Lecture 23: Green Chemistry and

Technology

Course Instructor: Prof. Abu Taleb Khan

Course code: CH 426
Credit: 6

11/6/2023
 What is the meaning of lonic liquids, and why are they
unique?

 lonic compounds present in the liquid state are called ionic liquids.
 In some contexts, the term has been restricted to salts whose melting point is
below some arbitrary temperature, such as 100 °C.
 Generally, ionic compounds are solid due to strong columbic interaction and
efficient packing due to the comparable size of cations and anions.
• Ionic liquids have discrete ion pairs, but other conditions do not match,

resulting in poor packing than salts like NaCl.

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 lonic Liquid

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 Some unique properties of Ionic Liquid (IL)
 The melting point is generally lower than inorganic salt and sometimes below room
temperature (room temperature ionic liquid or RTIL).

 They are liquid-like organic solvents, but their properties differ, like solubility

(soluble/miscible) in solvents like ether, H₂O, alcohols, DMSO, etc. Completely inverse
property or intermediate property (between organic and inorganic) liquid could be
obtained.

 The properties of IL could be significantly changed by changing the cationic centre, side
chain substitution, nature of anion, and purity. So, unlike inorganic salts, a lot of
chemical tuning is possible.

 Some uniquely functional group attachments may result in unique properties. Like
efficient CO adsorption using amine-functionalized.

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 Some unique properties of Ionic Liquid (IL)

 Very low vapour pressure: Such molecules have stronger attraction than simple

Vander Waals forces of attraction like common liquids.They are generally highly viscous.

 Generally Hygroscopic: Since they are ionic and mismatch between the cation and

anion, they like water to absorb from the atmosphere.

 Conducting liquid consists of ionic moieties, so they are conducting, but the

conductivity is less.

 Wide voltage window: Depending on the nature, they are far more redox tolerant

(generally up to 4 V) than water (1.23 V)—a good candidate for liquid for battery
applications.

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 Ionic Liquids Organic

The major advantage of using ionic liquids as solvents is their very low vapour
pressure, which, coupled with the fact that they can often act as both catalyst
and solvent, has sparked considerable interest. The main issues still to be
resolved centre on their toxicity (most ionic liquids have not been assessed) and,
despite the potential for recycling, the fate and protocol for their ultimate
disposal has not been established.

toxic , solvent , catalyst , low vapor pressure

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 Ionic Liquids Organic

Ionic liquids or, more correctly, non-aqueous ionic liquids have been known for
many years. In broad terms they can be viewed like common ionic materials
such as sodium chloride, the difference being that they are liquid at low
temperatures, this being due to poor packing of the respective ions. In order
to achieve this poor packing requirement, room-temperature ionic liquids are
generally made from relatively large, non-coordinating, asymmetric ions.
Invariably, at least one of these ions is organic in nature.

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 Ionic Liquids Organic
Based on this criterion there are many thousands of possible ionic liquids of
which only a few have been studied in any detail;
Ionic liquids are not currently available in significant quantities for most
commercial operations but their preparation is relatively straightforward
(although synthesis of very pure materials is more difficult). For example,
[NBupy]AlCl4 can simply be prepared by mixing the N-butylpyridinium chloride
with aluminium chloride, the resulting exothermic reaction producing the liquid
product. Metathesis reactions are also widely used for preparing ionic liquids,
for example [emim]BF4 can be prepared from reaction of [emim]I with
ammonium fluoroborate in acetone, the ammonium acetate remaining in the
solvent.

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 Some Common Room Temperature Ionic Liquids Organic
 Ionic liquid

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 Some Common Room Temperature Ionic Liquids
 Ionic liquid

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 Ionic Liquids Organic
When assessing the overall greenness of a process using an ionic liquid its
synthesis should also be taken into account since many literature routes employ
volatile and chlorinated solvents in synthesis or purification procedures. The
problem of using a volatile organic solvent may just be being moved back down
the overall process chain. For industrial use it is often vital to remove
contamination by chloride ions, since these may form trace chlorinated by-
products (particularly a problem for the pharmaceutical industry) and give
excessive corrosion in stainless-steel reactors.

