AMINATION BY REDUCTION

Introduction and definition

Amination by reduction involves the synthesis of amines by
reductive methods.

Amines may be defined as derivatives of ammonia, where one

or more of the hydrogens are replaced by alkyl, aryl, hydro aryl
(cycloalkyl),aralkyl, or heterocyclic groups.

Amines can be produced by reducing nitro, nitroso, hydroxyl

amino, azoxy, azo, and hydrazo compounds, as well as oximes ,
amides, nitriles, and azides. In each case, a carbon-to-nitrogen
bond already exists.

Amines may also be formed by reacting compounds containing

certain labile groups (e.g., halogens, hydroxyl and sulfonic) with
ammonia.
 Types of amines
Amines are divided into three classes-
primary, secondary, and tertiary,

Depending upon the number of replaced hydrogens

in the parent substance ammonia.

Primary amines contain two remaining hydrogen

atoms attached to the ammonia nitrogen, secondary
amines contain one, and tertiary amines have none
remaining.
 Amides & imides
Amides are derivatives of ammonia, where‘ the
hydrogens has been replaced by an organic acid-
derived group, aroyl, heteroyl, sulfonyl, etc.

An imide is one in which two hydrogen of the

parent ammonia have been replaced by two acyl
groups.
 Preparation of amines
Amides are generally prepared by ammonolysis reactions and not by
reductive methods. The methods generally used for the preparation of
primary amines are the following:
1. The reduction of nitro, nitroso, hydroxylamino, azoxy, azo, and hydrazo
compounds.
2. The reduction of nitriles, amides, oximes, and azides.
3. The replacement of labile groups, such as nitro, halogen, hydroxyl, and
sulfonic acid by reaction with ammonia or ammonia progenitors, such as
urea.
4. Intramolecular rearrangement of (a) hydrazobenzenes and hydroxylamines,
(b) amides, and (c) secondary and tertiary amines.
5. The hydrolysis of N-substituted amides.
6. Direct amination by means of hydroxylamine and sulfuric acid.
 Amines: occurrence and importance
• Amines occur
• as gases (methyl amine: BP, - 6. 7°C),
• liquids (aniline: BP,184°C),
• and solids (naphthyl amine: MP, 50°C).
• Amines are of very great importance as intermediates
in the chemical process industries.
• They are used in the production of dyes, rubber
chemicals, nylon, pharmaceuticals, gasoline additives,
surfactants, textileauxiliaries, photographic chemicals,
chelating agents, sweetening agents, agricultural
chemicals, polyurethanes, inks, plastics, etc.
 METHODS OF REDUCTION
Among the methods are:
1. Metal and acid. Iron and acid (Bechamp method) is the
major example in this category, but other metals (tin, zinc)
have also been employed. Generally, hydrochloric acid is
preferred, but sulfuric, acetic, and formic acids have also been
used.
2. Catalytic. This method involves the use of hydrogen (or
hydrogen containing gases) and a catalyst such as nickel,
copper, platinum, palladium, or molybdenum sulfide.
3. Sulfide. This is used mainly for the partial reduction of
polynitroaromatic compounds to nitroamines and for the
reduction of nitroanthraquinones to aminoanthraquinones.
4. Electrolytic.
5. Metal and alkali. This method is used mainly for the
production of azoxy, azo, and hydrazo compounds. The
latter are important in the manufacture of the benzidine
series.
6. Sodium hydrosulfite (hyposulfite).
7. Sulfite (Piria method). The reaction of sodium sulfite
and bisulfite on an aromatic nitro compound leads to a
mixture of amine and amino-aryl sulfonic acid.
8. Metal hydrides.
9. Sodium and sodium alcoholate.
10. Strong caustic oxidation reduction.
11. Hydrogenated quinolines and naphthalenes.
By selection of reducing agent and careful regulation of the process,
reductions may often be stopped at intermediate stages and valuable
products other than amines obtained.

Metal and acid reductions are most vigorous and usually yield amines
as end products.

When nitrobenzene is treated with zinc and a mineral acid, the

resultant product is aniline.

When an alkaline solution is employed, hydrazo-benzene is generally

obtained, but very vigorous conditions sometimes result in the
formation of aniline.

