Review Clean Products and Processes 1 (1999) 223236 Q Springer-Verlag 1999

223
Ionic Liquids
J.D. Holbrey, K.R. Seddon
Received: 14 May 1999 / Accepted: 10 July 1999
J.D. Holbrey, K.R. Seddon
The QUILL Centre, The Queens University of Belfast
Stranmillis Road, Belfast BT9 5AG UK
e-mail: J.Holbrey6qub.ac.uk
http://www.ch.qub.ac.uk/staff/personal/krs
e-mail: K.Seddon6qub.ac.uk
The authors would like to thank the ERDF Technology
Development Programme and the QUESTOR Centre (JDH) for
financial support, and the EPSRC and Royal Academy of
Engineering for the award of a Clean Technology Fellowship
(to K.R.S.).
Abstract Ionic liquids are receiving an upsurge of
interest as green solvents; primarily as replacements for
conventional media in chemical processes. This review
presents an overview of the chemistry that has been
developed utilising ionic liquids as either catalyst and/or
solvent, with particular emphasis on processes that have
been taken beyond the pre-competetive laboratory stage
and represent clean industrial technology with significant
cost and enviromental benefits.
Introduction
So what are ionic liquids, and what have they to do with
green chemistry? The answer to the first question has
been addressed in a number of reviews and articles
recently (Chauvin and Olivier-Bourbigou 1995, Chauvin
1996, Freemantle 1998a, Freemantle 1998b, Freemantle
1999, Hussey 1983, Hussey 1988, Seddon 1996, Seddon
1997, Seddon 1998, Welton 1999), and will not be
discussed in detail here. The answer to the second ques-
tion will become the main text of this article. Clean tech-
nology concerns the reduction of waste from an indus-
trial chemical process to a minimum: it requires the
rethinking and redesign of many current chemical proc-
esses. As defined by Roger Sheldon, the E-factor of a
process is the ratio (by weight) of the by-products to the
desired product(s) (Sheldon 1993, 1997).
The Table illustrates that the dirty end of the chem-
ical industry, oil refining and bulk chemicals, is remark-
ably waste conscious: it is the fine chemicals and phar-
maceutical companies who are using inefficient, dirty,
processes, albeit on a much smaller scale. Volatile
organic solvents are the normal media for the industrial
synthesis of organics (petrochemical and pharmaceutical),
with a current world-wide usage of ca. 4,000,000,000
Table 1. The Sheldon E-Factor (Sheldon 1993, 1997)
Industry Production / tons pa E-factor
Oil Refining 10
6
10
8
0.1
Bulk Chemicals 10
4
10
6
15
Fine Chemicals 10
2
10
4
550
Pharmaceuticals 10
1
10
3
25100
p.a. However, the Montreal Protocol has resulted in a
compelling need to re-evaluate many chemical processes
that have proved otherwise satisfactory for much of this
century. There are four main alternate strategies:
1. solvent-free synthesis,
2. the use of water as a solvent,
3. the use of supercritical fluids as solvents, and
4. the use of ionic liquids as solvents.
It is the purpose of this review to explore option (4),
to allow it to be evaluated against the other strategies,
and to demonstrate its viability for commercial develop-
ment in all sectors of the chemical industry.
As discussed elsewhere recently, (Chauvin and Olivier-
Bourbigou 1995, Chauvin 1996, Freemantle 1998a, Free-
mantle 1998b, Freemantle 1999, Hussey 1983, Hussey
1988, Seddon 1996, Seddon 1997, Seddon 1998), the past
fifty years have seen the melting point of ionic liquids
drop from c800 7C to 96 7C from high-temperature
corrosive environments to low-temperature benign
solvents. Although the archetypal ionic liquids are the N-
butylpyridinium chloride-aluminium(III) chloride,
[NBupy]Cl-AlCl
3
, and 1-ethyl-3-methylimidazolium chlo-
ride-aluminium(III) chloride, [emim]Cl-AlCl
3
, systems
(for phase diagram, see Fig. 1), the range of available
anions and cations has expanded enormously in the past
decade. Indeed, it is our best estimate that, if binary and
ternary mixtures are included (and there are very good
practical and economic reasons for doing that), there are
approximately one trillion (10
18
) accessible room temper-
ature ionic liquids.
Take, for example, the standard cations [NBupy]
c
and [emim]
c
, (see Fig. 2). If the butyl and ethyl groups,
respectively, are exchanged for a generic linear alkyl
function, R (where RpC
n
H
2nc1
; n B I [1, 18]), then a
series of cations is generated, all of which can be used as
the basis of ionic liquids. But is this just a case of
methyl, ethyl, butyl, futyl? No. Figs. 3 and 4 illustrate the
significant variation in properties which can be induced
by this simple change for the [Rmim][PF
6
] and
Clean Products and Processes 1 (1999)
224
Fig. 1. The experimental phase diagram for the [emim]Cl-AlCl
3
system, showing the formation of a compound, [emim][AlCl
4
],
with a congruent melting point (Fannin et al. 1984)
Fig. 2. The aromatic heterocyclic N-butylpyridinium and 1-
ethyl-3-methylimidazolium cations
Fig. 3. Melting point phase diagram for [Rmim][PF
6
] ionic
liquids as a function of alkyl chain length n showing the
melting transitions from crystalline (closed square) and glassy
(open square) materials and the clearing transition (closed
circle) of the liquid crystalline (LC) terms
Fig. 4. Melting point phase diagram for [Rmim][BF
4
] ionic
liquids as a function of alkyl chain length n showing the
melting transitions from crystalline (closed square) and glassy
(open square) materials and the clearing transition (closed
circle) of the liquid crystalline terms
[Rmim][BF
4
] ionic liquids, with data taken from our own
laboratories (Bowlas et al. 1996, Gordon et al. 1998,
Holbrey and Seddon 1999).
An interesting feature of these phase diagrams is the
appearance of liquid crystalline phases with the longer
alkyl chains, and this is confirmed when their optical
textures are examined (see Fig. 5). The crystal structure
of [C
14
-mim][PF
6
] is illustrated in Figs. 6 and 7. The
implications of the existence of these stable phases has
still to be explored in terms of stereochemical control of
reactions.
The wide range of reactions that have been under-
taken in low temperature ionic liquid solvents is quite
remarkable. The range is limited simply by imagination
and the time required for investigation. The specific and
selectable solvent properties are a key feature of ionic
liquids as solvents and have been utilised, especially in
combination with the catalytic properties of the chloroa-
luminate(III) ionic liquids, to develop a range of syntheti-
cally important catalytic reactions, some of which are
being investigated as economically and environmentally
viable alternatives to existing industrial processes. Room
temperature ionic liquids have developed, in less than 20
years, from an adjunct to the US Star Wars research on
battery electrolytes into an industrial reality as media for
catalytic chemical processes.
J.D. Holbrey, K.R. Seddon: Ionic Liquids
225
Fig. 5. The characteristic thermotropic (left) and lyotropic
(right) textures displayed by [C
14
-mim]Cl
Fig. 6. Single crystal X-ray
structure of [C
14
-mim][PF
6
]
Fig. 7. Packing for [C
14
-
mim][PF
6
] within the crystal,
showing the typical layered
structure with interdigitated
alkyl-chains
Clean Products and Processes 1 (1999)
226
Here, we will describe many of the catalytic processes
which use low temperature ionic liquids as reaction
media. In a number of indicated cases, these processes
have been taken through the development process to a
point of industrial commercialisation and represent first
generation ionic liquid processes, principally based on
chloroaluminate(III) ionic liquids which are currently
ready for industrial uptake.
Following this line, second generation ionic liquid
processes based on other, more benign, ionic liquids are
currently under investigation and development in a
variety of laboratories around the world. Many of these
processes utilise the ability of many ionic liquids to selec-
tively immobilise transition metal catalysts for liquid-
liquid two-phase catalysis while permitting easy, often
trivial, extraction of products. Areas under active study
include alkylation reactions, Diels-Alder cyclisations,
Heck coupling reactions, hydrogenation, hydroformyla-
tion, oligomerisation, dimerisation and polymerisation of
olefins, and Friedel-Crafts chemistry.
In the remainder of this paper, for the sake of
conciseness, the term ionic liquid should, in general, be
taken to mean ambient, or close-to-ambient, tempera-
ture ionic liquid containing organic cations in contrast
to the high temperature simple molten salts, such as
NaCl-AlCl
3
.
Many of the processes discussed (in this terminology,
first generation) make use of the chloroaluminate(III)
ionic liquids described above, in the acidic rgime (that
is, above 50 mol% AlCl
3
). Here, the ionic liquids contain
both [AlCl
4
]