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 Ionic Liquids Organic
The types of ionic liquids have been most extensively studied, especially ones
based on chloroaluminate. Whilst these chloroaluminate materials also display
useful Lewis acid properties they are highly air and moisture sensitive, which
renders them relatively commercially unattractive. Newer ionic liquids
containing ClO4- and NO3- anions, for example, which are less air and
moisture sensitive, are now being more widely studied, but these are less
catalytically active. Other than lack of vapour pressure and catalytic properties
there are several other features common to most ionic liquids that make them
attractive reaction solvents.

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 Ionic Liquids Organic
These include:
Tunability – by varying the cation/anion ratio, type and alkyl chain length
properties such as acidity/basicity, melting temperature and viscosity can be
varied to meet particular demands.
Many ionic liquids are stable at temperatures over 300oC, providing the
opportunity to carry out high-temperature reactions at low pressure.
Ionic liquids that are not miscible with organic solvents or water may be used to
aid product separation or used in liquid–liquid extraction processes.
For a given cation, the density and viscosity of an ionic liquid are dependent on
the anion; in general, density increases in the order BF4-, PF6-, (CF3SO2)2N and
viscosity increases in the order (CF3SO2)2N, BF4-, PF6-, NO3-.

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 Ionic Liquids as Catalyst
The highly acidic properties of [emim]AlCl4 have been used in several cationic
alkene oligomerization reactions. For example, refinery raffinate streams
containing high levels of butenes can be oligomerized/polymerized to give
materials ranging in molecular weight from 600 to 100 000; such materials are
used as lubricating oils. Such reactions are rapid, with conversions well over
90% being achieved within 30 min. The major benefit of these reactions lies
in product work-up. Whilst no solvent is required in conventional butene
oligomerization processes, a homogeneous ethyl aluminium chloride catalyst is
often used, this largely being lost in the heavy residue by-products and aqueous
wash. In contrast the organic product is not miscible with the ionic liquid and
can be readily decanted from the catalyst, which can be reused. No aqueous
wash is thought to be required.

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 Ionic Liquids Organic
Chloroaluminate ionic liquids are also highly active Friedel–Crafts catalysts,
in fact with active alkyl halides mono-alkylation is often difficult to
achieve owing to the very high activity of the catalyst. More success
has been achieved using alkenes as the alkylating agents, since they have lower
activity than alkyl halides. One potential application of this that has been
demonstrated at laboratory scale is the alkylation of benzene with dodecene,
with the ionic liquid being readily recoverable.

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 Ionic Liquids Organic
This route again offers advantages compared to traditional processes using AlCl3
(which is lost as waste) or HF (hazardous), although there are no clear
environmental advantages compared to the latest zeolite-catalysed processes.
Unfortunately, ionic liquid catalysts have not yet provided a solution to the need
for truly catalytic acylation reactions using unreactive substrates. As with
traditional Lewis acid catalysts the product complexes to the ionic liquid and can
only be separated by quenching with water, destroying the catalyst.

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 Ionic Liquids Organic
The acidic and catalytic properties of chloroaluminate(III) ionic liquids are
frequently said to arise from the species Al2Cl7-.
2AlCl4- = Cl- + Al2Cl7-

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 Ionic Liquids as Solvents
 If ionic liquids become widely used it is likely to be the less water and air
sensitive ones which prove to be more commercially attractive, and the
main emphasis will lie with their use as solvents rather than as catalysts.
An interesting contrast between catalytic and non-catalytic ionic liquids
is provided in Seddon’s synthesis of Pravadoline, a potential non-
steroidal anti-inflammatory drug. When the second stage acylation
reaction was carried out using [emim]AlCl4 the product co-ordinated
to the Lewis acid catalyst, requiring a water quench to isolate the
product.

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 Ionic Liquids as Solvents
 However, it was found that owing to the high activity of the indole group
towards acylation no Lewis acid catalyst was required. The reaction
could be carried out in high yield in the ionic liquid [bmim]PF6,
although a temperature of 150oC was required compared to 0oC when
using a catalyst. The non-catalysed route afforded simple product
separation and a recoverable solvent.

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 Ionic Liquids as Solvents
 Using IL

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 Ionic Liquids as Solvents
The Diels–Alder reaction is receiving much attention because of recent
findings of rate enhancements similar to, although smaller than, those
found when using water as a solvent. Endo selectivities are also found to
be generally good. Of course ionic liquids could be used to enhance the
rate of Diels–Alder reactions involving water sensitive reagents. In some
instances, e.g. the aza-Diels–Alder reaction illustrated, Lewis acid
catalysts are additionally required but use of ionic liquids greatly enhances
their ease of recovery and recycle.

