Assessing The Grenness of Some Typical Laboratory Ionic Liquid Preparations", M. Deetlefs, K. R. Seddon, Green Chem. 12, 17-30 (2010)
Assessing The Grenness of Some Typical Laboratory Ionic Liquid Preparations", M. Deetlefs, K. R. Seddon, Green Chem. 12, 17-30 (2010)
Assessing The Grenness of Some Typical Laboratory Ionic Liquid Preparations", M. Deetlefs, K. R. Seddon, Green Chem. 12, 17-30 (2010)
The greenness, or lack thereof, of various ionic liquid syntheses and purification methodologies are
assessed using a common tool used in strategic planning viz. strengths weaknesses opportunities
threats (SWOT) analysis, including their adherence to the twelve principles of green chemistry,
% atom economies and E-factors.
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When are ionic liquid syntheses green? it is challenging for a chemical process to incorporate all twelve
principles of green chemistry, but the sine qua non is that it
Although ionic liquids still uphold their baptism as ‘green’, must always be crystal-clear whether a reported process is truly
the use of the term, and indeed what constitutes a green green, or whether only parts of it are green. Needless to say, the
ionic liquid synthesis, continues to be misinterpreted. At the same overarching green approach should apply to ionic liquid
heart of the misinterpretation, and many spurious claims, lies syntheses too, and it must thus be spelled out, especially in
the assumption that ionic liquids are green because of their the open literature, what exactly is green about the ionic liquid
negligible vapour pressure.1,2 However, there are many other and/or its preparation or use, if anything at all.
factors that determine whether an ionic liquid is, or is not, green, Since many excellent reviews8–11 already exist that describe
particularly the ionic liquid preparation itself (which is generally various ionic liquid syntheses and purifications, here we have
not considered or reported in the literature). It is also often confined ourselves to assessing the ‘greenness’ of some common,
overlooked that the very designer classification3 of ionic liquids laboratory-scale ionic liquid preparative methods i.e. purifica-
means that they can be engineered to possess distinctly ‘non- tion procedures (Fig. 2)12 and synthetic routes (Fig. 3).9,12,13
green’ attributes (viz. toxicity, explosivity,4 non-biodegradability, Although it would be desirable to assess ionic liquid preparations
etc.), and they can be (and have been) obtained by distinctly dirty conducted at the industrial scale, the information is not available
procedures (e.g. using harmful organic solvents). In other words, for a credible study. Moreover, we have only assessed the
the term ‘green’ should only be applied to an ionic liquid if both preparative routes themselves and have not considered the fate14
the ionic liquid, and the process used to produce it are green, i.e. of the ionic liquid starting materials or products.
if all twelve principles of green chemistry apply (Fig. 1).5 In addition, we have also gauged the relative pros and cons of
The twelve principles of green chemistry have been formalised using differing energy sources to promote ionic liquid syntheses,
and extensively promoted since the 1990s by their progenitor, viz. conductive (conventional) heating, microwave irradiation,
Prof. Paul Anastas,5,6 and, recently, were elegantly condensed ultrasonic irradiation, and simultaneous microwave and ultra-
by Prof. Martyn Poliakoff and co-workers into a mnemonic sonic irradiation. For convenience, we have concentrated on
for easy communication, viz. PRODUCTIVELY.7 Undeniably, ionic liquids containing 1-alkyl-3-methylimidazolium cations,
[Cn mim]+ .
The QUILL Research Centre, David Keir Building, Stranmillis Road,
Although many other synthetic routes are also available to
Belfast, BT9 5AG, UK. E-mail: [email protected] prepare ionic liquids, e.g. carbene15 and alkylsulfate9,16 routes, the
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general principles outlined here apply only to the hydrophobic What principles of green chemistry are relevant to
and hydrophilic synthetic procedures discussed, but the method typical ionic liquid preparations?
of analysis could be applied.