and [Al
2
Cl
7
]

anions, and unsurprisingly
have been used as substitutes for conventional solid or
suspended sources of aluminium(III) chloride. However,
ionic liquids, in ideal cases, have no waste associated
with them, whereas supported aluminium(III) chloride
catalysts involve large (and annually rising) waste
disposal costs, and a very dirty process.
This review is conveniently separated into reactions of
alkenes and reactions of arenes with only a relatively
small amount of overlap (for instance in the section on
linear alkylbenzene production, which is the reaction of
an alkene with an arene!).
Reactions of Alkenes
The Dimersol/Difasol process
The Dimersol process developed by the IFP (Commereuc
et al. 1982) is widely used industrially for the dimerisa-
tion of alkenes, typically propene and butenes, to the
more valuable branched hexenes and octenes, with
twenty-five plants in operation world-wide producing ca.
3!10
6
tonnes per annum. The C
8
olefins produced are
usually hydroformylated to C
9
alcohols for use in the
manufacture of plasticisers. The dimerisation process is
commonly operated solvent-free with the active catalyst,
a cationic nickel complex of the general form
[LNiCH
2
R][AlCl
4
] (where L is PR
3
). The catalyst has
been found to be soluble in aromatic and halogenated
hydrocarbon solvents, and shows greater catalytic activity
in solution. Although this process is used widely, the
separation of products from the catalyst is a major
problem and leads to increased operational costs and
environmental impact. Chauvin and coworkers at the IFP
in France (Chauvin et al. 1988, 1990a, 1990b, 1994, 1995a,
1997, Einloft et al. 1996, Olivier et al. 1992) reasoned that
chloroaluminate ionic liquids would be good solvents for
the nickel catalyst, and discovered that by using a ternary
ionic liquid system ([bmim]Cl-AlCl
3
-EtAlCl
2
) (bmimpI-
butyl-3-methylimidazolium), it is possible to form the
active catalyst from a NiCl
2
L
2
precursor and that most
importantly, the ionic liquid solvent stabilises the active
nickel species.
Using the ionic liquid catalyst, the Dimersol reaction
can be performed as a two-phase liquid-liquid process at
atmospheric pressure at between 15 7C and 5 7C. Under
these conditions, alkenes are dimerised with activities
well in excess of that found in both solvent-free and
conventional solvent systems. The products of the reac-
tion are not soluble in the ionic liquid, and form a
second less-dense phase that can be easily separated. The
nickel catalyst remains selectively dissolved in the ionic
liquid phase, which permits both simple extraction of
pure products and efficient recycling of the liquid catalyst
phase. In addition to the ease of product/catalyst separa-
tion, the key benefits from using the ionic liquid solvent
are the increased activity of the catalyst ( 1250 kg of
propene dimerised per 1 g of Ni catalyst), better selec-
tivity to desirable dimers (rather than higher oligomers),
and the efficient use of valuable catalysts through simple
recycling of the ionic liquid.
This process, using the ionic liquid solvent system,
has recently been commercialised by the IFP, as the
Difasol process. In this process butene is dimerised in a
continuous two-phase procedure with high conversion of
olefin and high selectivity to the dimer. Most impor-
tantly, the Difasol system can be retro-fitted into existing
Dimersol plants to give improved yields, lower catalyst
consumption and associated cost and environmental
benefits.
Oligomerisation of butene
In addition to the nickel-catalysed Difasol processes
developed by the IFP, it has been know for some time
that acidic ionic liquids themselves act as catalysts for the
dimerisation and oligomerisation of olefins, all be it, in a
somewhat uncontrolled manner (Boon et al. 1986).
Developments in our laboratories, in collaboration
with BP Chemicals, have shown that a wide range of
acidic chloroaluminate(III) and alkylchloroaluminate(III)
ionic liquids catalyse the dimerisation and oligomerisa-
tion of olefins (Abdul-Sada et al. 1995a, 1995b, Ambler et
al. 1996). In what is an exceptionally simple system, the
olefinic feedstock may be mixed with, or simply bubbled
through, the ionic liquid catalyst to produce oligomeric
products which have low solubility in the ionic liquid
catalyst and separate as a less dense organic phase which
is readily removed by tapping off. Alternatively, in a
batch process (more commonly used for laboratory
testing), the ionic liquid is injected into a charged auto-
clave batch reactor (see Fig. 8): again product extraction
amounts to simply tapping off the reactor.
J.D. Holbrey, K.R. Seddon: Ionic Liquids
227
Fig. 8. An ionic liquid autoclave rig from our laboratories, used
for testing batch reactions