When zinc dust and water are used, the reaction product is phenyl-
hydroxyl amine.
 Reduction of nitrocompounds
The reduction of nitro compounds involves the
progressive removal and replacement by
hydrogen of the oxygen in the -NO2 group.

The intermediate products in the reduction of

nitrobenzene, are obtained by control of the
reduction potential of the system.
 Reaction Mechanism
Chemical Mechanism. The aryl amines, in contrast
to the alkylamines,dissociate on solvation only to a
slight extent, forming weak bases.

The salts of aromatic amines (e.g., aniline

hydrochloride) are thus and easily hydrolyzed. It is
this hydrolysis of the amine salt that gives the acidic
medium in which the reduction takes place. The
degree to which this hydrolysis occurs determines
the treatment given the final reducer charge prior
to isolation of the amine.
Hydrogen is evolved when iron powder and water
are intimately mixed. This reaction is greatly
accelerated by heating in the presence of salts
derived from strong acids.

When a nitro compound is introduced into such a

system, the hydrogen (possibly as hydrogen ions)
and ferrous hydroxide participate in the reduction
process.
The basic reactions may be represented as
follows:
When the reduction of nitrobenzene is carried out in a glass
vessel, the early formation of a greenish precipitate,
characteristic of ferrous hydroxide is observed.

This turns to a brown and finally to ,black color, which suggests

that the formation of the known end product, magnetic iron
oxide, is a secondary effect resulting from the interaction
of ferrous and ferric hydroxides.
The amine hydrochloride produced in Eq. may be presumed to react further with iron
and nitrobenzene in one or two steps:

The step which is implicit in Eq. and which permits the replacement of
acids by acidic salts is shown in Eq.

The reactions indicated show that weak bases such as aniline behave similarly to
ammonia. They unite with water to form weakly dissociated bases. These, like
ammonium hydroxide, precipitate the hydroxides of the heavy metals from solutions
of their salts.

The last step how the completion of the "catalytic" cycle and emphasizes the role of
iron in the regeneration of the "catalyst," ferrous chloride, and the amine
This reaction is in accord with practical observations that
aqueous solutions of aniline hydrochloride,
or other salts-that are hydrolyzed in the presence of metals
with the formation of hydrogen ions, are useful "catalyst."
The over-all reaction can be represented as

This is an idealized equation, since in practice it has been

found that the iron oxide sludge (after dehydration) often
contains some FeO. The FeCl2 is not a true catalyst in that it
is continually consumed and new FeCl2 formed from fresh
iron
 Electronic Mechanism
According to the electronic theory, the nitro
group is electrophilic and accepts electrons from
the iron. The nitrogen atom in this arrangement
is bound to be electrophilic because of the pull
on its electrons by the phenyl group and the two
oxygen atoms. the evolution of hydrogen during
the reduction is merely the result of a side
reaction between the iron and hydrogen ions.
 According to the electron theory, such a
roundabout hypothesis is unnecessary, since
electrons and protons are readily available from
the iron and the acid solution.
In practice, hydrogen is liberated regularly
during the reaction and, in efficient operations,
amounts to slightly more than 0.1 cu ft. per lb.
of nitrobenzene reduced.
 Chemical and Physical Factors
Amount of Iron Used. In plant practice, it is
customary to use slightly over 2 moles Fe per
mole of nitro compound to carry out the
reduction process. Under such circumstances,
not all the iron is converted to the ferrosoferric
oxide, some reducto-active ferrous hydroxide
also being present.
 Physical Condition of Iron
From a study of the equations outlining the
reduction process, it is obvious that the iron fed
into the reducer not only supplies the metal
absorption surface but enters into the reactions
by providing the iron for the regeneration of the
ferrous chloride upon the hydrolysis of the
phenyl ammonium chloride (aniline
hydrochloride) and also acts as an oxygen
carrier.
 Use of finely divided iron
Analysis of the residual sludge reveals that
the bulk of the iron is converted to iron oxides,
the degree of oxidation depending on the
quantity of iron employed. Since the reaction
velocity for nitro compound reduction is a
function of the rate of iron oxidation, it is clear
that the use of finely divided iron shortens the
time of reaction
 Amount of Water Used
Theoretical considerations involving the
progressive
oxidation of the iron indicate the desirability of
using 4-5 moles of water per mole of nitro
compound treated. This approximation is based
, on the assumption that the iron employed is
converted first to ferrous and then to ferric
hydroxide as intermediate products during its
oxidation to the oxide.
 Amount of Acid Used
This reaction requires the presence of small amounts of
ferrous ion to act as a catalyst. Generally about 0.05-0.2
of an equivalent of acid is used.
The acids usually employed in the reduction process are
hydrochloric and sulfuric. hydrochloric acid sometimes
causes the formation of small amounts of chlorinated
amines whereas sulfuric acid may rearrange the
intermediate arylhydroxylamines to hydroxyarylamines
and cause the formation of darker amines in lower yields,
particularly in the case of solid amines.
Where the danger of hydrolysis or contamination by such
products exists, acetic or formic acid is employed instead
 Effect of Agitation
Since the reduction process under consideration is a
multi phase reaction, it is clear that the best results are
obtainable only when the nitro compound, iron, and
water-soluble catalyst are in intimate contact.

A stirrer that merely pushes the iron around the bottom

of the vessel and permits the charge to separate out into
layers does not function efficiently. It is apparent,
therefore, that a sturdy sleeve-and-propeller or double-
impeller type of stirrer will in some cases be superior to
the slow moving plow type.
 Reaction Temperature
It has been found that the use of a high catalyst concentration (3 per
cent or more compared to nitrobenzene taken) during reduction results
in a finely divided iron sludge which, although it is generally a poorly
filtering sludge, is of possible commercial value (for removing sulfur
compounds from illuminating gas).

This result can be obtained by limiting the quantity of water introduced

into the jacketed reducer and utilizing the heat of reaction to carryon
the reaction. An obvious advantage arising from operating with such
concentrated solution is the fact that the charge is easily maintained at
the boiling temperature.

The vigorous reflux that characterizes such a reduction ensures against

the formation of intermediate products of reaction. The reaction is not
only rapid but is economical on account of the lower consumption of
steam.
 Additions of Solvents
• Where a very insoluble and difficultly
reducible nitro compound is to be reduced,
the addition of a solvent miscible with water,
such as ethyl alcohol, methanol, or pyridine, is
often of considerable help.
• This makes for a smoother and more rapid
reduction.
 Testing for Completion
• Reduction will not take place in the absence of
ferrous ions, which can be demonstrated by
the lack of a black precipitate on spot testing
with sodium sulfide solution.
• The reaction is considered complete when an
aliquot no longer increases its take-up of
sodium nitrite on further reduction with a
stronger reducing agent, such as zinc and
hydrochloric acid.
 Work-Up of Reaction Mixture
• Soluble iron is generally precipitated with alkali, using
caustic soda, soda ash, lime, or magnesia. Where the
amine is volatile, it may be isolated by steam
distillation or by vacuum distillation from the iron oxide
cake after distilling off the water.
• In the latter case, an efficient scraper agitator must be
used to keep the iron oxide from lumping and
occluding the product.
• Where the final amine is soluble in alkaline solution, as
is the case with sulfonic acids, carboxylic acids, or
sulfonamides, the iron oxide cake is filtered off and the
amine isolated from the filtrate.
 Work-Up of Reaction Mixture
• Where neither of these two methods may be applied, a
third and technically undesirable process is sometimes
used.
• This involves solvent extraction of the iron oxide cake,
which brings with it filtration problems and costly
solvent recovery. Where a cheap solvent, such as
naphtha, can be used, these difficulties are somewhat
mitigated. Where a water-miscible solvent can be used,
it is usually added to the reduction mixture initially.
• When the final amine is volatile but sensitive to alkali,
as is the case with some polychloroamines, the amine
may be steam distilled from the slightly acid mixture.
 Continuous Processing
• Although the Bechamp reduction is generally
carried out on a batch basis, it has been run
continuously. This involve passing an acidified
solution or emulsion of the nitro compound
through a suitable tower packed with iron
shavings or scrap iron and kept at the required
temperature.
 Recovery of By-Products
• In the technical preparation of amines by
catalytic reduction with iron and a soluble salt,
it is not customary to recover and utilize the
dissolved catalyst
 Yields of Amine
• In plant practice, yields in the range of 85-98
percent of theory are obtained with the Bechamp
reduction.
• Depending upon the solubility and stability of the
starting nitro and final amine, many variations of
this process can be used to obtain the highest
yield in the most economical fashion.
• Method and rate of addition of the nitro
compound, temperature, agitation, addition of a
solvent or an emulsifying agent may all influence
the yield
 Equipment
• Materials of Construction. Bechamp reductions are usually carried out in
cast-iron vessels and alkali reductions in carbon-steel vessels of desired
sizes.
• The larger ones (1,600-gal capacity) are favored by plant engineers
because of the possibilities of more economical operation. The standard
machines made by a number of equipment manufacturers resemble one
another quite closely.
• Each manufacturer has, however, introduced one or more accessories or
refinements calculated to appeal to the experienced chemical engineer.

