Nitro compound
Introduction: Organic compound having nitro(-NO2) group as
the functional group are called nitro compounds.
R-NO2 Ar-NO2
Where R is alkyl group Where Ar is aryl group
NO2 group can have two possible arrangement.
The NO2 group can be attached into the alkyl or aryl group through two
different atoms .i.e. oxygen and nitrogen atom. Hence NO2 group is an
example of ambident group.
Nomenclature: common name as well as IUPAC name of Nitroalkanes are
same. They are named by prefixing Nitro to the name of parent hydrocarbon.
Classification: Depending upon the type of carbon to which nitro
group is bonded, nitroalkanes are classified in to three types.
Primary Nitroalkane :
Secondary Nitroalkane:
Tertiary Nitroalkane:
• Nitrocompounds can also be classified in to aliphatic nitrocompound i.e.
nitroalkane and aromatic nitrocompound i.e. nitroarene.
Aliphatic nitrocompound:
R-NO2
Aromatic nitrocompound:
Ar-NO2
Isomerism
1. Chain isomerism : differ in the carbon chain
2 Position isomerism: differ in the position of the nitro group
[Link] isomerism: the nitro group is isomeric with the nitrite group.
General method of preparation of nitro compounds:
1. From haloalkanes: nitroalkane are obtained when alkyl halide are treated with
alcoholic solution of silver nitrite
• Potassium nitrite instead of silver nitrite gives alkyl nitrite.
• Aromatic nitro compound are not prepared by this method due to the less
reactivity of aryl halides towards nucleophilic substitution.
2. From alkane: Nitroalkane is prepared by heating alkane with fuming nitric
acid at 450-500oC
Physical properties :
1. Nitroalkanes are colourless liquid with a pleasant odour.
2. Lower member of nitroalkanes are sparingly soluble in water but
higher member are insoluble.
3. Nitrocompounds are highly polar and thus have strong
dipole-dipole interactions which cause them to have high boiling
point than hydrocarbons of comparable molecular mass.
Chemical properties:
Reduction: Nitro compounds are reduces to primary amines through the
following stages:
a) Catalytic reduction
Nitroalkanes on catalytic reduction with hydrogen in presence of Ni, pt give
primary amine.
b) Reduction in neutral medium:
Reduction of nitroalkanes with Zn/H2O or Zn/NH4Cl give
corresponding hydroxylamine.
c) Reduction in acidic medium
Both nitroalkanes can be reduced into corresponding amine by metal such as Sn,
Zn etc in the presence of conc. HCl
d) Reduction with Lithium aluminium hydride:
Nitroalkanes are reduced to 1o amines with LiAlH4.
Aromatic nitrocompounds (Nitrobenzene)
Preparation of nitrobenzene:
Nitrobenzene is prepared by heating benzene with conc. nitric acid in presence
of conc. Sulphuric acids up to 60oC
In this case, temperature should not exceed 60 oC. At temperature 80-100 oC
formation of m-dinitrobenzene takes place.
Physical properties:
1. Nitrobenzene is pale yellow oily liquid.
2. It boils at 210 oC and sp. gr. is 1.2.
3. It is highly toxic compound since its vapours are readily absorbed
through skin.
Chemical properties:
A. Reaction due to (-NO2) group (Reduction) :
a) Reduction in acidic medium:
The change takes place through the formation of nitrosobenzene and phenyl
hydroxylamine. They are very short lived species which can’t isolated in
acidic medium.
b) Reduction in neutral medium:
Reduction of nitrobenzene with Zn dust and water or Zn and NH4Cl gives
phenyl hydroxylamine. Nitrosobenzene is formed as intermediate product
which can’t be isolated.
c) Reduction in alkaline medium:
Nitrobenzene when reduces with zinc and sodium hydroxide (aq) gives
hydrazobenzene, zinc and sodium hydroxide(alc) gives azobenzene ,
alkaline sodium arsenite gives azoxybenzene.
In case of Zn/NaOH(aq) , first give nitrosobenzene and phenyl
hydroxylamine they rapidly reacts with azoxybenzene which reduces to
azobenzene and finally hydrobenzene.
d) Electrolytic reduction: nitrobenzene if reduced electrolytically in presence of
conc. H2SO4, phenyl hydroxylamine forms which undergoes intramolecular
rearrangement to yield p- aminophenol.
e) Catalytic reduction:
Nitrobenzene can be reduced catalytically into aniline with hydrogen in
presence of Ni or Pt or Pd catalyst.
Ni
h3H2
f) Reduction with lithium aluminium hydride: Nitrobenzene can be reduced
into azobenzene with lithium aluminium hydride.
Reaction due to benzene ring: nitro group is electron
withdrawing group (-I effect), it deactivates the benzene ring
towards electrophilic substitution reaction. Nitrobenzene
always gives the meta substituted product towards electrophilic
substitution reaction. Resonating structure shows, Positive
charge develops in ortho and para position results electron
density at meta position relatively higher than ortho and para
position.