In addition to simple oligomerisation reactions, chlo-
roaluminate(III) and alkylchloroaluminate(III) ionic
liquids are particularly good catalysts for the polymerisa-
tion of olefins. For example, isobutene can be polymer-
ised in an acidic ionic liquid to poly(isobutene) with a
higher molecular weight than is formed using other poly-
merisation processes (Ambler et al. 1996). The catalytic
activity of the ionic liquids increases towards higher
degrees of polymerisation from short-chain oligomers as
the alkylchain length of the 1-alkyl-3-methylimidazolium
or N-alkylpyridinium cation is increased, which provides
a very effective mechanism for controlling the product
distribution of this process from oligomers to polymers.
Poly(isobutene), traditionally prepared by the Cosden
process, is a valuable lubricant, and also a route to
higher value-added materials.
The ionic liquid polymerisation process has a number
of significant advantages over the industrial Cosden
process, which uses a supported or liquid phase alumi-
nium(III) chloride catalyst (Weissermel and Arpe 1997).
Using the ionic liquid process, the polymer forms a sepa-
rate layer, which is substantially free of catalyst and ionic
liquid solvent. This is readily removed by tapping off,
and the absence of chloroaluminate(III) contamination in
the polymer removes the need for a subsequent aqueous
washing stage to remove the catalyst. The fact that the
polymer is insoluble in the ionic liquid greatly enhances
the degree of control available to reduce undesirable
secondary reactions (i.e. isomerisations) without
requiring alkali quenching of the reaction. A secondary
benefit, in common with the Difasol process, is that the
separation of the products from the ionic liquid reaction
system and elimination of aqueous washing steps enables
the reuse rather than destruction of the catalyst, which
further reduces costs and wastage from the process.
This ionic liquid reaction system can be easily retro-
fitted to existing Cosden processes, providing a contin-
uous catalytic process with the elimination of costly
aqueous washing steps and associated destruction of the
catalyst.
Ziegler-Natta Polymerisation
Ziegler-Natta polymerisation of ethylene to linear a-
olefins currently has a world capacity in excess of
1.6!10
6
tonnes per year. The most common production
methods involve the use of triethylaluminium catalysts at
ca. 100 7C and 100 atmospheres pressure. Other more
modern processes can utilise organometallic transition
metal catalysts, typically nickel- or titanium-based, for
example, using a mixed alkylchloroaluminium(III) and
titanium(III) chloride catalyst in an organic solvent to
produce exceptionally pure a-olefins. Ziegler-Natta poly-
merisation of ethylene has been reported in an ionic
liquid solvent (Carlin and Wilkes 1990). Using dichloro-
bis(h
5
-cyclopentadienyl)titanium(IV) with an alkyl-chlo-
roaluminium(III) co-catalyst in an acidic [emim]Cl-AlCl
3
ionic liquid solvent, ethylene polymerisation was
reported. In comparison, analogous zirconium and
hafnium complexes failed to show catalytic activity.
Hydrodimerisation of dienes
The commercially important hydrodimerisation of 1,3-
butadiene to octa-2,7-dien-1-ol (Dullius et al. 1998, Silva
et al. 1998) has been demonstrated using palladium-based
catalysts in [bmim][BF
4
], a neutral, non-acidic ionic
liquid. The ionic liquid, in this case acts purely as a reac-
tion solvent. The catalyst precursor [Pd(mim)
2
Cl
2
] was
prepared in situ from an imidazolium tetrachloropallada-
te(II) salt, [bmim]
2
[PdCl
4
], dissolved in the ionic liquid
solvent. The reaction proceeds in a liquid-liquid two-
phase system, the products separate from the catalytic
reaction mixture as a separate layer on cooling, and are
removed by decantation.
The cyclo-dimerisation of dienes via Diels-Alder
mechanisms have been reported, and are covered in a
later section (see below).
Alkylation of olefins
Olefin alkylation is important as a route to produce
branched iso-alkenes. Of particular importance has been
the production of 2,3-dimethylbutene, which could be
then converted to a methoxy-ether for use as a fuel addi-
tive to increase the octane rating. This has been achieved
using ionic liquid solvents at the IFP with a modification
to the dimersol/difasol process (changing the bulkiness of
the phosphine ligands on the nickel catalyst to favour
formation of the desirable 2,3-dimethylbutenes from
propene) to optimise for high octane number fuel addi-
tives (Chauvin et al. 1995a).
One of the advantages of an ionic liquid catalyst for
this reaction over conventional liquid acid catalysts is
that the catalytic activity can be controlled by adjusting
the concentration of the active catalyst ([Al
2
Cl
7
]