Of the twelve principles of green chemistry, the 4th, 7th, 9th
and 10th principles5 are irrelevant to the laboratory-scale ionic
liquid preparations discussed here. This is because the 4th, 7th
The scales of justice and 10th principles of green chemistry apply to the ionic liquid
product itself rather than the procedure, while the 9th principle
The assessment of the greenness of ionic liquid syntheses is a is associated with catalytic methodologies and hence is also not
question of scale, and size really matters! This is because the relevant to the typical ionic liquid preparations summarised in
greenness factors associated with laboratory-scale ionic liquid Fig. 2 and 3. In contrast, the 8th, 11th and 12th principles
preparations are quite different than those that are relevant of green chemistry apply to all the ionic liquid syntheses
to industrial-scale syntheses. For example, in industrial-scale discussed here since (i) derivatisation (8th principle) is not used
processes, excess 1-haloalkanes are typically recycled, whereas in any of the ionic liquid syntheses, (ii) in-process monitoring
in the laboratory they are usually discarded. Another example (11th principle), although currently under development (e.g.
is that on an industrial scale, the use of conductive heating lab-on-a-chip),18 is not yet ready for im-
(e.g. superheated steam) is more convenient, energy efficient and plementation, and (iii) ionic liquids, by
economical than employing microwave irradiation, while the virtue of their negligible vapour pressure,
opposite is true for laboratory-scale preparations.17 Therefore, minimise the potential for chemical acci-
according to the 6th principle of green chemistry, industrial-scale dents such as fires and explosions (12th
ionic liquid preparations are greener than their laboratory-scale principle). To summarise, only eight of
cousins. the twelve principles of green chemistry
It is important to re-emphasise that in this paper, all are relevant to the synthetic procedures discussed here, viz. 1st,
greenness arguments are focussed solely on the preparative 2nd, 3rd, 5th, 6th, 8th, 11th and 12th.
steps of laboratory-scale ionic liquid preparations (<2 kg). Although, strictly speaking, the twelve principles of green
Although our approach will be expanded in the future to chemistry only apply to synthetic procedures, the 1st, 5th, 6th
include a cradle-to-grave approach for both small and large and 12th principles are relevant to ionic liquid purification
scales preparations, our primary aim was to first develop a user- procedures and, therefore, we have assessed the purification of
friendly greenness assessment protocol. As more information the salts according to these four principles too.
becomes available for large scale ionic liquid syntheses, our
evaluation protocol will be extended to gauge the greenness
of industrial scale ionic liquid preparations by including, for
Atom economy and the E-factor
example, the twelve principles of green engineering6 in our
assessments, as well as quantitative considerations of energy In addition to applying the twelve principles of green chemistry
efficiency using different heating sources. Ultimately, we en- to evaluate the green credentials of ionic liquid syntheses and
visage that our greenness analyses will also incorporate life purifications, these methods can also be assessed using two
cycle assessments, which take into account the greenness of additional measures, viz. atom economy19 and the E-factor.20
ionic liquid starting materials plus the ionic liquid product Atom economy (also known as atom efficiency) provides,
itself. for a given reaction, the ratio between the mass of the atoms
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making up the final product(s) and the mass of the atoms that Strengths, weaknesses, opportunities and threats
are incorporated in all the reactants, eqn (1). It should be noted (SWOT) analyses
that the atom economy is a theoretical construct based solely
on the stoicheiometry of a given reaction, and assumes 100% In order to simultaneously assess the green credentials of the
yield. Stated more simply, atom economy measures how many selected synthetic and purification procedures of ionic liquids in
of the atoms present in the starting materials form part of terms of the twelve principles of green chemistry, atom economy,
the final product, and is reported as a percentage value with and the E-factor, we have applied a common tool used in strate-
those values closest to 100% reflecting superior atom economies. gic planning, viz. strengths, weaknesses, opportunities, threats
For example, the preparation of 1-alkyl-3-methylimidazolium (SWOT) analysis.21 For ionic liquid preparation and purification
halide salts using quaternisation (Routes 1(a)–(d), Fig. 2) are methods, SWOT analyses involve specifying the objective(s) of
100% atom efficient, regardless of the yield obtained, since a given procedure (e.g. obtaining an ionic liquid that is >99%
no by-products are formed. On the other hand, ionic liquids pure) and identifying the internal and external factors that are
prepared using one-pot (Routes 2(a)–(c), Fig. 2) or metathesis favourable and unfavourable to achieving that objective. Thus,
reactions (Route 3, Fig. 2) will be <100% atom efficient since a SWOT analyses give an overview of the relative advantages or
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stoicheiometric amount of MCl waste is generated. disadvantages of ionic liquid syntheses and purifications. In
brief, the SWOT analyses provided here (represented skeletally
in Fig. 4) give a measure of the balance between good and
Molecular weight of desired product (s) bad for some common ionic liquid preparation and purification
%Atom economy = *100
Sum of molecular weight of all reagents procedures, and indicate potential directions for improving these
(1) methods.
