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Introduction
Most of the organic solvents are volatile that are used in organic synthesis. The toxic
and hazardous properties of many solvents, notably chlorinated hydrocarbons, combines with
serious environmental issues, such as atmospheric emission and contamination of aqueous
effluents is making their use prohibitive.
Recently ionic liquids (IL) are emerging as novel replacement for volatile organic
compounds traditionally used as solvents and reduce the volatility, environmental and human
health and safety concerns that accompany exposure to organic solvents.
The ionic bond is usually stronger than the Van der Waals forces between the molecules
of ordinary liquids. For that reason, common salts tend to melt at higher temperatures than
other solid molecules. Some salts are liquid at or below room temperature.
Ex: - Pyridinium chloride (C5H6N+Cl) that melts at 144.5 C (292.1 F), 1-ethyl-3methylimidazolium dicyanamide ((C2H5)(CH3)C3H3N+2N(CN)2) that melts at 21 C (6 F)
and 1-butyl-3,5-dimethylpyridinium bromide which becomes a glass below 24 C (11 F).
Low-temperature ionic liquid can be compared to ionic solutions, liquids that contain
both ions and neutral molecules, and in particular to the so-called deep eutectic solvents,
mixtures of ionic and non-ionic solid substances which have much lower melting points than
the pure compounds. Certain mixtures of nitrate salts can have melting points below 100 C.
Ionic liquid (IL) is a salt in the liquid state. In some contexts, the term has been
restricted to salts whose melting point is below some arbitrary temperature, such as 100 C
(212 F). While ordinary liquids such as water and gasoline are predominantly made of
electrically neutral molecules, ionic liquids are largely made of ions and short-lived ion pairs.
Any salt that melts without decomposing or vaporizing usually yields an ionic liquid.
Eg: - Sodium chloride (NaCl) melts at 801 C (1,474 F) into a liquid that consists largely of
sodium cations (Na+) and chloride anions (Cl).
liquid electrolytes
ionic melts
ionic fluids
fused salts
liquid salts or
ionic glasses.
Definition:
The ionic liquid (IL) implies an ionic material that is liquid at ambient temperature or
salt that are liquid at near-ambient temperature, is colorless, has a low viscosity and is easily
handled, i.e., a material with attractive properties for a solvent.
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Commonly
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1-Butyl-3-methylimidazolium
1-Butyl-3-methylimidazolium(bmim)
(bmim)salt
salt
Ionic liquids have many applications, such as powerful solvents and electrically
conducting fluids (electrolytes). Salts that are liquid at near-ambient temperature are important
for electric battery applications, and have been used as sealants due to their very low vapor
pressure.
Ionic liquids are made up of at least two components which can be varied (the cation
and the anion). Properties such as melting point, viscosity, density and hydrophobicity can be
varied by simple changes to the structure of ions.
Another important property that changes with structure is the miscibility of water in
these ionic liquids. By choosing the correct ionic liquid, higher product yield can be obtained
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and a reduced amount of waste can be produced in a given reaction. Often the ionic liquids can
be recycled and this leads to a reduction of the costs of the process. The reactions are often
quicker and easier to carry out than in conventional organic solvents.
Ionic liquids are good solvents for a wide range of both inorganic and organic materials.
They are often composed of poorly coordinating ions, so they have the potential to be highly
polar non-coordinating solvents. They are also immiscible with a number of organic solvents
and provide a non-aqueous, polar alternative for two phase system. Hydrophobic ionic liquids
can also be used as immiscible polar phases with water. The use of ionic liquids can enhance
activity, selectivity and stability of transition metal catalysts.
They have essentially no vapour pressure or negligible vapour pressures and therefore do
not evaporate under normal conditions.
ii.
They possess generally non-flammability and good thermal stability and do not
decompose over a large temperature range, thereby making it feasible to carry out
reactions requiring high temperature conveniently.
iii.
Ionic liquids have a wide range of solubilities and miscibilities and therefore, they are able to
They serve as good medium to solubilise gases such as H 2, CO, O2 and CO2 and many
reactions are now being performed using ionic liquids and supercritical CO2.
v.
The solubility of ionic liquids depends upon the nature of the cations and counteranions.
vi.