). Using
highly acidic ionic liquids, described for olefin oligomer-
isations, it is possible to alkylate isobutane (Abdul-Sada
et al. 1995b, Ambler et al. 1996, Chauvin et al. 1989) at
low temperatures (30c50 7C) with C
2
-C
4
olefins. This
is a reaction that is not effective using normal liquid
acidic catalysts (HF and H
2
SO
4
).
These two ionic liquid based routes to optimised 2,3-
dimethylbutene production from respectively propylene
and ethylene are very good homogeneous processes to
Clean Products and Processes 1 (1999)
228
Fig. 9. Ionic liquids permit
high yields and selectivity
(endo:exo ratios) for the Diels-
Alder reaction
compete with heterogeneous isomerisation and alkylation
routes currently used.
Diels-Alder reactions
Ionic liquids have been demonstrated as effective solvents
for Diels-Alder reactions (Jaeger and Tucker 1989, Earle
et al., 1999, Fischer et al., 1999) and show significant rate
enhancements, high yields and selectivities (see Fig. 9)
comparable with the best results obtained in conven-
tional solvents. To date, the biggest developments in
Diels-Alder chemistry have come through reactions in
Li[ClO
4
]-Et
2
O, where the high electrolyte concentrations
are cited as beneficial through salt-effects and the high
internal pressure of the solvent. It is clear from the
studies cited that extending this concept through to the
use of ionic liquid solvents will lead to further extensions
in the scope of these reactions and eliminate the need for
potentially explosive perchlorate-based reaction media.
Also, Chauvin (Chauvin and Olivier-Bourbigou 1995)
reports that Fe(NO)
2
catalysts for the dimerisation of
butadiene to 4vinylcyclohexene are effective in weakly
coordinating [bmim][AF
6
] (ApP or Sb) ionic liquids.
The effect of solvent on the reaction rates in moving
from conventional molecular solvents such as toluene
and THF (Huchette et al. 1978) to the ionic liquid is
exceptional.
Hydrogenation and hydroformylation
As seen earlier, olefins are very reactive in acidic ionic
liquids and dimerisation, polymerisation or oligomerisa-
tion reactions readily take place. However, acidic
[emim]Cl-AlCl
3
mixtures are not the only ionic liquids of
interest. A significant advantage of using ionic liquids as
reaction media over traditional molecular solvents is the
wide range and almost infinite tunability of solvent and
catalytic properties.
The activity and properties of the liquid can readily be
controlled by changing composition or by changing the
nature of either the anion or the cations present. In
neutral ionic liquids containing for example [BF
4
]

,
[PF
6
]

, [SbF
6
]

and [CuCl
2
]

anions, the reactive poly-
merisation and oligomerisation reactions of olefins cata-
lysed by acidic anions are not observed and more
controlled, specific, reactions can be catalysed. These
ionic liquids are often generically referred to as non-chlo-
roaluminates, though clearly this description is derived
from an immature view of the breadth of ionic liquid
development, since ionic liquids containing chloroalumi-
nate anions comprise only one of many possible anion
types. More useful, is the consideration of neutral ionic
liquids (in terms of Franklin acidity), in which the anion
exists as only a single species, in contrast to the equili-
brium seen in the tetrachloroaluminate(III) systems:
2[AlCl
4
]

a [Al
2
Cl
7
]

cCl

Since these ionic liquids can not support the existence

of reactive Lewis acid conjugate anions (such as [Al
2
Cl
7
]

i.e. there is no analogous mechanism to support

2[BF
4
]

a [B
2
F
7
]

cF

), they are much less reactive and

can be used as innocent solvents. Under these condi-
tions, many conventional transition metal catalysts can
be utilised. Modification of the ionic liquid solvents
allows the potential to immobilise catalysts, stabilising
the active species and to optimise reactant/product solu-
bilities to permit facile extraction of products.
Hydrogenation of olefins catalysed by transition metal
complexes dissolved in ionic liquid solvents have been
reported using rhodium- (Suarez et al. 1996), and ruthe-
nium- and cobalt-containing catalysts (Suarez et al. 1997).
Hydrogenation rates have been shown to be up to five
times higher than the comparable reactions in propa-
none, or in analogous two-phase aqueous-organic
systems. The solubilities of the alkene reagents, TOFs,
and product distributions are strongly influenced by the
nature of the anion in the ionic liquid solvent, which can
be used to improve the selectivity of the hydrogenation
(Chauvin et al. 1995b). Pentene has been hydrogenated
using the Osborne rhodium catalyst [Rh(nbd)(PPh
3
)
2
]
[PF
6
] (where nbdpnorbornadiene) in ionic liquids
containing [BF
4
]

