Assessing The Grenness of Some Typical Laboratory Ionic Liquid Preparations", M. Deetlefs, K. R. Seddon, Green Chem. 12, 17-30 (2010)

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PERSPECTIVE www.rsc.org/greenchem | Green Chemistry

Assessing the greenness of some typical laboratory ionic liquid preparations


Maggel Deetlefs* and Kenneth R. Seddon
Received 27th July 2009, Accepted 22nd October 2009
First published as an Advance Article on the web 8th December 2009
DOI: 10.1039/b915049h

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

Maggel joined the QUILL Ken Seddon was appointed as


Research Centre as a post- chair of Inorganic Chemistry
doctoral researcher in 2001 and at the Queen’s University of
has since advanced to the posi- Belfast in 1993, where in 1999,
tion of Assistant Director, with he also co-founded the QUILL
the dual-purpose of managing Centre with Prof. W. J. Swin-
the Centre and maintaining her dall OBE. The QUILL Centre
own research portfolio. Her re- currently has a complement of
search interests focus on the 89 staff, including 64 research
green synthesis and applica- staff, students and technicians,
tions of ionic liquids, including as well as 14 associated aca-
purpose-specific design and de- demics. For more details about
veloping simple methods to pre- Ken, Maggel, and QUILL see
Maggel Deetlefs dict their physical properties. Ken Seddon http://quill.qub.ac.uk

This journal is © The Royal Society of Chemistry 2010 Green Chem., 2010, 12, 17–30 | 17
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Fig. 1 The twelve principles of green chemistry.5

Fig. 2 Typical ionic liquid purification routes.12

18 | Green Chem., 2010, 12, 17–30 This journal is © The Royal Society of Chemistry 2010
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Fig. 3 Typical ionic liquid synthetic routes.

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 problem with employing atom economy to evaluate the


green credentials of a reaction is that it does not take into
account that some reactions with favourable stoicheiometries
require large excesses of reagents, give poor yields, and often
generate large amounts of unwanted by-products. This, of
course, highlights the basic flavour in the atom economy concept,
viz. it is necessary but not sufficient, since a reaction giving 0.5%
yield can still be described as 100% atom efficient. As a result,
the E-factor concept was introduced, where all compounds that
are not product are classified as waste. The nature of the E-factor
equation, eqn (2), dictates that the greenest chemical reactions
have E-factor values close to zero. In brief, the E-factor gives
a much truer reflection of the greenness of a chemical reaction
than atom economy, since all generated waste is accounted for.

Amount of waste produced in the process / kg


E-factor =
Amount of the desired product (s) produced in the process/kg Fig. 4 Skeletal strengths weaknesses opportunities threats (SWOT)
analysis.
(2)

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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Scheme 1 Schematic for the purification of [C4 mim]X ionic liquids.

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

summarised in Scheme 1, complies with none of the relevant


principles of green chemistry viz. the 1st, 5th, 6th and 12th.

SWOT analysis: conductively-heated preparation of


1-alkyl-3-methylimidazolium halide salts and their
subsequent purification
Examination of the SWOT analysis for the preparation of 1-
alkyl-3-methylimidazolium halide salts using conductive heating
and their subsequent purification (Fig. 6) shows that the overall
methodology is dirty. Nevertheless, the procedure possesses
some strengths, viz. the processes are well-established, simple,
can be performed in even the most basic of laboratories to
produce the salts on a small to medium scale (<1 kg), and possess
100% atom economies. On the other hand, both the preparations
and purifications share the weakness of poor E-factors, since
extensive purification is necessary to remove the excess of 1-
haloalkane employed, which generates large volumes of solvent
waste. Further weaknesses are that large-scale preparations (>1 Fig. 6 SWOT analysis: conductively-heated preparation of 1-alkyl-3-
kg) and purifications are laborious, and the use of conductive methylimidazolium halide salts and their subsequent purification.
heating to promote the reactions, as well as to remove some resid-
ual water and organic solvents, is slow and energy inefficient. All methylimidazolium halide salts using conductive heating, and
the aforementioned weaknesses show that opportunities exist thus reduce the costs of their manufacture, especially on large
to develop a greener methodology to prepare pure 1-alkyl-3- scales.

