nitro compounds

1) From haloalkanes
When haloalkanes are treated with alcoholic solution of silver nitrite, nitroalkanes are obtained.

CH3 – CH2 - I + AgNO2(alc.) 

 CH3 – CH2 - NO2 + AgI

Iodoethane Nitroethane

2 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075
 Note: Due to less electropositive nature of silver, AgNO2 has covalent character and nitrogen atom has lone pair of electron.
So, nucleophilic substitution reaction takes place with haloalkane due to presence of this lone pair. That is why
nitrogen atom goes to be attached with alkyl group in this reaction.
O
..  
Ag - O - N = O + R X R - N = O + AgX
Nitroalkane
But, if NaNO2 is used, alkyl nitrite will be produced because NaNO2 is ionic compound and -NO2 group is
attached through oxygen atom.

2) From nitration of hydrocarbon: When hydrocarbons are heated with nitric acid at 500oC, nitro
compounds are formed.

CH3 – CH3 + HNO3 (fuming) 500

 c 
 CH3 – CH2 - NO2 + H2O

Properties of Nitro compounds

1) State, colour and odour:

Nitroalkanes are colourless liquids with a pleasant odour
2) Solubility:
Nitroalkanes are slightly soluble in water but are soluble in organic solvents.
3) Boiling points:
Nitro compounds are polar in nature (dipole moment = 3.6 D). Due to strong dipole-dipole interactions,
these compounds show higher boiling points than the hydrocarbons of comparable mass.

Chemical properties
1. Reduction: Reduction of nitro compounds can be carried out in different conditions.
a) Catalytic reduction: Primary amines (R- NH2) are produced when nitroalkanes are reduced by
hydrogen gas in presence of catalyst Ni or Pt.
Ni or Pt
R - NO2 + H2 R - NH2 + H2O

Nitroalkane 1o amine
Ni or Pt
CH3 - CH2 - NO2 + H2 CH3 - CH2 - NH2 + H2O

Nitroethane Ethanamine
b) Reduction in acidic medium
Nitroalkanes are reduced into the corresponding amine by metals such as Zn, Sn, Fe etc. in presence of
HCl.

R - NO2 + 6[H] Sn

 / HCl

 R - NH2 + 2H2O
Nitroalkane 1°amine

CH3 – CH2 - NO2 + 6[H] Sn

 / HCl

 CH3 - CH2 - NH2 + 2H2O
Nitroethane Ethanamine

3 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075
 c) Reduction with LiAlH4
Nitrocompounds are reduced to primary amine with LiAlH4.
LiAlH4
R - NO2 + 6[H] R -NH2 + 2H2O
nitroalkane 1o amine

CH3 - CH2 - NO2 + 6[H] LiAlH4

CH3 -CH2 -NH2 + 2H2O
nitroethane ethanamine
d) Reduction in neutral medium
Reduction of nitro compounds with Zn/H2O or Zn/NH4Cl gives corresponding hydroxylamine.
Zn / NH4Cl
R - NO2 + 4[H] R -NH - OH + H2O
N-alkylhydroxyl amine
Zn / NH4Cl
C2H5 NO2 + 4[H] C2H5 -NH-OH + H2O
N-ethylhydroxyl amine

2) Reaction with nitrous acid, HNO2 (NaNO2 + HCl)

 Primary nitroalkanes react with nitrous acid to form nitrolic acid which gives blood red colouration
with aqueous alkali.
 NaOH (aq)
R–CH2–NO2 + HNO2 
 R–C–NO2   R–C–NO2
1° niroalkane nitrous acid || ||
N - OH N–ONa
nitrolic acid Sodium nitrolate (blood red)

 Secondary nitroalkanes react with nitrous acid to form pseudonitrol which gives blue colouration with
aq. alkali.
N=O
|
aq.NaOH
R–CH - NO2 + HNO2 
 R - C - NO2  Blue colour
| |
R R
2° nitroalkane Pseudonitrol
 Tertiary nitroalkanes don't react with nitrous acid due to absence of replaceable hydrogen atom and
give no coloration with aq. NaOH.