, [PF
6
]

, [SbF
6
]

and [CuCl
2
]

anions.
There are significant solvent effects in this reaction; in
the best case (the [SbF
6
]

ionic liquid), hydrogenation
rates were five times higher than the comparable reaction
in propanone. In contrast, using a chloride-containing
ionic liquid as solvent resulted in only isomerisation of
pent-1-ene to pent-2-ene, presumably through chloride
coordination to the metal-centre deactivating the catalyst.
J.D. Holbrey, K.R. Seddon: Ionic Liquids
229
Conjugated dienes are more soluble in the ionic liquids
than simple olefins, which allows for selective hydrogena-
tion. For example, cyclohexadiene is five times more
soluble than cyclohexene in [bmim][SbF
6
] ionic liquid,
and is selectively hydrogenated (98% selectivity, 96%
conversion) to cyclohexene, which separates from the
ionic liquid. Cyclohexene has also been hydrogenated
using Wilkinsons catalyst [RhCl(PPh
3
)
3
] or
[Rh(cod)
2
][BF
4
] (codp1,4-cyclooctadiene) in ionic liquids
containing [BF
4
]

and [PF
6
]

anions.
Asymmetric hydrogenations of a-acetamidocinnamic
acid (Chauvin et al. 1995b) to (S)-phenylalanine with a
cationic chiral rhodium catalyst in [bmim][SbF
6
] ionic
liquid, and 2-arylacrylic acids (Monteiro et al. 1997) with
chiral ruthenium catalysts in [bmim][BF
4
] ionic liquids,
have been reported with a reasonable 64% ee. Palladium
catalysts (Carlin and Fuller 1997) immobilised in an ionic
liquid-polymer gel membrane (Fuller et al. 1997)
containing either [emim][OTf] or [emim][BF
4
] have also
been reported as catalysts for heterogeneous hydrogena-
tion reactions.
Hydroformylation (Fuller et al. 1997) of pent-1-ene in
[bmim][PF
6
] with rhodium catalysts shows high catalytic
activity; again, the products separate as a second organic
phase. It was noted that a small part of the neutral cata-
lyst leached into the organic phase. In general, charged,
especially cationic transition metal complexes are most
effectively immobilised in the ionic liquid solvents.
Hydrogenation reactions occur readily using ionic
liquids as the catalyst-containing components of a two-
phase systems. The key feature is that the transition
metal catalysts can be immobilised in the polar ionic
liquid phase and are not preferentially extracted into
organic solvents. The activity may be higher than
conventional homogeneous hydrogenations in, for
example, propanone or as two-phase aqueous-organic
systems where expensive, often synthetically challenging,
modified ligands are often required.
In the communications described, it is not only
demonstrated that hydrogenation reactions occur in
neutral (or, more correctly, non-acidic) ionic liquids, but
also more generally that many catalytically-active transi-
tion metal complexes can be immobilised in ionic liquid
solvents without the need for specially modified ligands.
The reaction rates and selectivities depend on the relative
solubilities of reactants and products in the ionic liquid
phase. This is demonstrated by the selective and specific
hydrogenation of cyclohexadiene to cyclohexene, and
illustrates the potential to tailor reactions by modifying
the properties of the ionic liquid solvent.
Miscellaneous reactions of alkenes
Alkylammonium and phosphonium salts have been used
as solvents for the Heck coupling of aromatic halides
with activated olefins using palladium catalysts (Kauf-
mann et al. 1996): the excess of PPh
3
required in conven-
tional solvents is not required to stabilise the palladium
catalyst in ionic liquid solvents. Although Heck coupling
reactions are not utilised on an industrial scale, and in
general produce one equivalent of salt, they are widely
used in the pharmaceutical and fine chemical sectors. In
a recent example, the Heck coupling of benzoic acid
anhydride with linear a-olefins has been demonstrated in
a process which produces no salt by-products (Stephan et
al. 1998) and presents an alternative route to the forma-
tion of linear alkylbenzenes (LABs) described later. The
benefits of ionic liquid solvents (reactivity, product
extraction, etc.) could provide further enhancements to
these series of reactions. Nucleophilic aromatic substitu-
tion reactions have also been studied in molten dodecyl-
tributylphosphonium salts (Fry and Pienta 1985).
Reactions of Arenes
Using the acidic, chloroaluminate(III) ionic liquids as
catalytic solvents, aromatic rings show a high reactivity
to olefins and undergo a wide range of Lewis acid cata-
lysed chemistry, including clean electrochemical and
photochemical polymerisation to form conducting polym-
eric films, a commercially important alkylation of
benzene with olefins, and Friedel-Crafts alkylation and
acylation reactions.
Formation of poly(p-phenylenes)
Poly(p-phenylenes) have attracted a lot of attention as
highly stable conducting polymers for the development of
conductive polymeric films and electrolytes (Kovacic and
Jones 1987). Polymers can be obtained by polymerisation
of benzene using many different chemical methods, but
the polymers produced are often of poor quality
(contaminated with catalyst and chlorinated and oxygen-
ated residues) and are usually obtained as powders with
low relative molecular mass. Electrochemical polymerisa-
tion of arenes (Abuabdoun 1989) in acidic chloroalumi-
nate(III) ionic liquids with either N-alkylpyridinium or
1,3dialkylimidazolium cations has been shown to
produce conducting polymers with superior purity,
conductivity and greater molecular mass than can be
obtained by chemical methods. In addition, electrochem-
ical polymerisation allows the preparation of desirable
conducting films. For example, benzene can be electropo-
lymerised to condensed ring conducting polymers
(Trivedi 1989), and more importantly, to linear poly(p-
phenylene) (Arnautov 1997, Kobryanskii and Arnautov