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 Ionic Liquids as Solvents
Diels-Alder reaction:

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 Ionic Liquids as Solvents
Diels-Alder reaction:

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 Ionic Liquids as Solvents
Ionic liquids are proving to be valuable solvents for carrying out what
usually would be considered to be homogeneously catalysed reactions,
since in many cases the catalyst stays in the ionic liquid and can be readily
reused, bringing in many of the advantages of heterogeneous reactions.
Where reported, catalyst leaching is normally very low. Hydrogenation
reactions have been well studied, with rates several times those found in
organic solvents often being obtained; this has been attributed to stabiliza-
tion of intermediate catalyst species by the ionic liquid. The scope of the
reaction is wide and, by tuning reaction conditions, catalyst and ionic
liquid, high levels of product selectivity can be obtained.

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 Ionic Liquids as Solvents
Pentene, for example, can be hydrogenated to pentane using
Rh(nbd)(PPh3)2 [nbd = norbornadiene) as catalyst in [emim]PF6. Dienes
are more soluble in ionic liquids than monoalkenes, which has led to a
highly selective conversion of cyclohexadiene to cyclohexene, whilst
butadiene can be selectively reduced to but-2-ene using [bmim]3CO(CN)5.
There are several reported examples of enantioselective hydrogenations
being carried out, for example hydrogenation of 2-phenyl acrylic acid and
the related synthesis of (S)-Naproxen.

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 Ionic Liquids as Solvents
Asymmetric Synthesis

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 Ionic Liquids as Solvents
Because of their potential for easy recycle and low catalyst losses, Pd-
catalysed reactions have received much attention. In principle, the use of
ionic liquids could overcome many of the catalyst loss issues that have
prevented wider commercial use of valuable Pd-catalysed coupling
reactions such as those developed by Heck or Suzuki. Possibly the simplest
(and least expensive) examples of an ionic liquid being used in a Heck
reaction is the synthesis of trans-cinnamic acid derivatives using simple
molten tetraalkylammonium bromides.

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 Ionic Liquids as Solvents
Although these are not liquids at room temperature many melt below
typical reaction temperatures of 100oC. Use of these salts has led to
excellent yield improvements, by a factor of five in some cases, compared
to traditionally employed solvents such as dimethyl formamide (DMF). The
product can usually be isolated by vacuum distillation, and the molten
salt/catalyst mix reused without loss of activity. Pd-catalysed carbonylation
of aryl bromides has also been studied and whilst in limited studies the
reactions proved to be significantly more efficient than those run without
solvent, catalyst activity did decline on subsequent reuse.

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 Ionic Liquids as Solvents
Heck reaction

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 Ionic Liquids as Solvents
From reviewing much of the literature it is easy to conclude that ionic
liquids are excellent solvents for catalysts and reagents but not for
products, which is obviously not the case. Whilst some products can be
decanted from the liquid and others can be recovered by distillation, there
are many useful reactions in which removal of the product (or residual
reactants) from the ionic liquid is challenging. Extraction with an organic
solvent, or even water, would reduce the overall eco-efficiency. Initial
studies in which scCO2 has been used to extract material from a variety of
ionic liquids show promise, with, for example, naphthalene being readily
extracted from [bmim]PF6.

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 Ionic Liquids as Solvents

Before leaving ionic liquids it is worth mentioning their potential value in

separation processes. Organic solvents are frequently used in multiphase
extraction processes and pose the same problems in terms of VOC
containment and recovery as they do in syntheses, hence ionic liquids
could offer a more benign alternative. Interesting applications along this
line which have been studied include separation of spent nuclear fuel from
other nuclear waste and extraction of the antibiotic erythromycin-A.

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 Conclusion

 They are considered solvents for the future due to these unique properties.

 More opportunities are available for scientists to tune different properties by

changing the parameters, like cation, anion, other functional groups, etc.

 They are like highly soluble organic compounds.

 Their electrochemical and CO₂ adsorption capability could open up a new

window for scientists.

 Their toxicity and environmental impacts must be studied before their disposal

into the environment.

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