Summary of preparation and chemical properties

Methods of Preparation Chemical Properties
Sn / HCl
CH3 – CH2 – NH2
ethanamine
AgNO2
CH3 – CH2 – I Zn / NH4Cl
CH3 – CH2 – NH – OH
(iodoethane)
N-ethyl hydroxyl amine
CH3 – CH2 – NO2
Nitroethane H2 / Ni
HNO3 CH3 – CH2 – NH2
CH3 – CH3
400°C ethanamine
(ethane)
LiAlH4
CH3 – CH2 – NH2
ethanamine

4 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075
 Uses of nitroalkanes
1. Lower members of nitroalkanes are used as solvents for fats, waxes, dyes etc.
2. They are used to prepare amines, dyes, explosives etc.

Aromatic Nitro compound:

Nitrobenzene:
Laboratory preparation of nitrobenzene
Principle:
In lab, nitrobenzene is prepared by heating benzene with conc. HNO3 in presence of conc. H2SO4 at
60oC.
NO2

Conc. H2SO4 + H2O

+ HNO3
conc. 60oC

Benzene Nitrobenzene

Mechanism of nitration:

1) Formation of electrophile NO2+ ( Nitronium ion):

HNO3 (conc.) + H2SO4 (conc.) NO2+ + HSO4- + H2O

Nitronium ion
2) Formation of carbocation:

H NO2 H NO2 H NO2 H NO2

+ NO2+ +

Benzene Resonance hybrid

3) Formation of nitrobenzene:

H NO2 NO2

+ HSO4- + H2SO4

Nitrobenzene

The temperature should not exceed 60°C because at higher temperature ( 80°C - 100°C ) m-dinitrobenzene is
formed
NO2

Conc. H2SO4 + H2O

+ HNO3
conc. 90oC
NO2
Benzene m- dinitrobenzene

5 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075
 Figure: Lab preparation of nitrobenzene

Procedure:
60ml Conc.HNO3 and 60 ml Conc. H2SO4 are taken in RB flask. About 50 ml of benzene is gradually
added to the flask, a little at a times with shaking and cooling after each addition. When the all benzene is
added, the mixture is refluxed on a water bath at 60oC about one and half hour till yellow oily layer appears
on surface with bitter almond smell.

Purification:
The upper layer is separated by separating funnel. It is washed with aq. Na2CO3 to remove acidic
impurities then with water several times and dried over anhydrous CaCl2 it is finally redistilled at around
208oC to 212oC to obtain pure nitrobenzene.

Figure: purification of nitrobenzene

6 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075
 Physical properties
1) Nitrobenzene is a pale yellow oily liquid with bitter almond smell.
2) It boils at 210°C and its specific gravity is 1.2
3) It is insoluble in water and soluble in organic solvents.
4) It is a toxic compound since its vapours are absorbed through skin.

Chemical properties
1) Reduction of Nitrobenzene
The nitrobenzene is reduced to different products in different mediums.
a) Reduction in acidic medium
In acidic medium i.e. by HCl and metals like iron, tin or zinc, nitrobenzene is reduced to aniline.

NO2 NH2
Sn/HCl
+6[H] +2H2O

Nitrobenzene Aniline

b) Reduction in neutral medium

Nitrobenzene is reduced to N-phenyl hydroxyl amine in neutral medium by using Zn/H2O or
Zn/NH4Cl

NO2 NH - OH
Zn/NH4Cl
+ 4[H] + H2O

nitrobenzene N-phenyl hydroxyl amine

C) Reduction in alkaline medium

In alkaline medium, nitrobenzene gives different bimolecular reduction products depending upon the
nature of reducing agent used.