1992b, 1993b) with superior chain lengths.
Chemical oxidative polymerisation of benzene to
poly(p-phenylenes) (Kobryanskii and Arnautov 1992a,
1993a, 1993c) using [N-butylpyridinium][AlCl
4
] ionic
liquid solvent has also been achieved, the relative molec-
ular mass of the polymers being higher than in conven-
tional solvents. This is attributed to the much higher
solubility of the polymer in ionic liquid solvents, which
allows extended polymerisation.
Electrochemical studies of anthracene (Carlin et al.
1992), methylanthracene (Lee et al. 1996), tetrathiaful-
valene (Carter and Osteryoung 1994) and 9,10-anthraqui-
none (Cheek and Osteryoung 1982, Cheek and Spencer
1994), photoelectrochemical oxidation of aromatic hydro-
carbons and decamethylferrocene (Thapar and Rajeshwar
1982), and photochemical oligomerisation of anthracene
(Hondrogiannis et al. 1993) have all been reported in
ionic liquids. In addition, the synthesis of silane polymer
films for electrodes (Carlin and Osteryoung 1994), and
Clean Products and Processes 1 (1999)
230
the electrochemical oxidation and polymerisation of
ethylbenzene (Kobryanskii and Arnautov 1993b) have
also been reported.
Reduction of aromatic rings
Lewis acid/redox chemistry of 1,2-diarylethanes
(Buchanan et al. 1985), hydrogenation of polycyclic
aromatics (Buchanan et al. 1981a, 1982), hydride extrac-
tion from polycyclic aromatics (Buchanan et al. 1981b,
Smith et al. 1980, Zingg et al. 1984), bond cleavage in
phenylalkanes (Buchanan et al. 1983), chlorination vs. C-
C coupling of anthracene radicals (Chapman et al. 1985a,
1985b) and reduction of aromatic ketones (Cheek 1987,
1990, 1991, 1992a, 1992b, Cheek and Herzog 1984a,
1984b) and phenazine and perylene (Coffield et al. 1990,
1991, 1992) have all been reported in the literature using
higher temperature ionic liquid systems. No studies have
been published concerning room-temperature ionic
liquids, but work from our own laboratories (Adams et
al. 1999) reports the facile reduction of arenes to cyclic
hydrocarbons with a variety of reducing agents: e.g.
Perylene is similarly reduced:
Both of these reduction sequences is stepwise, each
isomer representing a thermodynamic minimum.
Electophilic substitution (Skrzynecki-Cooke and
Lander 1987) and other reactions of naphthalenes (alkyla-
tion, acylation, condensation and migration) in acidic
ionic liquids (Ota 1987a, 1987b) (including a one-pot
synthesis of anthraquinone from benzene in 94% yield)
have been reported. Anthracene undergoes photochemical
[4c4] cycloaddition reactions (Hondrogiannis et al. 1993,
Pagni et al. 1994) in acidic chloroaluminate(III) ionic
liquids. A much wider range of redox products are
formed than occur in conventional solvents; the strong
Brnsted acidity of the ionic liquid induces protonation
of anthracene, by residual traces of HCl, to form an
anthracenium species which couples readily via photo-
chemically- driven electron-transfer mechanisms.
Synthesis of linear alkylbenzenes (LABs)
The alkylation of arenes with long-chain linear olefins is
an example of Friedel-Crafts alkylation which has parti-
cular global industrial importance for the synthesis of
linear alkylbenzenes (LABs) (Almeida et al. 1994), which
are used in the formulation of detergents. The industrial
scale of this reaction, coupled with the implications that
switching to an ionic liquid process may entail, merits its
discussion as a particular example.
LAB was first introduced in the 1960s as a precursor
to alkylbenzenesulfonates, which are widely used as
detergents, and also as emulsifiers, wetting agents, dry-
cleaning additives, lubricants and greases. The global
market for LAB is in excess of 2.5!10
6
tonnes per year.
Although LABs are produced by alkylation of benzene
with chloroalkane feeds, the principal industrial processes
for the formation of LAB are alkylation of benzene with
do decene over liquid HF or AlCl
3
catalysts. A fixed-bed
heterogeneous non-corrosive acid catalyst system (Detal
from UOP) (Imai et al. 1995) has also recently been
introduced. In the liquid acid catalyst processes, espe-
cially with HF, the handling of corrosive catalysts leads to
increases in the capital cost of the plants and has impli-
cations for the disposal of neutralisation products gener-
ated within the process.
The production of LAB using chloroaluminate(III)
ionic liquids as the acid catalyst has been recently
described in the patent literature (Abdul-Sada et al.
1995b, Ambler et al. 1996, Lacroix et al. 1998); this is a
specific example of the general activation and alkylation
with olefins in ionic liquids under acidic conditions. The
application of an acidic ionic liquid catalyst as a direct
replacement for solid AlCl
3
promises significant improve-
ment in the reaction selectivity combined with ease of
product separation and elimination of catalyst leaching.
Again, as with the Difasol process, the potential to
retrofit existing plants will lead to massively reduced
catalyst consumption and simplify the production process
through the elimination of caustic quenching steps asso-
ciated with catalyst leaching.
Friedel-Crafts chemistry
The Franklin acidic chloroaluminate(III) ionic liquids
(containing X(AlCl
3
) 10.5) are very aggressive solvents
most organic materials are dissolved at high concentra-
tions. However, the acidic nature of the solvent causes
ready reaction of the solutes usually via hydride abstrac-
tion reactions leading to oligomerisation or isomerisa-
tion, and Friedel-Crafts alkylation or acylation reactions.
J.D. Holbrey, K.R. Seddon: Ionic Liquids
231
Although several Friedel-Crafts reactions have been
covered in isolation in earlier sections (i.e. alkylation of
arenes), a generalisation of Friedel-Crafts reactions, cata-
