Nitro compounds

The structure of the nitro group

Nitro compounds are organic compounds that contain one or more nitro functional
groups (-NO2). They are often highly explosive, especially when the compound
contains more than one nitro group. The presence of impurities or improper handling
can trigger a violent exothermic decomposition.

Aromatic nitro compounds are typically synthesized by the action of a mixture of

nitric and sulfuric acids on a suitable organic molecule. Some examples of such
compounds are trinitrophenol (picric acid), trinitrotoluene (TNT), and
trinitroresorcinol (styphnic acid). Chloramphenicol is a rare example of a naturally
occurring nitro compound.

1. Preparation
In organic synthesis various methods exists to prepare nitro compounds.

1.1. Aliphatic nitro compounds

• Nitromethane adds to aldehydes in 1,2-addition in the nitroaldol

reaction
• Nitromethane adds to alpha-beta unsaturated carbonyl compounds as a
1,4-addition in the Michael reaction as a Michael donor
• Nitroethylene is a Michael acceptor in a Michael reaction with enolate
compounds
 • In nucleophilic aliphatic substitution sodium nitrite (NaNO2) replaces
an alkyl halide. In the so-called ter Meer reaction (1876) named after
Edmund ter Meer.

the reactant is a 1,1-halonitroalkane:

In one study, a reaction mechanism is proposed in which in the first slow step a
proton is abstracted from nitroalkane 1 to a carbanion 2 followed by isomerization to
a sodium nitronate 3 and finally nucleophilic displacement of chlorine based on an
experimentally observed kinetic isotope effect of 3.3. When the same reactant is
reacted with potassium hydroxide the reaction product is the 1,2-dinitro dimer

1.2. Aromatic nitro compounds

• In electrophilic substitution, nitric acid reacts with aromatic

compounds in nitration.
• A classic method starting from halogenated phenols is the Zinke
nitration.

2. Reactions
Nitro compounds participate in several organic reactions.

2.1. Aliphatic nitro compounds

• Aliphatic nitro compounds are reduced to amines with hydrochloric

acid and an iron catalyst
• Nitronates form by adding acids to nitro salts.
• Hydrolysis of the salts of nitro compounds yield aldehydes or ketones
in the Nef reaction

2.2. Aromatic nitro compounds

• Reduction of aromatic nitro compounds with hydrogen gas over a

platinum catalyst gives anilines.
• The presence of nitro groups facilitates nucleophilic aromatic
substitution.

3. Nitration
Nitration is a a general chemical process for the introduction of a nitro group into a
chemical compound. Examples of nitrations are the conversion of glycerin to
nitroglycerin and the conversion of toluene to trinitrotoluene. Both of these
conversions use nitric acid and sulfuric acid.

3.1. Aromatic nitration

In "aromatic nitration," aromatic organic compounds are nitrated via an electrophilic
aromatic substitution mechanism involving the attack of the electron-rich benzene
ring by the nitronium ion. Alternative mechanisms have also been proposed, as the
one involving single electron transfer (SET). Aromatic nitro compounds are important
intermediates to anilines by action of a reducing agent. Benzene is nitrated by
refluxing with concentrated sulfuric acid and concentrated nitric acid at 50 °C.

2 H2SO4 + HNO3 → 2 HSO4- + NO2+ + H3O+

C6H6 + NO2+ → C6H5NO2 + H+
H+ + H3O+ + 2 HSO4- → H2O + 2H2SO4

The sulfuric acid is regenerated and hence acts as a catalyst. It also absorbs water.

Nitration of benzene

The formation of a nitronium ion (the electrophile) from nitric acid and sulfuric acid
is shown below:

Reaction of nitric acid and sulfuric acid

- Scope

Selectivity is always a challenge in nitrations, The nitration of fluorenone is selective

and yields a tri-nitro compound or tetra-nitro compound by modifying reaction
conditions. Another example of trinitration can be found in the synthesis of
phloroglucinol.