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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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Greenness assessment: ionic liquid syntheses


to a minimum.
promoted by microwave irradiation
The first papers describing microwave syntheses of ionic
It has long been recognised that much more efficient energy liquids employed domestic microwave ovens that offered no
sources exist to promote chemical reactions than conduc- temperature and pressure control and thus gave irreproducible
tive heating. In particular, microwave irradiation,13,28–31 has results.31–33 Since then, more reliable results have been obtained
started to attract attention for the preparation of ionic liq- using commercial microwave reactors (Fig. 7), which have
uids (Routes 1(b) and 2(a), Fig. 3), and a wide variety of allowed the temperature and pressure of reactions to be moder-
ionic liquids have been prepared to date using microwave ated, rendering the procedures far safer and more reproducible
reactors.32 than their domestic predecessors.34
The promotion of 1-alkyl-3-methylimidazolium halide syn- It is worth noting that while the first reports describing
theses using microwave irradiation is favoured by an ionic microwave-assisted ionic liquid syntheses focussed on their
conduction heating mechanism.30 This is because ionic liquids preparation via quaternisation (Route 1(b), Fig. 3), later
absorb microwave irradiation not only by a dipole rotation reports33,35,36 showed that a one-pot approach (Route 2(a),
mechanism, but they also oscillate back and forth under Fig. 3) could also be used. Since the microwave-assisted pro-
the influence of the electric field of the microwave.13,30 These cedures require much smaller 1-haloalkane excesses (~1 mol%)
‘ionic oscillations’ result in collisions with neighbouring ions compared to conventional preparations (up to 400 mol%),24
and molecules, which generate heat, and thus speed up the they align well with the 1st principle of green chemistry and
reaction. In other words, the more ionic liquid product that their E-factors are far superior to traditional synthetic routes,
has formed during a given preparation, the faster the re- especially conducted in the absence of additional solvent. In
action will proceed. In brief, microwave irradiation repre- other words, if no organic solvent is used during the synthesis, the

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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preparations also align with the 2nd principle of green chemistry


and the best E-factors for the preparations are obtained. In
brief, the microwave-assisted syntheses
of 1-alkyl-3-methylimidazolium halide
salts comply with seven of the eight
relevant principles of green chemistry
(viz. the 1st, 2nd, 5th, 6th, 8th, 11th
and 12th) while the analogous one-
pot microwave-assisted syntheses align
with six (viz. the 1st, 5th, 6th, 8th,
11th and 12th). It must be noted that although the one-pot
microwave-assisted ionic liquid syntheses
generate a stoicheiometric amount of
MX waste (e.g. NaCl), the waste salt is far
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less harmful/toxic and straightforward