Zn/NaOH(aq) H H
2 NO2 + 10[H] N N + 4 H2O

Nitrobenzene hydrazobenzene

Zn/NaOH in CH3OH
2 NO2 + 8[H] N N + 4 H2O

Nitrobenzene azobenzene
O
Na3AsO3/NaOH(aq)
2 NO2 + 6[H] N N + 3 H2O
glucose / NaOH
Nitrobenzene azoxybenzene

7 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075
 Mechanism:

Zn/NaOH 2[H]
NO2 + 2 [H] N=O NH - OH

Nitrobenzene Nitrosobenzene Phenyl hydroxyl amine

N=O O H H
2[H] 2[H]
+ N=N N=N N= N
- H2O - H2O

NH - OH Azoxybenzene Azobenzene Hydrazobenzene

d) Electrolytic reduction:

When nitrobenzene is reduced electrolytically in presence of acid, p-amino phenol is formed.

NO2 NH2
Electrolytic reduction
+ 4[H] + H2O
H+
nitrobenzene OH
p - aminophenol

e) Catalytic reduction:

Nitrobenzene is reduced to aniline by hydrogen in the presence of Ni or Pt.

NO2 NH2
Ni or Pt
+ 3H2 + 2H2O

nitrobenzene aniline

f) Reduction with LiAlH4:

Nitrobenzene is reduced to azobenzene with LiAlH4.

LiAlH4
2 NO2 + 8 [H] N N + 4 H2O

Nitrobenzene azobenzene

2. Electrophilic substitution in benzene ring.

The nitro group attached to aromatic ring is electron withdrawing group. It is meta-directing and ring
deactivator towards electrophilic substitution. This can be shown by resonance structures of
nitrobenzene.

 O

O O O O O O O O O O
O
N N N N
N N
 


Resonating structure of nitrobenzene Resonance hybrid

8 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075
 In ortho and para positions, positive charge is developed. So, meta position contains more electron
density than ortho and para positions. Therefore, nitrobenzene undergoes electrophilic substitution on
meta-position.

NO2

Cl2 / FeCl3 + HCl [Halogenation]

Cl
m-chloronitrobenzene

NO2
conc. H2SO4
+ H2O [Sulphonation]
NO2 
SO3H
m-nitrobenzenesulphonic acid

NO2

conc. HNO3/conc. H2SO4 + H 2O [Nitration]

o
90 C NO2
m-di nitrobenzene
NO2
conc. HNO3/conc. H2SO4
+ H2O [Nitration]
100oC
O2N NO2
1,3,5- trinitrobenzene

Note: The ring of nitrobenzene is deactivated by electron withdrawing nitro group. So, the Friedel–craft’s
reaction doesn't take place since only the activated aromatic ring shows this reaction.
Uses
Nitrobenzene is used
1. for the manufacture of aniline and large number of dye stuffs.
2. for making shoe-polishes
3. as an oxidizing agent in organic synthesis
4. for scenting soaps.

9 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075
 Summary of chemical properties:
Sn / HCl
NH2

aniline
Zn / NH4Cl
NH - OH

phenyl hydroxyl amine

Zn/NaOH,CH3OH N N

azobenzene
H H
Zn /NaOH(aq)
N N

hydrazobenzene
O
Na3AsO3 / NaOH(aq)
N N

azoxybenzene
Electrolytic reduction HO NH2
+
H
p-amino phenol
NO2 LiAlH4
N N

azobenzene

Nitrobenzene H2 / Ni or Pt
NH2

aniline
Cl2 / FeCl3
NO2

Cl
m-chloro nitrobenzene
conc. HNO3
NO2
conc. H2SO4 90oC
O2N
m-di nitrobenzene
O2N
conc. HNO3 (fumming)
NO2
conc. H2SO4 ,100oC
O2N
1,3,5-trinitrobenzene
conc. H2SO4
 NO2

HO3S
m-nitrobenzene sulphonic acid

10 | Page © Jay Prakash Paudel / Jaya Ram Ghimire / Department of Chemistry || Uniglobe SS/College -2075