The ‘ideal’ E-factor is reflected in the 2nd principle of green Greenness assessment: traditional synthesis of
chemistry that states: ‘Synthetic methods should be designed to
1-alkyl-3-methylimidazolium halide salts
maximise the incorporation of all materials used in the process
into the final product’.5 In other words, for a chemical process to It is safe to say that the methods used to prepare 1-alkyl-3-
have an E-factor of zero, all materials used in a process (and not methylimidazolium halide salts11 have changed very little since
just the reagents) should be contained in the final product if the they were first reported in 1982;22 most reported syntheses
process is truly green. still involve reaction of 1-methylimidazole with an excess of 1-
If we necessarily assume the process of producing an ionic haloalkane and are promoted using conductive heating, Route
liquid is the process of producing a pure, isolated ionic liquid, 1(a), Fig. 2. However, from a green chemistry perspective, much
then the E-factor for the process, which combines Fig. 2 and room for improvement exists in the syntheses of 1-alkyl-3-
Fig. 3, must be considered. Although every chemical reaction methylimidazolium halide salts, particularly regarding the use
will have its own unique % atom economy and E-factor, to of more efficient energy sources and reducing/eliminating the
simplify discussion, the atom economies and E-factors asso- need for organic solvents during both synthesis and purification;
ciated with ionic liquid preparations and purifications (Fig. 2 all these issues are discussed below.
and 3) have respectively been designated as low/medium/high The literature shows that the vast majority of 1-alkyl-3-
and poor/good/excellent, since the literature has rarely given methylimidazolium halide salt preparations are executed using
enough detail to allow definitive values to be assigned. traditional heating under reflux, although nowadays an atmo-
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sphere of dry dinitrogen is sometimes used since it has been flask, for example. Therefore, microwave-promoted preparations
found to promote the production of colourless ionic liquids11 align better with the 6th principle of green chemistry than
and also prevents the formation of hydrated halide salts from conventionally-heated ionic liquid syntheses.
adventitious water.23 When all the above-mentioned negative factors associated
Almost without exception, reported preparations of 1-alkyl-3- with the traditional syntheses of 1-alkyl-3-methylimidazolium
methylimidazolium halide salts use an excess of 1-haloalkane,24 halide ionic liquids are considered, it is safe to say that
which means that the reactions are not in line with the 2nd their preparations are not green. Indeed, of the eight rel-
principle of green chemistry that states: ‘Synthetic methods evant principles of green chemistry, they only comply with
should be designed to maximize the incorporation of all materials three principles (viz. the 8th, 11th and
used in the process into the final product’.5 It also means 12th) which apply to all the ionic liq-
that although the preparations of the halide salts are 100% uid syntheses discussed here anyway.
atom efficient, with every atom of the starting materials being On the other hand, the E-factors for
incorporated into the final product, their E-factors are very poor, the preparations fall between good and
since excess 1-haloalkane is required to promote completion of excellent, provided excess 1-haloalkane
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the reactions at a reasonable rate. It also follows that the smaller is kept to a minimum and no harm-
the excess of 1-haloalkane, the lower the E-factor value will be, ful organic solvent is used during the
provided no organic solvent is used during the preparation. For preparation, and any solvent that is used is recycled. As a
example, the E-factors for the preparation of [C4 mim]Cl (molar whole, however, the conductively-heated preparations of 1-alkyl-
mass = 174.1 g mol-1 ) are 0.106 and 0.005 when 20% and 1% 3-methylimidazolium halide salts possess a lot of room for
mol excesses of 1-chlorobutane (molar mass = 92.56 g mol-1 ) improvement, as indicated by their SWOT analysis (vide infra).
are employed, respectively.