lysed in acidic ionic liquids, warrants further considera-
tion.
For a general discussion of Friedel-Crafts chemistry,
readers are recommended to look at the classic text
book (Olah 1964). Friedel-Crafts alkylations and acyla-
tions are of great commercial importance, although there
are considerable problems, especially with misnamed
catalytic Friedel-Crafts acylation reactions, which are
actually stoicheometric, consuming 1 mole of AlCl
3
per
mole of reactant. The nett result is massive usage of
aluminium(III) chloride and associated problems with
disposal of salt and oxide by-products. Typically, Friedel-
Crafts alkylation and acylation reactions are run in an
inert solvent with suspended or dissolved aluminium(III)
chloride as a catalyst, and may take six hours and go
only to 80% completion to give a mixture of isomeric
products.
Both alkylation and acylation reactions under Friedel-
Crafts conditions have been demonstrated using chloroa-
luminate(III) ionic liquids as both solvent and catalysts
(Adams et al. 1998, Boon et al. 1987a, 1987b, 1986, Jones
et al. 1985, Levisky et al. 1984, Ota 1987a, 1987b, Piersma
and Merchant 1990, Wilkes 1987). Reaction rates are
much faster (often essentially instantaneous) with total
reagent conversion, and often with surprising specificity
to a single product.
Alkylation
The alkylation of benzene with a wide number of alkyl
halides in acidic chloroaluminate(III) ionic liquids (Boon
et al. 1986) leads to rapid and largely uncontrolled
polyalkylation with evolution of hydrogen chloride. For
example, the alkylation of benzene with chloromethane in
an acidic ionic liquid gives a mixture of mono- to hexa-
substituted products. The ionic liquid solvent/catalyst
activates the reaction and the alkylation can be
performed even at temperatures as low as 20 7C in the
ionic liquid solvent. The products have a low solubility in
the ionic liquid and are easily separated.
General organic reactions in low melting chloroalumi-
nate ionic liquids have been described (Levisky et al.
1983, 1984) including Friedel-Craft alkylations, acylations,
chlorinations and nitrations in acidic ionic liquids (Boon
et al. 1987a, 1987b, 1986, Piersma and Merchant 1990).
The alkylation of arenes using an olefin (Abdul-Sada
et al. 1995b, Ambler et al. 1996) rather that alkylhalide
has been described for the LAB process. In a typical,
generalised procedure, the reaction is performed between
80200 7C using 0.5% ionic liquid catalyst. For example,
benzene is efficiently alkylated with ethylene to ethylben-
zene, which can then be dehydrogenated as a source of
styrene. This forms the basis of a competetive procedure
for alkylation of benzene without using ethyl chloride.
Acylation
Classical Friedel-Crafts acylation reactions typically use
AlCl
3
catalysts for the acylation of arenes with acylchlo-
rides. However, these are not truly catalytic reactions and
actually consume one molar equivalent of AlCl
3
through
reaction with the acyl group (see Fig. 10). Friedel-Crafts
acylation reactions are industrially important, despite the
lack of a true catalytic process, and the associated
massive consumption of aluminium(III) chloride. Many
acylation reactions have been demonstrated in acidic
chloroaluminate(III) ionic liquids liquids (Adams et al.
1998, Boon et al. 1986). As with the conventional proc-
esses, difficulties remain from the reaction being non-
catalytic in aluminium(III) chloride which necessitates
destroying the ionic liquid catalyst by quenching with
water to extract the products. However, regioselectivity
and reaction rates observed from acylation reactions in
ionic liquids are equal to the best published results.
Friedel-Crafts acylation of benzene is promoted by
Franklin acidic chloroaluminate(III) ionic liquids (Boon
et al. 1986): as is typical for acylation reactions, selec-
tively monoacylated products are formed through deacti-
vation of the aromatic ring by the first acyl substituent.
The acylated products of these reactions show high selec-
tivities to a single isomer: for example toluene, chloro-
benzene and anisole are acylated in the 4-position with
98% specificity. Naphthalene is acylated in the 1-position
which is the thermodynamically unfavoured product
under conventional Friedel-Crafts acylation conditions
compared to the derivatisation at the 2-position, the
normal product (Adams et al. 1998).
This apparent reversal of selectivity in the ionic liquid
system is because the acylating species is a fully ionised
linear acylium ion ([RCO]
c
), which is small (see Fig. 11)
compared to the (acyl chloride)-AlCl
3
aducts responsible
for acylation in conventional systems. The acylium ion is
stable in the ionic liquid and has been crystallised as a
salt from a chloroaluminate(III) ionic liquid. However, so
far the greatest problems with Friedel-Crafts acylations,
namely the non-catalytic reactivity with respect to AlCl
3
has not been adequately addressed. In addition to
benzene and other simple aromatic rings, a range of
organic and organometallic substrates (e.g. ferrocene)
(Dyson et al. 1997, Surette et al. 1996) have been acylated
in acidic chloroaluminate(III) ionic liquids. Predomi-
nantly mono-acylated products were prepared in good
yields.
The reactivity of chloroaluminate(III) ionic liquids is
such that even coals and other carbonaceous materials
can be dissolved and reacted. Coals can be acylated in
chloroaluminate(III) ionic liquids under much milder
conditions than can be used with just AlCl
3
as catalyst
(Newman et al. 1987, 1980, 1984). Acylation of coals is
used as a primary step in liquifaction and desulfurisation
processing.
Photogalvanic cells
Hydrophobic ionic liquids containing triflate and bis{(tri-
fluoromethyl)sulfonyl}amide (bis(triflyl)amide;
[N{SO
2
CF
3
}
2
]