to dispose of compared to 1-haloalkane
waste and thus the methodology aligns
reasonably well with the 1st principle of
green chemistry too.
Fig. 8 SWOT analysis for the preparation of ionic liquids using
microwave irradiation.
Microwave-assisted vs. traditional ionic liquid
preparations
The superior E-factors and energy efficiencies of microwave-
assisted syntheses of ionic liquids show that they are far greener
preparations. All the these strengths render the microwave-
than conductively-heated preparations. However, the ‘degree
promoted syntheses of ionic liquids very green indeed.
of greenness’ depends on (i) the type of quaternisation being
Weaknesses associated with microwave-assisted preparation
performed, since the kinetics of the reaction typically follow the
of ionic liquids are:
order: Cn H2n+1 Cl < Cn H2n+1 Br < Cn H2n+1 I, (ii) the 1-haloalkane
∑ Currently, there is a lack of energy efficiency data for
excess required to achieve complete conversion to product, (iii)
syntheses vs. other methodologies
the scale of the reaction, and (iv) whether any solvent is necessary
∑ Microwave reactors are expensive compared to traditional
to reduce the viscosity and/or reduce product scrambling.26
synthetic apparatus
The proviso for the use of solvent in terms of green chemistry
∑ Discoloured ionic liquids are sometimes obtained at tem-
is that the solvent itself will have to be green (e.g. ethanol)
peratures >75 ◦ C38
and/or recycled to uphold the overall green credentials of a
∑ Ionic liquids decompose if overheated13,26,39
given preparation.
∑ The high viscosity of ionic liquids can produce mass
The preparation of ionic liquids on scales >2 kg also requires
transport problems during synthesis
special consideration, as this is moving from bench scale to
∑ The scale-up of the syntheses is very expensive.
semi-pilot plant scales. However, at semi-pilot plant scale, the
Despite the weaknesses mentioned above, opportunities exist
twelve principles of green engineering6 must also be considered,
for the development of green microwave reactor technology
but this falls outside the scope of this review. Nevertheless,
to produce ionic liquids. One major opportunity is green
current indications are that continuous flow reactors (see Fig. 7)
process development by establishing quantitative energy input
represent the way forward in producing ionic liquids on large
data to definitively assess the greenness of microwave-assisted
scales.32,37
preparations vs. other methodologies. Another opportunity is
the design and manufacture of custom-made reactors to produce
SWOT analysis: microwave-promoted syntheses of ionic liquids on large scales.37 Both these opportunities may
generate valuable intellectual property and could also reduce
ionic liquids
the cost of producing ionic liquids on large scales.
The SWOT analysis for the preparation of ionic liquids using The largest threat to the development of microwave technol-
microwave irradiation is shown in Fig. 8. ogy to produce ionic liquids on large scales by continuous flow is
The greatest green strengths of performing microwave- that it proves too expensive. Further threats include the inability,
assisted ionic liquid preparations on a laboratory scale are via design constraints, to incorporate in situ reaction monitoring
the energy reduction by virtue of reduced reaction times (which aligns with the 11th principle of green chemistry) and
and low 1-haloalkane excesses. Further strengths are that (i) the inability (albeit unlikely) to incorporate safety controls in
different microwave reactors30 can be employed to execute the industrial reactors to produce ionic liquids on large scales (which
preparations on different scales,32 (ii) syntheses can be performed aligns with the 12th principle of green chemistry). Also, the low
solvent-free, (iii) the reactions are 100% atom efficient and (iv) penetration of microwaves limits the size of the reactor; syntheses
have excellent (low) E-factor values compared to traditional of over 2 kg will require a flow system.

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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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theses) is improved mass transport. However, almost without