Some reported syntheses of 1-alkyl-3-methylimidazolium
halide salts also make use of an organic solvent;25 to reduce the Greenness assessment: purification of
viscosity of the reaction mixture and thus improve mass transfer,
1-alkyl-3-methylimidazolium halide salts
but also to control the reaction temperature and prevent product
scrambling.26 However, the employed molecular solvent, as well The purifications of 1-alkyl-3-methylimidazolium halide salts
as the employed excess of 1-haloalkane, require removal and (Scheme 1) are generally dirty, with poor E-factors, since the
subsequent disposal, which also do not comply with the 1st excess 1-haloalkane, unconverted 1-methylimidazole, as well as
principle of green chemistry that states: ‘It is better to prevent any solvent used during their preparation, require removal and
waste than to treat or clean up waste after it has formed’.5 are thus out of line with the 5th principle of green chemistry.5
Therefore, the practice of employing an organic solvent during In our laboratories, removal of the excess 1-haloalkane and
the preparation of 1-alkyl-3-methylimidazolium halide salts unconverted 1-methylimidazole is typically achieved by first
further increases the E-factor and is highly undesirable. For adding a solvent such as ethanenitrile to the crude ionic liquid
example, if 100 g of toluene is used during the synthesis of mixture and then repeatedly washing this phase with ethyl
[C4 mim]Cl (and using a 20 mol% excess of 1-chlorobutane), the ethanoate. Once the washing process is complete, the two organic
E-factor increases from 0.106 to 0.681. solvents are removed under reduced pressure (using a rotary
The 5th principle of green chemistry states that: ‘The use of evaporator). Since the amount of organic solvent used for the
auxiliary substances (e.g. solvents, separation agents, etc.) should purification, as well as the excess of reagents, are classified as
be made unnecessary wherever possible and innocuous when used,’5 waste in the E-factor equation, the more of each that is used, the
which means that, ideally, no solvent should be used during higher the E-factor will be for a given purification procedure.
preparation, but if a solvent is to be used, it must be green and In less experienced groups, the purification of 1-alkyl-3-
recycled. In order to align with the 1st, 2nd and 5th principles of methylimidazolium halide salts is often performed on the bench,
green chemistry, and have low E-factor values, neither an excess and thus the salts absorb water from the atmosphere, that
of 1-haloalkane nor organic solvent should be used during the also requires removal. It must be noted, however, that this
synthesis of 1-alkyl-3-methylimidazolium halide salts. adventitious water cannot be completely removed from ionic
The use of conductive heating (usually an oil bath or heating liquids containing halide anions (especially chloride), as they
mantle) to prepare 1-alkyl-3-methylimidazolium halide salts is form, typically, very stable hydrates (see, for example, Fig. 5).23
also in opposition with the 6th principle of green chemistry Therefore, if water-free ionic liquids containing halide ions are
that states: ‘Energy requirements should be recognized for their desired, their preparation and purification must be conducted
environmental and economic impacts and should be minimised. under strictly anhydrous conditions from start to finish, e.g.
Synthetic methods should be conducted at ambient temperature using Schlenk techniques, with rigorously predried reagents.
and pressure.’5 Therefore, since conductive heating is slow, it Nevertheless, some adventitious water can be removed by
is also energy inefficient because the transfer of heat from the heating 1-alkyl-3-methylimidazolium halide salts under reduced
heat source to the reaction mixture depends on the thermal pressure at ca. 70 ◦ C for several hours. Almost needless to
conductivities of all the materials that must be penetrated say, removing water in this way requires a large energy input
such as the flask and solvent. In contrast, microwave-promoted and thus contributes further to the green inefficiency (via non-
ionic liquid preparations require lower (heating) energy inputs compliance with the 6th principle of green chemistry)5 of the
since microwaves penetrate the reaction mixture directly and purification of 1-alkyl-3-methylimidazolium halide salts. Indeed,
are not limited by the thermal conductivities of the reaction the purification of 1-alkyl-3-methylimidazolium halide salts, as
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Fig. 5 Structures of 1,3-dimethylimidazolium chloride hemihydrate (left) and 1,2-dimethyl-3-ethylimidazolium chloride hemihydrate (right) showing
hydrogen bonding (dashed lines), as determined by single crystal X-ray diffraction.23
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At present, the implementation of REACH (registration, eval- sents a far more efficient mode of heating to prepare ionic
uation, authorisation and restriction of chemicals)27 legislation liquids than conductively-heated syntheses. In other words,
is a threat to the continued low-cost manufacturer of many ionic liquids represent a superlative method for microwave
chemicals, but especially for new products, since they require heating.