• The reducers for iron and acid reductions are sometimes equipped with
side and bottom cast-iron lining plates, which may be reversed or
replaced, in order to protect the vessel against the continuous erosive
action of the iron borings.
 Agitation
• In some reducers. a vertical shaft carries a set
of cast-iron plows which can be removed
through the side door to the reactor.
• These plows travel at the rate of 30-50 rpm
and serve to keep the iron particles in
suspension in the lower part of the vessel
 Jacketing of Reducers
• Practically all the iron reducers employed for
the Bechamp reduction of liquid nitro
compounds are equipped with jackets.
• Although the reduction process is distinctly
exothermic, the reaction proceeds best at
slightly elevated temperatures.
• It is customary, therefore, to warm the
reactants at the start
 Reducer Accessories
• The reducer is, of course, equipped with a
suitable feeding device, which will deliver the
iron borings as required. The borings bin is
frequently attached to a scale so that the
charge entering the reducer is being weighed
continuously and accurately.
• Suitable flanged or screwed openings are
provided for the introduction of the liquid
nitro compound and catalyst solution.
• Steam connections are made in accordance
with specific requirements, depending on
whether or not the vessel is jacketed and
whether or not the resulting amine is to be
distilled with steam.
• A sight box is placed in the reflux line.
 Manufacture of Aniline
• An accurately weighed charge of nitrobenzene
(Table 5-4) is delivered to the reducer from a
lower floor level to avoid the danger of
contamination, About 10-20 per cent of the
total iron, water, and catalyst is added, and
the charge is warmed to the reflux
temperature,maintaining a constant effective
agitation.
• It is entirely feasible to add all the water, iron,
and soluble catalyst at the start. This mass is then
thoroughly heated and agitated to etch the iron.
• The aromatic nitro compounds can there upon be
introduced at definite time intervals, the
precaution being taken that each portion is
completely reduced before continuing with
further addition.
• This technique gives satisfactory results in the
reduction of many nitro compounds.
• After all the reactants have been introduced,
external heat is required to maintain a lively
reflux. Steam may be introduced directly into
the reducer charge, or it may be circulated
through the jacket of the reducer.
• The condenser water is throttled down to
avoid overcooling of the condensate, as this
should be only slightly below the boiling point.
 Recovery of Aniline
The most important problem in the preparation of
aniline concerns its separation from the reducer
charge. The problem is essentially one of chemical
engineering. The engineer's goal is to provide
for the continual mechanical separation of the
aniline and water from the iron oxide sludge and to
recover the latter as a finely divided dry powder of
commercial value, where a market exists.
 Selection of equipment
The following criteria were suggested as a guide in the selection of
equipment:
1. Simplicity. Minimum handling of material.
2. Yields. Reduction to a minimum of the known sources of loss.
3. Productivity. Discharging the batch immediately after reduction is
complete.
4. Water balance. Elimination of methods that cause an accumulation
of aniline water, as this involves a great loss in yield and an increase in
power costs.
5. Power load. The consumption of steam, water, and electricity is an
important factor in determining the cost.
6. By-product sludge. In some localities, a market can be obtained for a
dry, clean, finely divided aniline-free iron oxide.