) anions have been used as inert,

conducting solvents for solar cells (Bonhte et al. 1996,
Papageorgiou et al. 1996, Bonhte and Dias 1997).
Conventional solar cell technology utilises either organic
solvents containing dissolved electrolytes or conducting
solid electrolytes. Both models present a range of prob-
Clean Products and Processes 1 (1999)
232
Fig. 10. The (Benzoyl chloride)-AlCl
3
aduct formed from the reaction between
benzoyl chloride and aluminium(III)
chloride (Nieuenhuyzen et al., unpub-
lished results)
Fig. 11. The linear [CH
3
CO]
c
ion and
tetrahedral [AlCl
4
]

ion, as isolated in
the ionic [CH
3
CO][AlCl
4
] salt (Le
Carpentier and Weiss 1972)
lems, including difficulty maintaining good interface
contacts with solid electrolytes, the volatility of organic
solvents which necessitates using sealed cells, electrolyte
solubility and problems of incompatability of organic
solvents with the epoxy resins used in the cell construc-
tion. Conducting polymer electrolytes have been devel-
oped to overcome some of these problems; ionic liquid
electrolytes combine the advantages of liquid, solvent-
based electrolytes with those of polymer-electrolytes.
By using ionic liquids as the electrolytes, large electro-
chemical windows ( 14 V), good conductivity, and
thermal stability, are achieved with excellent resistance to
J.D. Holbrey, K.R. Seddon: Ionic Liquids
233
oxidation which is caused by uv-excitation of the TiO
2
semiconductor supports. The negligible vapour pressure
of the ionic liquids, hydrophobicity and compatability
with the epoxy resins used permits simple cell construc-
tion. Although difficulties with the viscosity of some of
the ionic liquid electrolytes is still a feature, solar cells
have been prepared which are especially good under low
light intensities with sensitiser turnovers in excess of 50
million.
Miscellaneous reactions
A number of investigations of chlorination reactions have
been made in Lewis acidic ionic liquids. In 1,3-dialkylim-
idazolium-chloroaluminate ionic liquids, the imidazolium
cation undergoes electrophilic substitution at the C(4)
and C(5) positions to yield 1,3dialkyl-4,5-dichloroimida-
zolium ionic liquids (Donahue et al. 1985, Lipsztajn and
Osteryoung 1984). The dichlorinated ionic liquids do not
appear to undergo further chlorination and are excellent
solvents for chlorination reactions (Boon et al. 1987a,
1987b, Lipsztajn and Osteryoung 1984, Lipsztajn et al.
1986). The chlorination of anthracene in [SbF
6
]

ionic
liquids (Chapman et al. 1985a) has been reported, and
other conventional Lewis acid catalysts have been used in
ionic liquids solvents, for example in a mixed tetraalky-
lammonium nitrate/CuCl
2
mixture, the difficult synthesis
of a-chloroketones (Atlamsani and Bregeault 1991) has
been achieved.
Tetraalkylammonium and 1,3-dialkylimidazolium
bromides have been used as highly regioselective solvents
for O-alkylation of b-naphthoxide (Badri and Brunet
1992). Recent work from our own laboratories has
extended this to efficient generalised N- and O-alkylation
(Earle et al. 1998) and has made the observation that the
ionic liquids mimic the behaviour of dipolar aprotic
solvents. Consequently, they can be used as clean replace-
ment solvents for DMF and DMSO in a wide range of
reactions. Importantly, the ionic liquids are non-volatile,
easy to dry and can be quantitatively recovered at the
end of the reaction; the products were easily extracted
from the ionic liquid into an organic ether phase.
Summary
These studies have shown that classical transition-metal-
catalysed hydrogenation, hydroformylation, isomerisa-
tion, dimerisation and coupling reactions can be
performed in ionic liquid solvents. Using conventional
solvents, selectivities, TOF and reaction rates are effec-
tively uncontrolled: however by using ionic liquid media
for the catalysis, it is possible to have a profound
influence on all these factors. A combination of subtle
(i.e. changing cation substitution patterns) and gross
(anion type) modifications to the ionic liquid solvent can
permit very precise tuning of reactions.
Ionic liquids have been used as effective solvents and
catalysts for clean chemical reactions; as replacements for
volatile organic and dipolar aprotic solvents (i.e. DMF,
DMSO) and solid acid catalysts in reactions ranging from
the laboratory to industrial scale. They provide a medium
for clean reactions with minimal waste and efficient
product extraction, an area which is currently being
investigated (Huddleston et al. 1998, Blanchard et al.
1999). The future directions for catalytic reactions in
ionic liquid solvents clearly rely on screening existing
catalysts and a greater depth of understanding of the
features influencing the specific solvent properties of the
different types of ionic liquids. It is anticipated that
combinatorial techniques will have a significant role to
play.
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