a large initial financial investment. Therefore, research scientists At present, the implementation of microwave irradiation
aiming to develop any new industrial-scale ionic liquid synthesis to prepare ionic liquids continues to evolve, but a question
need to be extremely familiar with REACH legislation in order that remains unanswered is: how much greener are microwave-
to achieve their aim. A further threat that exists for the synthesis promoted preparations than traditional methods? From a
of 1-alkyl-3-methylimidazolium halide salts using conductive very simplistic standpoint, tremendous energy savings have
heating is that starting material costs will undoubtedly rise and, already been demonstrated for laboratory-scale ionic liquid
therefore, the challenge facing chemists is to render preparations syntheses,13,29 since microwave-promoted reactions occur far
greener and concomitantly cheaper. more rapidly than the same preparations performed using
conductive heating. This strongly aligns with the 6th principle
of green chemistry5 by keeping the energy input of the syntheses
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Fig. 7 Commercially available microwave reactors for batch synthesis (left) and for continuous flow synthesis (right). Photographs courtesy of
Milestone s.r.l., Sorisole, BG, Italy.
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Greenness assessment: syntheses of ionic liquids liquid syntheses considered here have
promoted by ultrasonic irradiation poor E-factors too and thus are not as
green as their microwave-assisted ana-
At about the same time that the first reports describing the logues.
microwave-assisted preparations of ionic liquids were published,
reports also began to appear describing ultrasound-promoted
preparations of ionic liquids.40,41
The promotion of chemical reactions with ultrasound is due
to a physical phenomenon known as cavitation, which is the SWOT analysis: ultrasound-promoted syntheses of
formation, growth, and implosive collapse of bubbles in a ionic liquids
liquid.42 The collapse or implosion of such bubbles results in The SWOT analysis for the preparation of ionic liquids pro-
some fascinating physical effects, which include the formation moted by ultrasonic irradiation (Fig. 9) reveals that its unique
of localised ‘hotspots’ in an elastic liquid and reduction of strength (compared to traditional and microwave-assisted syn-
bubble size.43 In terms of ionic liquid synthesis, the formation
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[C4 mim][NTf2 ] and [C4 mim][OTf] is achieved by washing the reused, although some contaminated ionic liquid, now severely
crude ionic liquid product with water, although the ease with contaminated with MX, will remain, since even hydrophobic
which this is achieved, and the respective green performances, ionic liquids exhibit mutual solubility with water.2 Moreover,
vary considerably. the water must be removed in order to obtain the pure salt; this
Although a stoicheiometric amount of MX waste is generated is achieved by drying the salt in vacuo at ~70 ◦ C for many hours,
during two-step ionic liquid syntheses, it is not toxic waste, which is extremely energy inefficient.
and thus does not require incineration. Furthermore, the metal In brief, the purification procedure of [C4 mim][OTf] is far less
halide waste is not contaminated with organics, which means efficient than that of its [C4 mim][NTf2 ] cousin, since a significant
that both one- and two-step syntheses to produce [C4 mim][NTf2 ] amount of the ionic liquid is ‘lost’ to the organic phase and
and [C4 mim][OTf] closely align with the 1st principle of green higher levels of MX also remain in the purified ionic liquid.
chemistry.5 This is evidenced by the lower chloride content levels achievable
for [C4 mim][NTf2 ]49 than for [C4 mim][OTf].12,50 In addition, less
energy is required to remove residual water from [C4 mim][NTf2 ]
Greenness assessment: purification of hydrophobic than for [C4 mim][OTf] by heating the salts in vacuo, as the former
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vs. hydrophilic ionic liquids should, by definition, hold less water than the latter. Although
In order to remove MX from hydrophilic [C4 mim][OTf], the purification of these ionic liquids does not comply with the
dichloromethane, a dense solvent, is usually added to the relevant principles of green chemistry (viz. the 1st, 5th, and 6th),
crude ionic liquid mixture. The dichloromethane is added the hydrophobic ionic liquid processes are much greener than
since the ionic liquid preferentially dissolves therein, allowing the hydrophilic, both in total isolated yield and avoidance of
repeated washing of the ionic liquid-containing phase with organic solvents.