of hotspots favours quaternisations (Route 1(c), Fig. 3), while exception, the preparations have very poor E-factors due to
the reduction of bubble size favours both quaternisations and the discoloured ionic liquid products, which require extensive
metathesis (Route 3, Fig. 3)40 since improved mass transport purification and decolourisation efforts that produce large
overcomes the viscosity issues generally associated with ionic volumes of organic solvent and solid waste (vide supra). In
liquid syntheses. Hotspot formation, bubble size reduction and addition to the major weakness of a poor E-factor, other
the reduced preparation times compared to traditional methods weaknesses of ultrasound-assisted ionic liquid syntheses include
all combine to speed up ionic liquid syntheses, and thus represent the lack of quantitative energy efficiency data, the cost of the
a significant green advantage, especially if the preparations apparatus, and the lack of demonstrated large-scale production.
are performed solvent-free. Indeed, it is worth noting that at It must be pointed out that ionic liquid discolouration is far
present, the majority of papers describing ultrasound-promoted more severe under ultrasonic conditions than under microwave
syntheses of ionic liquids have focussed on ‘one-pot’ reactions irradiation and, furthermore, the salts decompose under even
(Route 2(b), Fig. 3). mild ultrasonic conditions.44
Despite the apparent green advantages of ultrasound-assisted
ionic liquid preparations, a phenomenon which renders these
preparations inadequate is that, almost without exception,
ionic liquids discolour and decompose when exposed to ul-
trasonic irradiation for the time required to obtain acceptable
conversions.44,45 Needless to say, this decomposition of ionic
liquids is a severe disadvantage to the successful and widespread
implementation of the technology and, from a green chemistry
perspective, does not align with the 1st principle of green
chemistry, since very dirty purification and decolourisation of
the salts is required, which also gives very poor E-factors.
In addition, in a recent review, the highest reported tabu-
lated yields to produce 1-alkyl-3-methylimidazolium halides
and similar salts without halide anions are 95 and 90%,
respectively.46 This contrasts with yields of >99% obtained
by thermally-induced and microwave-assisted preparations,
rendering ultrasound-assisted ionic liquid syntheses far less
green.
Although ultrasound-assisted synthe-
ses of 1-alkyl-3-methylimidazolium ionic
liquids (Route 1(c) and 2(b), Fig. 3) Fig. 9 SWOT analysis for the preparation of ionic liquids using
comply with five of the eight relevant ultrasonic irradiation.
principles of green chemistry (viz. the
5th, 6th, 8th, 11th and 12th), they do The greatest opportunities that exist for ultrasound-promoted
not follow the 1st and 2nd principles, ionic liquid syntheses are (i) to develop green procedures that
since they give poor yields (compared do not lead to the discolouration and decomposition of ionic
to thermal and microwave routes), and the ionic liquid prod- liquids, and (ii) to determine the true energy efficiency of the
ucts require extensive purification. This is especially true for preparations compared to other methodologies by collecting
ionic liquids prepared by anion exchange under the influ- quantitative energy input data, thus creating the opportunity
ence of ultrasonic irradiation (Route 3, Fig. 3), which only for (iii) reactor design and (iv) generating valuable intellectual
comply with three of the eight (viz. 8th, 11th and 12th) property.
principles of green chemistry, and these are met by all ionic It must be reiterated that ultrasound-assisted ionic liquid
liquid preparations anyway. All the ultrasound-assisted ionic preparation will probably only find commercial application if its

This journal is © The Royal Society of Chemistry 2010 Green Chem., 2010, 12, 17–30 | 25
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severe shortcomings (or threats in terms of the SWOT analysis)


are overcome by future research and development efforts. Such
research and development efforts will, similarly to microwave-
assisted preparations, have to include safety controls and in situ
reaction monitoring to align with the 11th and 12th principles
of green chemistry.

Greenness assessment: simultaneous use of


microwave and ultrasonic irradiation to prepare ionic
liquids
Recent studies have shown that the simultaneous use of mi-
crowave and ultrasonic irradiation can be used to promote
ionic liquid syntheses by one-step (Route 1(d), Fig. 3), two-step
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(Routes 1(a) then Route 3, Fig. 3), as well as one-pot (Route