They generally do not co-ordinate to metal complexes, enzymes and different organic
substrates.
vii.
Most of the ionic liquids can be stored without decomposition for a long period of time.
viii.
ix.
x.
xi.
Ionic liquids can be used as reaction media and, or catalysts for a wide variety of chemical
reactions.
xii.
Ionic liquids can also be used for separations and extractions of chemicals from aqueous
and molecular organic solvents.
xiii.
The physical, chemical and biological properties of ionic liquids can be tuned or
tailored by:
a. switching anions or cations,
b. by designing specific functionalities into the cations and/or anions,
c. by mixing two or more simple ionic liquids.
xiv.
Because ionic liquids consist of cations and anions, they have dual functionality. They
therefore impart a unique architectural platform compared with molecular liquids.
Consequently, ionic liquids can potentially be exploited as solvents and new materials
for wide- ranging applications spanning, for example, electrochemistry, organic
chemistry, inorganic chemistry, biochemistry, materials science and pharmaceuticals.
xv.
Ionic liquids could contribute significantly to the development of green chemistry and
green technology by, for example:
a. replacing toxic, flammable volatile organic solvents,
b. reducing or preventing chemical wastage and pollution,
c. improving the safety of chemical processes and products.
b). [C4mim]Cl is commonly used as a precursor for preparing other ionic liquids. It is
obtained by the reaction of 1-methylimididazoles and 1-chlorobutane.
c). Halogenalkanes are also used to alkylate pyridine in the preparation of alkylpyridinium
salts. [C2py]Br is prepared by the reaction of pyridine and bromoethane.
The aliphatic quaternary ammonium cations are prepared from alkylammonium halides
which are commercially available or they can be prepared simply by the reaction of the
appropriate halogenoalkane and amine.
2). Anion exchange preparation
Ionic liquids with the [NTf2] anion, are prepared by exchange reaction between an
organic halide salt and lithium bis[tri(fluoromethyl)sulfonyl]amide (Li[NTf2]).
In the first step, the tert.amine, N-methylimidazole or pyridine, was protonated with an
acid, giving the ammonium salt, and the anion of the final ionic liquid was introduced in this
step. In the second step, the protonated amine was reacted with a,-unsaturated compound in the
presence of weak and volatile bases such as pyridine at 70C for about 16 h to yield the ionic
liquid.
Hydroformylation
Hydroformylation of olefins is industrially important reaction. The reaction is carried
out in aqueous-organic biphasic system catalyzed by water soluble Rh catalyst. But, the use of
water as polar phase limits this process to C 1-C5 olefins due to low water solubility of higher
olefins.
This solubility problem is overcome by using ionic liquids containing PF, SbF and BF
in an ionic liquid organic biphasic system. The products are separated as an organic phase and
the catalyst can also be used. A small amount of catalyst leaching into organic phase causes
some loss in activity after each run. These problems have been improved by varying the ligand
and the ions of ionic liquids. The platinum catalyzed hydroformylation of 1-octene in
chlorostannate melts in [bmim][Cl] give high n/iso selectivities. The biphasic nature of the
reaction enabled very simple product isolation and leaching of the platinum catalyst into the
product phase was not observed.
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obtained in 91% yield after 5 h at room temperature using Pd(OAc)2/PPh3 as the catalyst system
and K2CO3 as the base.
Biphasic TrostTsuji couplings have been conducted by de Bellefon et al., in [bmim]
[Cl]/methylcyclohexane. These workers observed a tenfold improvement in the catalytic
activity due to the higher solubility of the substrates in the ionic liquid (eq 17). Enhanced
selectivity was also achieved, since the formation of cinnamyl alcohol and phosphonium salts
was suppressed.
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Background
There is growing interest in Ionic Liquids (IL's) as a green solvent
Features that make ILs attractive for use in organic synthesis in general and catalytic processes in
particular are
Another important feature is the possibility of tuning their physical and chemical properties by
varying the nature of the anion and side chain.
The drawback is that they are expensive. However, their high cost stems not from the cost of
ingredients but from the challenges faced in the synthesis (which is usually carried out in batch).
The synthesis is highly exothermic, and in batch must be carefully controlled in case hotspots form in
the reactor which will lessen the overall purity of the product. Reaction times may be up to 24 hrs,
with temperatures kept low, and dilution solvents are used which must be removed later.
