Unit process
PCH-4803
Halogenation
Prof. [Link]
Halogenation may be defined as the process
whereby one or more halogen atoms are introduced
into an organic compound.
The preparation of organic compounds containing
fluorine, chlorine, bromine and iodine can be done
by a variety of methods.
The conditions and procedures differ, not only for
each member of the halogen family but also with
the type and structure of the compound undergoing
treatment.
The chlorine derivatives, because of the greater
economy preparation, are the most important
compound.
Halogenations may involve reactions of
Addition
Substitution i.e. of hydrogen,
Replacement, of groups
for example, the hydroxyl or sulfonic acid group
Many catalysts are halogen carriers.
Iron, antimony, and phosphorous, which are able to
exist in two valences as halogen compounds, are used
as they are less stable at higher valence and give up part
of their halogen during the process.
In the presence of free halogen, such compounds
alternatively add on and give up halogen to carry on the
reaction. Iodine, bromine and chlorine, which are
capable of forming mixed halogens, are also frequently
used as catalysts in halogenation processes.
Active carbon, clays, and other compounds are also
catalyses halogenations processes.
METHODS FOR PREPARATION OF
CHLORINE COMPOUNDS:
Addition reaction:
Substitution reaction:
Replacement Reaction:
Sodium hypochlorite as chlorinating agent:
Chlorination with phosgene (COCI2) and
Benzotrichloride (C6H5CCl3)
BROMINATION
Bromination may be carried out in a manner
similar to that employed for the preparation of
chlorine derivatives.
Bromine, bromides, bromates and alkaline
hypobromites may be used instead of the
corresponding chlorine compounds.
Reaction involving addition and substitution are
common. Bromine dissolved in water is
frequently employed, particularly in the
bromination of phenols. Potassium bromide is
generally added to aqueous bromine solution to
increase the concentration of soluble molecular
halogen.
Concentrated bromide solutions are in the following
equilibrium. .
Bromine, hydrobromic acid and alkali hypobromites,
like the corresponding chlorine compounds
employed in technical brominations.
N- Bromo acetamide NBS
organic compound carriers for bromide to produce
specific types of bromine containing compounds
have also been used.
IODINATION
The relatively weak C-l bond makes permanent,
direct union of carbon to iodine by the replacement of
hydrogen possible only in exceptional cases.
The hydrogen iodide tends to effect de-iodination of
the halogenated compounds and indeed is sometimes
thus employed.
The removal of the hydrogen iodide by such means
as oxidation or absorption in alkali is essential for
successful iodination. Then nitric acid is employed as
the oxidant
Direct halogenations in the absence of an oxidizing
agent, half the reacting halogen is converted to the
hydrogen halide.
Iodine monochloride because of its activity under
mild operating is a useful catalyst for the iodination of
amino compounds.
Hydroiodic acid and alkali hypoiodites; like the
corresponding chlorine and bromine compounds, find
employment in iodination.
FLUORINATION:
Fluorine acts directly on hydrocarbons to produce
fluorides, but the reaction is violent and constitutes an
explosion hazard.
Some reactions can be carried out by careful control
of temperature and fluorine concentration, but even
then there may be a cleavage of carbon-carbon bonds.
Direct fluorination :
Direct vapour phase fluorination using elemental
fluorine is done by using large volumes of an inert
gaseous fluorine and hydrocarbon carrier, such as
nitrogen, a mixing system that rapidly and intimately
brings the two reactants into contact and a reactor
design that effectively removes the heat of reaction.
Dilute fluorine reacts with metal carbides such as
UC2, ThC2, and CaC2 producing fluorocarbons and
metal fluorides.
All these direct fluorination reaction are
accompanied with high energy type of condensation
reactions where fluorocarbons of higher carbon chain
length are formed
The use of elemental fluorine as a condensing
agent in liquid phase reactions to form higher
molecular weight compounds.
Liquid phase fluorination has been demonstrated
on number of compounds, but the hazards of
violent detonations and wide diversity of products
so far have limited the use of these procedures.
HF as a fluorinating agent :
Hydrogen fluoride adds in vapour phase by means of
catalysts to acetylene .
Hydrogen fluoride in a liquid-phase reaction readily
replaced chlorine in many organic compounds.
Fluorination with metal fluorides :
The majority of organic fluorides produced today are
still made by the antimony halide process, starting
with hydrogen fluoride and antimony pentachloride
A number of the polyvalent metal fluorides are
excellent fluorinating agents and are used in
commercial reactions.
Fluorination with alkali metal fluorides
Sodium and potassium fluorides/ react with alkyl
hydrogen sulfates and with acid chlorides to produce
organic fluorides.
Diazo reaction :
Aromatic diazo compounds react with hydrogen
fluoride and boron trifluoride to form aromatic
fluorides with the liberation of nitrogen
N-Fluoro reagents:
A variety of N-fluorinated amines, quaternary salts,
amides and sulfonamides have been proposed as
reagents for selective electrophilic fluorination under
mild conditions.
These are usually stable, easily-handled solids, and
provide a range of fluorinating power from mild to
moderate, depending on the structure of the reagent and
the nature of the substrate.
Another advantage is that, since free hydrogen fluoride
is not a major by- product in fluorination reactions with
this type of reagent, conventional glass equipment is
often suitable.
N-Fluorobenzenesulfonimide
N-Fluoropyridinium
trifluoromethane sulfonate
Other electrophilic reagents:
Xenon fluorides, especially the difluoride, can be
used in the selective fluorination of substrates including
arenes,alkenes and active methylenes, and also in the
fluoro- decarboxylation of carboxylic acids.
The use of cobalt(III) fluoride or cobalt(II) fluoride/ fluorine] is used for the
fluorination of hydrocarbons, ethers, etc., but requires high temperatures and
specialised equipment.
Silver(II) fluoride has found some limited use in the
fluorination of aromatics.
Several highly reactive species can be generated from
elemental fluorine, including trifluoromethyl
hypofluorite, acetyl hypofluorite(explosive), and
cesium fluoroxy- sulfate (unstable, shock-sensitive),
CHLOROBENZENE /DICHLOROBENZENE
Raw materials
Basis - 1 ton chlorobenzene
Benzene - 1,900 lb
Chlorine- 1,750 1b
Iron turnings small (1 %)
Manufacture /Batch process:
Dry benzene is charged into a tall cast iron or steel
tank or chlorinator lined with lead or glass.
About 1% by weight (of the benzene charge) iron
turnings is used as the catalyst and remains in the
chlorinator after each batch.
Chlorine is bubbled into the charge at p the
temperature at 400C to 60°C.
The chlorination is continued until the proper density
is reached.
When only mono-chlorobenzene is desired, the
chlorination temperature is maintained at about 40°C.
HCl
When all the benzene is chlorinated, the reaction is
run at the temperature 55-60°C and a density of 1.280
gm/cm3 (15°C) is reached in about 6hr.
HCl given off during the reaction is scrubbed with
benzene or chlorobenzene to remove organic spray
and is absorbed in water in a suitable absorption
system to give hydrochloric acid.
The chlorinated benzene is delivered to the
neutralizer a jacketed steel tank equipped with a
reflux condenser and vent containing an aqueous
solution (10%) of caustic soda.
The charge is thoroughly agitated to ensure
neutrality and is kept warm by jacketed steam.
The alkaline chlorinated benzene is allowed to settle
in the separator.
Sludge collected from the bottom for distillation.
The bulk of the material is distilled and separated
into several fractions.
The following fractions are obtained.
The composition of the chlorinated products varies
according to the chlorination temperature, rate,
degree and catalyst.
However, 100 percent chlorination will yield
approximately the following composition: