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Reduction of Submitted to

nitro
compounds Maam tooba

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chem-18140
,141,142,159,166
 Reduction of nitro compound
content
1 introduction
2 Aromatic nitro compounds
▪ Reduction to anilines
▪ Reduction to hydroxylamines
▪ Reduction to hydrazino compounds
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3 Aliphatic nitro compounds

▪ Reduction to hydrocarbons
▪ Reduction to amines
▪ Reduction to hydroxylamines

4 Rererence
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Introduction Nitro compounds

▪ Organic compounds containing nitrogen can be broadly classified into

two groups.

▪ Compounds containing nitro functional group - NO2

▪ Compounds containing amine functional group - NH2 and their

derivatives.

▪ In this nitro compounds are primary source of organic compounds with

functional group -NO2 to start the synthesis of many other important
compounds Nitro Compound
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Reduction of nitro compounds

▪ The chemical reactions described as reduction of nitro

compounds can be facilitated by many different reagents and reaction
conditions. Historically, the nitro group was one of the first functional
groups to be reduced, due to the ease of nitro-group reduction.

▪ Nitro-groups behave differently whether a neighboring hydrogen is

present or not. Thus, reduction conditions can be initially classified by
starting materials: aliphatic nitro compounds or aromatic nitro
compounds. Secondary classifications are based upon reaction
products.
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Aromatic Nitro-
compounds.

Compounds in which nitro group

( -NO 2) is directly bonded to
benzene (aromatic) ring are called
aromatic nitro compounds or
simply nitroarenes. These are
also regarded as nitro derivatives
of arenas.
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Reduction to anilines

▪Nitrobenzene is given as
the product. Nitrobenzene is
reduced to aniline by Sn and
concentrated HCl. Instead of
Sn, Zn or Fe also can be
used. Aniline salt is given
from this reaction. Then
aqueous NaOH is added to
the aniline salt to get
released aniline. Aniline salt
has weak acidic
characteristics. Therefore it
reacts with strong alkalis
such as NaOH, KOH and
release aniline.
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Reduction to hydroxylamines
▪ Hydroxylamine (NH 2 OH), or hydroxylamines (R-NHOH)
can be reduced to amines. Hydroxylamine explodes with heat:
The high reactivity comes in part from the partial
isomerisation of the NH 2 OH structure to ammonia oxide
(also known as azane oxide), with structure NH 3+ O

▪ Several methods have been described for the production of

aryl hydroxylamines from aryl nitro compounds:

• Raney nickel and hydrazine at 0-10 °C

• Electrolytic reductionZinc metal in aqueous ammonium

chloride

• Catalytic Rhodium on carbon with excess hydrazine

monohydrate at room temperatur
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Reduction to hydrazino compounds

▪ Treatment of nitroarenes with excess zinc metal results in the

formation of N,N'-diarylhydrazine

▪ Hydrazine is the most common and effective reducing agent used

to convert graphene oxide (GO) to reduced graphene oxide
(rGO) via hydrothermal treatment. Hydrazinium salts. Hydrazine
can be monoprotonated to form various solid salts of the
hydrazinium cation (N 2 H 5 +) by treatment with mineral acids
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Reduction to azo compounds

▪ Treatment of aromatic
nitro compounds with
metal hydrides gives
good yields of azo
compounds. For example,
one could use:

• Lithium aluminium
hydride Zinc metal
with sodium hydroxide
(Excess zinc will reduce
the azo group to a
hydrazino compound.
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Aliphatic nitro compounds

Reduction to hydrocarbons

▪ Hydrodenitration (replacement of a
nitro group with hydrogen) is
difficult to achieve but can be
effected by catalytic hydrogenation
over platinum on silica gel at high
temperaturesThe reaction can also be
effected through radical reaction
with tributyltin hydride and a radical
initiator, AIBN as an example
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Reduction to amines

▪Aliphatic nitro compounds can be reduced to

aliphatic amines by several reagents:
▪Catalytic hydrogenation using platinum(IV) oxide (PtO2
or Raney nickel
▪Iron metal in refluxing acetic acid
▪Samarium diiodide[
▪Raney nickel, platinum on carbon, or zinc dust
and formic acid or ammonium formate

▪α,β-Unsaturated nitro compounds can be

reduced to saturated amines by:

▪Catalytic hydrogenation over palladium-on-carbon

▪Iron metal
▪Lithium aluminium hydride
▪Lithium borohydride or sodium
borohydride and trimethylsilyl chloride
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Reduction to hydroxylamines

▪ Aliphatic nitro compounds

can be reduced to
aliphatic hydroxylamines usin
g diborane.

The reaction can also be carried

out with zinc dust
and ammonium chloride
R-NO2 + 4 NH4Cl + 2 Zn → R-
NH-OH + 2 ZnCl2 + 4
NH3 + H2O
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Reduction to oximes

▪ Nitro compounds are

typically reduced
to oximes using metal
salts, such as stannous
chlorideor chromium(II)
chloride Additionally,
catalytic hydrogenation
using a controlled amount
of hydrogen can generate
oximes.
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References

▪ Gerald Booth (2007). "Nitro Compounds, Aromatic". Ullmann's Encyclopedia of Industrial

Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_411.

▪ Allen, C. F. H.; VanAllan, J. (1955). "2-Amino-p-cymene". Organic Syntheses.; Collective

Volume, 3, p. 63

▪ Bavin, P. M. G. (1973). "2-Aminofluorene". Organic Syntheses.; Collective Volume, 5, p. 30

▪ Smith, Michael B.; March, Jerry (2007). March's Advanced Organic Chemistry (6th ed.). John
Wiley & Sons. p. 1816

▪ Bigelow, H. E.; Robinson, D. B. (1955). "Azobenzene". Organic Syntheses.; Collective Volume

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