In continuous flow, however, these challenges are straightforward to address. Large surface area to
volume ratios and consistent, steady conditions throughout the reactor enable ILs to be synthesized
using neat reagents, at far higher reaction temperatures (resulting in radically shorter reaction
tiomes, of the order of minutes).
Application Note 16 - Bromination of Alkenes with NBS under continuous flow
Bromination of unsaturated C-C bonds with NBS is a well known and widely used procedure,
although when carried out in batch, slow and careful addition of the NBS is often required in order to
prevent over-bromination & avoid thermal runaway. This study demonstrates how with flow
chemistry these factors are no longer an issue.
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Bromination with molecular bromine in batch mode usually requires slow and careful addition of the
bromine reagent to control thermal kinetics, and often results in poor selectivity. This study
demonstrates safe bromination in flow, giving rapid complete conversion and high selectivity.
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The conversion of aryl hydrazones to indoles; requires elevated temperatures and the addition of
Brnsted or Lewis acids. Some interesting enhancements have been published recently; for example a
milder conversion when N-trifluoroacetyl enehydrazines are used as substrates. .
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The total synthesis of the pharmaceutical Pravadoline was carried out in ILs as shown
below. In this two-step reaction, a base promoted nucleophilic displacement reaction and a
Friedal-Crafts acylation readily occur in [bmim]PF 6] IL giving 94% yield of the
pharmaceutical.
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Ionic
Liquids
Ionic Liquids are a peculiar and fascinating class of new chemicals with the potential to improve development in organic
chemistry and chemical technology, stimulating progress in a lot of different research fields. The designing of chemical
processes and products that reduce or eliminate the use and generation of hazardous substances has become a new
focus in many aspects of pure and applied chemistry. In this context, Ionic Liquids are regarded as environmentally friendly
substitutes for volatile organic compounds (VOCs) essentially because of their low vapour pressures and their specific
advantage to act as solvent or catalyst.
WHAT'S SO SPECIAL ABOUT IONIC LIQUIDS?
Ionic Liquids are compounds consisting entirely of ionic species with an organic cation and an inorganic or organic anion.
They have intrinsically useful properties such as high ionic conductivity, thermal stability (over 300 C), negligible vapour
pressure and a large electrochemical window. Depending on the anion and substitute groups of the cation, these
compounds can solubilize alcohols, alkyl halides, carbonyl compounds, supercritical CO2 (scC02) and also transition
metal complexes. Simultaneously, they present a low miscibility in alkanes, dialkyl ethers and water.
APLICATIONS OF IONIC LIQUIDS
ORGANIC
CHEMISTRY
The use of ionic liquids as a recyclable and environmentally benign medium has been attracting considerable attention for
chemical transformations including non-catalytic reactions, biocatalytic and catalytic reactions in monophasic systems
(both substract and catalyst dissolved in the ionic liquid, and sometimes the ionic liquid works like a catalyst itself),
biphasic systems (with the catalyst dissolved in the ionic liquid and the substract/product in a second phase or vice versa)
and triphasic systems( with an ionic liquid phase, an organic phase and an aqueous phase).
Reactions like oxidations, hydrogenations, hydroformylations, Heck reaction, olefin oligomerisation, Trost-Tsuji coupling,
dihydroxylations and epoxidations among several others have been tried successfully using such systems.
Organic
synthesis
Catalysis
ELECTROCHEMISTRY
Electrolytes
ANALYTICAL CHEMISTRY
. Stationary phase for chromatography
Matrices for MS
PHYSICAL CHEMISTRY
Solute extraction and recovery using supported liquid membranes is recognized as one of the most promising membranebased processes. The use of ionic liquids (RTILs) as an immobilized phase in a supporting membrane is particularly
interesting due to the nonvolatile character of the RTILs and their solubility properties in the surrounding phases, which
makes it possible to obtain very stable supported liquid membranes without any observable loss of the RTIL to the
atmosphere or the contacting phases.
Separation processes
Extraction processes
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BIOTECHNOLOGY
Enzymes
ENERGY
Fuel and solar cells
Lubricants
Batteries
MATERIALS
Nanomaterials
Liquid Crystals
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