cold water to remove the MX waste more easily. The residual
dichloromethane, as well as the water that remains in the ionic SWOT analyses: purification of hydrophobic and
liquid as a result of the washing procedure, require removal hydrophilic ionic liquids
that is achieved by first using a rotary evaporator and then
drying the salt in vacuo at ~70 ◦ C for many hours, which is The SWOT analyses for the purification of [C4 mim][NTf2 ] and
extremely energy inefficient. Almost needless to say, the use of [C4 mim][OTf] show that the former procedure is the greener
dichloromethane to purify [C4 mim][OTf] is an extremely dirty (Fig. 11). This is mainly due to the purification of [C4 mim][OTf]
practice, since it is a toxic solvent that is detrimental to both requiring the use of dichloromethane, which is an extremely
humans and the environment.48 Furthermore, the larger the harmful compound. Another major reason why the purification
volume of dichloromethane used, the poorer the E-factor of of [C4 mim][OTf] is dirty, is because much greater losses of
the procedure. the ionic liquid to the water phase occur compared to the
The removal of MX from hydrophobic [C4 mim][NTf2 ] is far purification of [C4 mim][NTf2 ] and it also requires longer heating
easier than its removal from [C4 mim][OTf] because it does not in vacuo to remove residual water.
readily mix with water and, therefore, washing the salt with water
to extract MX is both faster and more efficient. This purification
Decolourisation of ionic liquids
is also greener, since no organic solvent is required, as is the
case for hydrophilic salts, to aid with the removal of MX. In All practicing ionic liquid synthetic chemists know that the
principle, the water phase can also be recycled by distillation and salts are sometimes obtained as pale yellow to black prod-
Fig. 11 SWOT analyses for the purification of [C4 mim][NTf2 ] (left) and [C4 mim][OTf] (right).
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x
8
Methodology E-factor Atom economy Principles of green chemistry uphelda
Route 1 (b) Excellent High 7 (1st, 2nd, 5th, 6th, 8th, 11th, 12th)
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Route 2 (a) Poor–good Low–medium 7 (1st, 2nd, 5th, 6th, 8th, 11th, 12th)
Route 2 (c) Very poor Low–medium 5 (5th, 6th, 8th, 11th, 12th)
a
The 4th, 7th, 9th and 10th principles of green chemistry do not apply.
ucts. Ionic liquids containing halide anions are particularly the extremely low levels of the chromophores in ionic liquids
susceptible to discolouration, and the cause of the colour can (probably ppb levels). It is worth noting that even some of the
be transferred to derived ionic liquids prepared by metathesis most intensely coloured ionic liquids are usually analytically
(Route 3, Fig. 3). Although intense chromophores (extinction pure to NMR spectroscopy and mass spectrometric techniques.
coefficients > 106 mol l-1 cm-1 ) are the suspected discolouration The colour of an ionic liquid is usually not detrimental when
culprits,51 the true cause (and indeed the types of chromophores using the salts as solvents (provided that they contain minimal
responsible) remains a mystery. To date, attempts to isolate levels of other impurities such as chloride and/or water), but
the chromophores by column chromatography have failed to colourless ionic liquids are essential for spectroscopic studies, in
provide enough material for identification. This failure indicates order to eliminate interference from the suspected chromophoric
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impurity resonances that usually appear in the UV-Vis spectra; 9 A. J. Carmichael, M. Deetlefs, M. J. Earle, U. Fröhlich and K. R.
the impurity is also often strongly luminescent. Seddon, in Ionic Liquids as Green Solvents: Progress and Prospects,
eds. R. D. Rogers and K. R. Seddon, American Chemical Society,
Washington D.C., 2003, pp. 14–31.
Conclusions 10 A. Stark, and K. R. Seddon, in Kirk-Othmer Encyclopaedia of
Chemical Technology, ed. A. Seidel, John Wiley & Sons, Inc.,
In conclusion, we believe this is the first critical assessment Hoboken, New Jersey, 2007, pp. 836–920.
11 C. M. Gordon, and M. J. Muldoon, in Ionic Liquids in Synthesis,
of the greenness of the synthetic procedures and purification eds. P. Wasserscheid and T. Welton, Wiley-VCH, Weinheim, 2008,
methodologies commonly used for the synthesis of ionic liquids, pp. 7–25.
which are summarised in Table 1. 12 K. R. Seddon, A. Stark and M.-J. Torres, Pure Appl. Chem., 2000,
72, 2275–2287.
To maintain green credibility, ionic liquids must be both green
13 M. Deetlefs and K. R. Seddon, Green Chem., 2003, 5, 181–186.
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assisted synthesis is employed. It is also clear that the purifi-
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the use thereof for the synthesis of ionic liquids, WO Pat. 2001077081
cation of hydrophobic ionic liquids is intrinsically greener than (2001).
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