2(c), Fig. 3) procedures.36,46,47
The simultaneous use of microwave and ultrasonic irradiation
to prepare ionic liquids should offer the cumulative benefits of
the individual irradiations, viz. excellent coupling of microwaves
Fig. 10 SWOT analysis for the preparation of ionic liquids using
with ionic liquids plus improved mass transport. Therefore,
simultaneous ultrasound and microwave irradiation.
the time and energy saved using microwave and ultrasonic
irradiation simultaneously would represent a significant green
ductive heating and microwave-assisted preparations), (iv) the
advantage, especially if the syntheses are solvent-free. However,
potential to perform the transformations solvent-free, and (v)
using this technology to prepare 1-alkyl-3-methylimidazolium
high atom economies. At present, however, the limited number
halide salts (Route 1(d), Fig. 3) gives very poor yields (<5%)
of studies describing syntheses have shown that the technology
and can also take significantly longer than using microwave
works best for one-pot preparations (Route 2(c), Fig. 3), and
or ultrasound irradiation alone.36 Therefore, the combined use
is less successful for preparing ionic liquids containing halide
of microwave and ultrasonic irradiation to prepare 1-alkyl-3-
anions.36 The SWOT analysis clearly shows, without labouring
methylimidazolium halide salts has a very poor E-factor, and
the point, that at present, the combined microwave/ultrasound
uses significantly more energy than using the individual types of
irradiation technology has both obvious advantages and severe
irradiation alone, rendering the syntheses dirty. In addition, a
disadvantages.
major problem that is anticipated for all ionic liquid syntheses
using microwave and ultrasonic irradiation simultaneously is
that discoloured ionic liquid products will be obtained, requiring Greenness assessment: purification of ionic liquids
extensive decolourisation, which will have a further negative with non-halide anions
effect on the E-factors.
Although the simultaneous microwave/ultrasound-assisted Ionic liquid purification procedures can be divided into two
preparations of 1-alkyl-3-methylimidazolium halide (Route main categories, viz. purification of hydrophobic ionic liquids
1(d), Fig. 3) and non-halide (Route 2(c), Fig. 3) salts comply and purification of hydrophilic ionic liquids (Fig. 2). To
with five of the eight relevant principles of green chemistry simplify discussion for the former and latter categories, we
(viz. the 5th, 6th, 8th, 11th and 12th), they do not follow have selected two stereotypical salts as representatives, viz.
the 1st and 2nd principles, since they give 1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}-
poor yields (compared to thermal and amide, [C4 mim][NTf2 ], and 1-butyl-3-methylimidazolium
microwave routes) and the ionic liquid trifluoromethanesulfonate, [C4 mim][OTf]. It must be noted
products require extensive purification. that 1-alkyl-3-methylimidzaolium halide salts fall in the
In addition, the E-factors of the prepa- above-mentioned hydrophilic category, but their purification
rations are poor due to the need to and associated green performance have already been discussed
decolourise the ionic liquid products. (vide supra).
On examination of the twelve principles of green chemistry,
SWOT analysis: simultaneous use of microwave and it is clear that only the 1st, 5th, 6th and 12th principles
are relevant to ionic liquid purification. This is because the
ultrasonic irradiation to prepare ionic liquids
remaining principles of green chemistry only address synthetic
The simultaneous use of microwave and ultrasonic irradiation methodologies.
to prepare ionic liquids offers both the best and worst of the Regardless of whether a one- or two-step methodology is
individual technologies (A Tale of Two Technologies?), and the employed to prepare [C4 mim][NTf2 ] or [C4 mim][OTf] (Fig. 3),
SWOT analysis shows that this is indeed true (Fig. 10). a stoicheiometric amount of MX waste (usually NaCl) is
The expected strengths of the technology include (i) rapid generated. If not removed from the ionic liquid product, the
preparations with (ii) good energy efficiencies compared to presence of the metal halide waste will severely affect the physical
traditional methods, (iii) improved mass transport (vs. con- properties of the ionic liquid.10,12 The removal of MX from both

26 | Green Chem., 2010, 12, 17–30 This journal is © The Royal Society of Chemistry 2010
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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).

This journal is © The Royal Society of Chemistry 2010 Green Chem., 2010, 12, 17–30 | 27
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Table 1 How green is my procedure?

x
8
Methodology E-factor Atom economy Principles of green chemistry uphelda

Route 1 (a) Good–excellent High 3 (8th, 11th, 12th)

Route 1 (b) Excellent High 7 (1st, 2nd, 5th, 6th, 8th, 11th, 12th)
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Route 1 (c) Poor Low–high 5 (5th, 6th, 8th, 11th, 12th)

Route 1 (d) Poor High 5 (5th, 6th, 8th, 11th, 12th)

Route 2 (a) Poor–good Low–medium 7 (1st, 2nd, 5th, 6th, 8th, 11th, 12th)

Route 2 (b) Poor Low–medium 5 (5th, 6th, 8th, 11th, 12th)

Route 2 (c) Very poor Low–medium 5 (5th, 6th, 8th, 11th, 12th)

Route 3 Poor Low–medium 3 (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.
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13 M. Deetlefs and K. R. Seddon, Green Chem., 2003, 5, 181–186.
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