Other nitration reagents include nitronium tetrafluoroborate, a nitronium salt. This

compound can be prepared from hydrogen fluoride, nitric acid, and boron trifluoride.

The substituents on aromatic rings affect the rate of this electrophilic aromatic
substitution. Deactivating groups such as other nitro groups have an electron-
withdrawing effect. Such groups deactivate (slow) the reaction and directs the
electrophilic nitronium ion to attack the aromatic meta position. Deactivating meta-
directoring substituents include sulfonyl, cyano groups, keto, esters, and carboxylates.
Nitration can be accelerated by activating groups such as amino, hydroxy and methyl
groups also amides and ethers resulting in para and ortho isomers.

The direct nitration of aniline with nitric acid and sulfuric acid, according to one
source results in a 50/50 mixture of para and meta nitroaniline. In this reaction the
fast-reacting and activating aniline (ArNH2) is in equilibrium with the more abundant
but less reactive and deactivating anilinium ion (ArNH3+), which may explain this
reaction product distribution. According to another source a more controlled nitration
of aniline starts with the formation of acetanilide by reaction with acetic anhydride
followed by the actual nitration. Because the amide is a regular activating group the
products formed are the para and ortho isomers. Heating the reaction mixture is
sufficient to hydrolyze the nitroamide back to the nitroamine.

In the Wolfenstein-Boters reaction, benzene reacts with nitric acid and mercury nitrate
to give picric acid.

4. 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.

4.1. Aliphatic nitro compounds

4.1.1. Reduction to hydrocarbons

Hydrodenitration (replacement of a nitro group with hydrogen) is difficult to achieve,

but can be completed by catalytic hydrogenation over platinum on silica gel at high
temperatures.
4.1.2. Reduction to amines

Aliphatic nitro compounds can be reduced to aliphatic amines using several different
reagents:

• Catalytic hydrogenation using platinum oxide (PtO2) or Raney nickel

• Iron metal in refluxing acetic acid
• Samarium diiodide

α,β-Unsaturated nitro compounds can be reduced to saturated amines using:

• Catalytic hydrogenation over palladium-on-carbon

• Iron metal
• Lithium aluminium hydride[6] (Note: Hydroxylamine and oxime
impurities are typically found.)

4.1.3. Reduction to hydroxyl amines

Aliphatic nitro compounds can be reduced to aliphatic hydroxylamines using

diborane.

4.1.4. Reduction to oximes

Nitro compounds are typically reduced to oximes using metal salts, such as stannous
chloride or chromium(II) chloride. dditionally, catalytic hydrogenation using a
controlled amount of hydrogen can generate oximes.

4.2. Aromatic nitro compounds

The reduction of aryl nitro compounds can be finely tuned to obtain a different
products typically in high yields.

4.2.1. Reduction to anilines

Many methods for the production of anilines from aryl nitro compounds exist, such
as:

• Catalytic hydrogenation using palladium-on-carbon, platinum oxide, or

Raney nickel
• Iron in acidic media (Note: Iron is particularly well suited for this
reduction as the reaction conditions are typically gentle and also because iron
has a high functional group tolerance.)
• Sodium hydrosulfite
• Sodium sulfide (or hydrogen sulfide and base)
• Tin(II) chloride
• Titanium(III) chloride
• Zinc

It is also possible to form a nitroaniline by reduction of a dinitroarene using sodium

sulfide.

Metal hydrides are typically not used to reduce aryl nitro compounds to anilines
because they tend to produce azo compounds.

4.2.2. Reduction to hydroxylamines

Several methods for the production of aryl hydroxylamines from aryl nitro
compounds exist:

• Raney nickel and hydrazine at 0-10 °C

• Electrolytic reduction
• Zinc metal in aqueous ammonium chloride

4.2.3. Reduction to hydrazo compounds

Treatment of nitroarenes with excess zinc metal results in the formation of N,N'-
diarylhydrazine.

4.2.4. 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.)